A-AO?9 67 FLORIDA UNIV GAINESVILLE DEPT OF CHEMISTRY F4G21/2ATONIC AND M4OLECULAR GAS PHASE SPECTROMETRY.(U)

0 1979 J D WINEFORDNER F44620-76-C-0OO5

UNCLASSIFIED AFOSR-TR-79-1315 NL

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~ '8AFOSR 791SI,9 FINAL .CY3NTIFIC $EP.T,

T 1 '7 -m cand-Molecular Gas P,$ase Spectrometry.

2. PRINCIPAL INVESTIGA~CRTJamesJ D.Wine fordn e r

UInivcrsity of F-loridaGainesville, FL 32611 LEL

INCLUSIVE DAE-Setme 1, 1975S September 30, 1979

104.CONTRAkCT NUMBk ~F446 i Il@'1

COSTS AND FY SOURCE: $100,000 - FY 76; $110,000 - FY 77;$125,000 - FY 78; $125,000 - FY 79

tv.SENIOR RESEARCH PERSONNEL:Dr.' James D. 1%'riefordner0Dr. Radu MavrodineanuDr. Piet WaltersDr. Robert MichelDr. Christian FavezDr. David JohnsonDr. Alan Uli-manDr. Hiroki HaraguchiDr. Howard LatzDr. Nicolo Omen-IttoDr. Al MassoumITTDr. J"can Michel MermaetDr. Kitao FujiwaraD)r. Roger Reeves

7. JUNIOR RESEARCH PERSONNEL:Benjamin Smith - ~AStephan ',,eeks 16/ - Z (IJerry Messman CJohn Fi tzgeraldLucas; HartFBruce Pollard1Mariana BlackburnGlenn Routi.1ier D E CThomaF Chester 218

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Sief NikdelRicky BatchTe rry ti c I ID~avid Boton -Mol]an~i c HIder.Johni I 01-'aIt I 'J

c;3~ I. V Approved f or public rel ezns;

Et~ldlad i~a distributionlunI iUmited.LAO)

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SECURITY CLASSIFICATION OF THIS PAGE (When Date Entered)

READ INSTRUCTIONSREPORT DOCUMENTATION PAGE BEFORE COMPLETING FORM"eDfl" NIIMBER 2. GOVT ACCESSION NO. 3. RECIPIENT'S CATALOG NUMBER

* AOSR -TR. Of9 13 1 54. TITLE (and Subtitle) -S. TYPE OF REPORT & PERIOD COVERED

FinalAtomic and Molecular Gas PHase Spectrometry 1 Sep 75 - 30 Sep 79

6. PERFORMING ORG. REPORT NUMBER

7. AUTHOR(s) S. CONTRACT OR GRANT NUMBER(&)

James D. Winefordner F44520-76-C-0005'

9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT PROJECT, TASKAREA & WORK UNIT NUMBERS

University of FloridaDepartment of Chemistry / 230AGainesville, FL 32611 2303/AI

I. CONTROLLING OFFICE NAME AND ADDRESS 12. REPORT DATE

AF Office of Scientific Research/NC 1979Building 410 13. NUMBER OF PAGES

Bolline AFB, D.C. 20332 4314. MONITORING AGENCY NAME & ADDRESS(Il different from Controlling Office) 15. SECURITY CLASS. (of this report)

Unclassified

1Sa. DECLASSI FICATION/DOWNGRADINGSCHEDULE

IS. DISTRIBUTION STATEMENT (of this Report)

Approved for public release; distribution unlimited.

17. DISTRIBUTION STATEMENT (of the abstract entered in Block 20, if different from Report)

IS. SUPPLEMENTARY NOTES

19. KErY WORDS (Continue on reverse side it necessary and identify by block number)

Combustion Fluorescence Plasmas NebulizedDiagnostics Flame Temperature Multislement Analysis

Analytical Quantum Efficiencies Pulsed Tunable Dye Laser

Atomic Spectroscopy Molecular Spectroscopy Spatial Profiles

SABSTRACT (Continue on reverse side It necessary and identify by block number)

The research is divided into combustion diagnostics and analytical gas phaseatomic and molecular spectrometry. New and improved techniques to spatiallyand temporally measure flame gas temperatures and species have been and arebeing developed. These techniques are all based upon fluorescence detection.By measuring the ratio of two fluorescence transitions (in a probe, such asindium) excited with two different wavelengths, the flame temperature can be

measured with a precision and accuracy better than 50 K. The two main temper-

ature techniques developed depend upon either the linear relationship 'between

! , ORM 1473

UnclssifiedS CURITY CLASSIFCATION OF THIS PAGE(Wh.e Data Fnfarad)

tem 20 (cont).uorescence and the excitation flux on the approach to saturation of the

fluorescence with high excitation fluxes. The measurement of total species* concentrations in flames and fluorescence quantum efficiencies is readily

performed by measurement of the absolute fluorescence flux reaching a cali-brated detector as a function of absolute laser flux. A rather simple graphi-cal method allows both species concentration and species fluorescence quantumefficiencies to be measure Using these approaches, both flame temperatureand species concentration tial profiles in a variety of laboratory flames(acetylene/air, acetylene/N20, H2/air, H2 /02/Ar, etc.) have been measured.Experimental analytical gas phase spectrometric studies have involved; thedevelopment and refinement of pulsed (and cw) tunable dye laser excitation ofatoms produced by spraying aerosols into combustion flames, furnaces, andinductively coupled plasmas; the development and refinement of an EIHAC xenonarc source-flame-slew scan atomic fluorescence spectrometer for multielementanalysis in real samples, such as engine oils, biological materials, etc.;the development and refinement of an innovative source for atomic fluorescenceflame spectrometry, namely the use of an ICP source which has the benefits ofboth a continuum source in terms of wavelength selectivity and line sourcesin terms of intense narrow line output; and development of chemiluminescenceproduced above a furnace (into which samples are nebulized) as an analyticalmethod.

KTIS GIth"WC TABUhemouncedJustification_

By

Distribution/

AvailabilitYCodes

Avail and/or

Dist., spec al

Unclassified

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8. PUBLICATIONS:

1. "INTERFERENCE OF MAGNESIUM BY TRACE CONCOMITANTS IN FLAME ATOMICABSORPTION SPECTROMETRY", C. Chen and J.D. WlVnefordner, Can. J.Spectrosc., 20, 87(1975).

2. "SOME CONSIDERATIONS ON THE MICROWAVE ELECTRODELESS DISCHARGE PLASMADIAGNOSTICS IN ARGON, HELIUM OR NITROGEN ATMOSPHERES", R. Avniand J.D. Winefordner, Spectrochim. Acta B, 30B, 281(1975).

3. "A COMPARISON OF SIGNAL-TO-NOISE RATIOS FOR SINGLE CHANNEL METHODS(SEQUENTIAL AND MULTIPLEX) VS MULTICHANNEL METHODS IN OPTICALSPECTROSCOPY", J.D. Winefordner, R. Avni, T.L. Chester, J.J. Fitz-gerald, L.P. Hart, D.J. Johnson, and P.W'. Plankey, Spectrochim.Acta 31B, 1-19(1976).

4. "AN EXPRESSION FOR THE ATOMIC FLUORESCENCE AND THERM.AL-EMISSIONINTENSITY UNDER CONDITIONS OF NEAR SATURATION AND ARBITRARYSELF-ABSORPTION", N. Omenetto, J.D. Winefordner, and C.Th.J.Alkemade, Spectrochim. Acta 30B, 335(1975).

S. "EVALUATION OF THE ANALYTICAL CAPABILITIES OF FREQUENCY MODULATEDSOURCES IN MULTI-ELEMENT NON-DISPERSIVE FLAME ATOMIC FLUORESCENCESPECTROMETRY", T.L. Chester and J.D. Winefordner, Spectrochim.Acta, 31B, 21(1976).

6. "ATOMIC FLUORESCENCE SPECTROMETRY WITH AN EI.IAC CONTINUUM EXCITATIOSOURCE AND A GRAPHITE FILAMENT ATO:,IlZER", P.S. Chuang and J.D.Winefordner, Appl. Spectrosc,29, 412(1975).

7. "A NEW HYDROLYSIS PROCEDURE FOR PREPARATION OF ORANGE JUICE FORTRACE ELEMENT ANALYSIS BY ATOMIC ABSORPTION SPECTROMETRY", J.A.McHard, J.D. Winefordner, and J.A. Attaway, J. AR. Food Chem., 24,41(1976).

8. "ATOMIC FLUORESCENCE SPECTROMETRY WITH A PREMIXED ARGON/OXYGEN/ACETYLENEFLAME", D.J. Johnson and J.D. Winefordner, Anal. Chem., 48,341(1976).

9. "IDETERMINATION OF LEAD IN CONFECTION WRAPPERS BY ATOMIC ABSORPTIONSPECTROMETRY", D. Watkins, T. Corbyons, J. Bradshaw, and J.D.Winefordner, Anal. Chim. Acta, 85, 403(1976).

10. "MULTI-ELEMENT ANALYSIS VIA RAPID-SCAN COMPUTER CONTROLLED ATOMICFLUORESCENCE SPECTROMETRY, USING A CONTINUUM SOURCE", D.J. Johnson,P.IV. Plankey and J.D. Winefordner, Anal. Chem., 47, 1739(1975).

11. "MEASUREMENT OF EXCITATION IONIZATION AND ELECTRON TEMPERATURESAND POSITIVE ION CONCENTRATIONS 144 MHz INDUCTIVELY COUPLEDRADIOFREQUENCY PLASMA", P.E. Walters, T.L. Chester, and J.D.inefordner, App. Spectrosc., 31, 1-19(1977).

12. "SELECTIVELY-MODULATED INTERFEROMETRIC DISPERSIVE SPECTROMETER FORUV-VISIBI.E ATOMIC AND MOLECULAR SPECTROMIITRY", J.J. Fitzgerald, T.L.Chester, and J.1). Winefordner, Anal. Chem., 47, 2330(1975).

13. "USE OF AN SIT IMAGE DETECTOR FOR ATOMIC EMISSION/FLUORESCENCESPECTROMETRY", T.L. Chester, H. 11araguchi, fl.O. Knapp, J.D. Messnian,and J.D. Winefordner, Appi. Spectrosc., 30, 409(1976).

14. "MOLECULAR FLUORESCENCE SPECTROSCOPY OF PHOSPHORUM MONOXIDE INFLAMES STUDIED BY A SIT-OMIA SYSTEM", Ii. Haraguchi, W.K. Fowler,D.J. Johnson, and J.D. Winefordner, Spcctrochim. Acta A, 32A,1539(1976).

1."ATOMIC ABSORPTION SPECTROMETRIC DETERMINATION OF CA, CU, FE, K,MG, MN, NA AND ZN IN ORANGE JUICE FOLLOWING HYDROLYTIC PREPARATION",J.A. McHard, J.D. Winefordner, and S.V. Ting, J g.Food Chem,.,24 , 95 0(1976) .

*16. "THEORETICAL COMPARISON OF FOURIER TRANSFORM SPECTROMETRY WITH SINGLESLIT LINEAR AND SLEIVED SCAN SPECTROME3TRIC METHODS FOR THE PHOTONNOISE LIMITED SITUATION", T.L. Chester, J.J. Fitzgerald,- and J.D.Winefordner, Anal. Chemn. (Correspondence), 48, 779(1976).

17. "PULSED NITROGEN-LASER IN ANALYTICAL SPECTROMETRY OF IMOLECULES INTHE CONDENSED PHASE",3 T.F. Van Geel and J.D. Winefordner,Anal. Chemn., 48, 335(1976).

18. "ATOMIC FLUORESCENCE SPECTROSCOPY WITH LASERS", N. Ornenetto, ed.,Wiley-Interscience, NY, in press.

19. "THE THROUGHPUT ADVANTAGE AND DISADVANTAGE IN ANALYTICAL UV-VlSTBLESPECTROMETRY: CONSIDERATIONS OF SIGNAL AND NOISE SPECTRALBANDPASSES", T.L. Chester and J.D. Winefordner, Anal. Chem., 49,119(1977). -

20. "MEASUREMENT OF LOCAL. FLAME TEMPERATURES BY THE TWO-LINE ATOIMICFLUORESCFNCE MEFTHOD", H-. Haraguchi, B. Smith, S. Weeks, D.J.Johnson, and J.D. Winefordner, Appl. Spcctrosc., 31, 156(1977).

21. "THE ANALYTICAL CAPABILITIES OF THE SELECTIVELY MODULATED INTER-FEROMETRIC DISPERSIVE SPECTROMETER (SEMIDS)", T. L. Chester andJ.D. Winefordner, Anal. Cheiri., 49, 113(1977).

22. "FLAME DIAGNOSTICS: LOCAL TEMPERATURE PROFILES AND ATOMIC FLUORE-SCENCE INTENSITY PROFILES IN AIR-ACETYLENE FLAMES", H. Haraguchiand J.D. Winefordncr, Appl. Spectrosc., 31, 195(1977).

23. "TEMPERATURE PROFILES OF AIR-H1YDROGEN FLAMES MEASURED BY TWO-LINEATOMIC FLUORESCEiNCE METHOD", 11. Iaraguchi and J .D. Winefordner,Appi. Spectrosc., 31, 330(1977).

24. "COMPARISON 01: PULSED SOURCE WITH CIV SOURCE EXCITATION IN ATOMICAND MOLECULAR LUMI NESCENCE SPECTROMNETRY V IA SI GNAL -TO - NO ISERATIO CALCULATIONS", G.D. Boutilier, J.D. Bradshaw, S.J. Weeks,aind J.D. IWinefordner, AEpi . Spectrosc ., 31, 107(1977).

;t -4-25. "EVALUATION OF A PULSED ETMAC SOURCE FOR ATOMIC FLUORESCENCE

sPEcTROMI.-iRY", I).J. Johnson, W.K. Fowler, and J.D. Wincfordner,Talanta,, 24, 227(1977).

26. "A REPRODUCIBLE METHOD FOR PREPARATION AND OPERATION OF MICROWAVEEXCITED ELECTRODELESS DISCHARGE LAMPS: SIMPLEX OPTIMIZATION OFEXPERIMENTAL FACTORS FOR A CADMIUM LAMP", R.G. Michel, JuliaColeman, and J.D. Wincfordner, Spectrochim. Acta B,

27. "COMPARISON OF IMAGE DEVICES VS PHOTOMULTIPLIER DETECTORS IN ATOMICAND MOLECULAR LUMINESCENCE SPECTROMETRY VIA SIGNAL-TO-NOISE RATIOCALCULATIONS", R.P. Cooney, G.D. Boutilier, and J.D. Winefordner,Anal. Chem., 49, 1048(1977).

28. "1PULSED VS C11 ATOMIC FLUORESCENCE SPECTROSCOPY", N. Omenett3,G.D. Boutilier, S.J. Weeks, B.W. Smith, and J.D. W1inefordner,Anal. Chem., 49, 107S(1977).

29. "THlE USE OF RADIO-FREQUENCY EXCITED ELECTRODELESS DISCHARGE LAMPSFOR ATOMIC FLUORESCENCE SPECTROSCOPY", A.H. Ullman, C.M.P. Favez,and J.D. Winefordner, Can. J. Spectrosc.., 22, 43(1977).

30. "BACKGROUND FLUORESCENCE SPECTRA OBSERVED IN ATOMIC FLUORESCENCESPECTROMETRY WITH A CONTINUUM SOURCE", W.K. Fowler and J.D.W1inefordner, Anal. Chem., 49, 944(1977).

31. "THE ATOMIC FLUORESCENCE OF SODIUM UNDER CONTINUOUS WkXE LASEREXCITATION", B. Smith, J.D. hfinefordner, and N. Omenetto, J.Ap_. Physics, 48, 2676(1977).

32. "A REVIEW AND TUTORIAL DISCUSSION OF NOISE AND SIGNAL-TO-NOI1SERATIOS IN ANALYTICAL SPECTROMETRY", C.Th.J. Alkemade, W. Snellernan,G.D. Boutilier, B.D. Pollard, J.D. Winefordncr, T.L. Chester, andN. Omenetto, Spectrochim. Acta B, Vol. 33B, 383(1978). PART I

33. A REVIEW AND TUTORIAL DISCUSSION OF NOISE AND SIGNAL-TO-NOISERATIOS IN ANALYTICAL SPECTROMETRY - PART 11", C.Th.J. Alkemade,1W4. Snellemen, G.D. Boutilier, B.D. Pollard, J.D. Winefordner,T.L. Chester, and N. Omenetto, Spectrochim. Acta B, Vol. 33B,401(1978).

34. "PROFILES OF TEMPERATUJRE AND ATOMIC FLUORESCENCE INTENSITIES INIfYIROGEN-ARGON FLAMES", If. Ifaraguchi, S. Wecks, and J.I). Winefordncr,Can. J. Spectrosc., 22, 61(1977).

35. "ATOMIC FLUORESCENCE FLAME SPECTROMETRY WITH A CONTINUOUS WAVE DYELASER",I B .W. Smith, NMariana Blackburn, and J.D. Winefordner,Can. J. Spcctrosc., 22, 57(1977).

-36. "ATOMIC ABSORPTION INHIBITION RELEASE TITRATION AS A METHOD FORSTU'DYI NG 01: II I.E:A~ rNG ANI) I NHII BI TION EFFECTS"', 1). S to 1 ; ov ic, ..Bradshaw, and J.I). Wincfordner, Anal. Chini. Acta, 96, 45(1978).

37. "CW-LASER EXCITED MOLECULAR FLUORESCENCE OF SPECIES IN FLAMES",M.B. Blackburn, J.M. Mermet, and J.D. Winefordner, Spectrochim.Acta A, 34A, 847(1978).

38. "PRINCIPLES, METHODOLOGIES, AND APPLICATIONS OF ATOMIC FLUORESCENCESPECTROMETRY", J.D. Winefordner, J. Chem. Ed., 55, 72(1978).

39. "IMPROVEMENT OF THE DETECTION LIMITS IN LASER-EXCITED ATOMICFLUORESCENCE FLAME SPECTROMETRY", S.J. Weeks, H. Haraguchi, andJ.D. Winefordner, Anal. Chem., 50, 360(1978).

40. "SELECTIVE EXCITATION OF MOLECULAR SPECIES IN FLAMES BY LASER-EXCITED MOLECULAR FLUORESCNECE", H. Haraguchi, S.J. Weeks, andJ.D. Winefordner, Spectrochim. Acta A, 35A, 391(1979).

41. "LASER-EXCITED MOLECULAR FLUORESCENCE OF CaOH AND SrOH IN ANAIR-ACETYLENE FLAME", S.J. Weeks, H. Haraguchi, and J.D. Winefordner,JQSRT, 19, 633(1978).

42. "STEADY STATE ATOMIC FLUORESCENCE RADIANCE EXPRESSIONS FORCONTINUUM EXCITATION", G.D. Boutilier, M.B. Blackburn, J.M.Mermet, S.J. Weeks, H. Haraguchi, J.D. Winefordner, and N.Omenetto, Appl. Optics, 17, 2291(1978).

43. "STEADY STATE MOLECULAR LUMINESCENCE RADIANCE EXPRESSIONS ASSUMINGNARROW BAND EXCITATION", G.D. Boutilier, J.D. Winefordner, andN. Omenetto, Appi. Optics, 17, 3482(1978).

44. "A CONTINUUM SOURCE, SINGLE DETECTOR RESONANCE MONOCHROMATOR FORATOMIC ABSORPTION SPECTROMETRY", J. Bower, J. Bradshaw, and J.D.Winefordner, Talanta, submitted.

45. "AN EVALUATION OF THE SPECTRAL NOISE DISTRIBUTION IN ANALYTICALFLAMES", K. Fujiwara, A.II. Ullman, J.D. Bradshaw, and J.D.Winefordner, Spectrochim. Acta B, 34B, No. 4, 137(1979).

46. "ATOMIC FLUORESCENCE SPECTROMETRY IN THE INDUCTIVELY COUPLED PLASMAWITH A CONTINUOUS WAVE DYE LASER", B.D. Pollard, M.B. Blackburn,S. Nikdel, A. Massoumi, and J.D. Winefordner, Appl. Spectrosc.,Vol. 33(l), 5-8(1979).

47. "DETECTION LIMITS OF RARE EARTHS BY INDUCTIVELY-COUPLED PLASMAATOMIC EMISSION SPECTROSCOPY", S. Nikdel, A. Massoumi, andJ.D. Winefordner, Microchem. J., 24, 1-7(1979).

48. "APPLICATION OF TilE TWO LINE ATOMIC FLUORESCENCE TECHNIQUE TO THETEMPORAL MEASUREMENT OF SMALL FLAME VOLUMES", J. Bradshaw, J.Bower, S. Weeks, K. Fujiwara, N. Omenetto, H. Ilaraguchi, and J.D.Winefordner, 10th Materials Research Symposium on Characterizationof High Temperature Vapors and Gases.

49. "IXPERIMENTAL VERIFICATION OF SATURATION IN LASER EXCITED ATOMICFTLUORES('11NCE SECTR.IhETRY , M.B. B] ackburn, J. M. Mermet, G.DBoutilier, and J.D). Winefordner, App - Optics, submitted.

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50. "A VERSATILE COMPUTER-CONTROLLED MULTIELEMENT ATOMIC EMISSION/FLUORESCENCE SPECTROMETER SYSTEM", A.H. Ullman, B. D. Pollard,R.P. Bateh, and J.D. Winefordner, Anal. Chem., submitted.

51. "A COMPARATIVE STUDY OF STANDARDS AND SAMPLING PROCEDURES FOR

ANALYSIS OF TRACE WEAR METALS IN JET ENGINE OILS", T.M. Tucll,A.1I. Ullman, B.D. Pollard, A. Massoumi, J.D. Bradshaw, J.B. Bower,and J.D. Winefordner, Anal. Chim. Acta, 108(1979)351-356.

52. "ANALYTICAL AND SPECTRAL FEATURES OF ARSENIC AND ANTIMONY BY GAS

PHASE CHEMILUMINESCENCE SPECTROMETRY", K. Fujiwara, J. Bower,J. Bradshaw, and J.D. Winefordner, Anal. Chim. Acta, 109(1979)229-239.

53. "A COMPARATIVE INVESTIGATION OF ANALYTICAL FIGURES OF MERIT FORSEVERAL ELEMENTS IN ORANGE JUICE BY FLAME ATOMIC ABSORPTIONSPECTROMETRY, FLAME ATOMIC EMISSION/FLUORESCENCE SPECTROMETRY,DC PLASML EMISSION SPECTROMETRY, AND INDUCTIVELY COUPLED PLASMAATOMIC EMISSION SPECTROMETRY", J.A. McHard, S.J. Foulk, S. Nikdel,A.H. Ullman, B.D. Pollard, and J.D. Winefordner, Anal. Chem.Vol. 51, NO. 11, p 1613.

54. "A REVIEW AND TUTORIAL DISCUSSION OF SIGNAL-TO-NOISE RATIOS INANALYTICAL SPECTROMETRY - III, MULTIPLICATIVE NOISES", C.Th.J.Alkemade, W. Snelleman, G.D. Boutilier, and J.D. Winefordner,Spectro. Chim. Acta B., submitted.

55. "SOME DIAGNOSTIC AND ANALYTICAL STUDIES OF THE INDUCTIVELYCOUPLED PLASMA BY ATOMIC FLUORESCENCE SPECTROMETRY", N. Omenetto,S. Nikdel, J.D. Bradshaw, M.S. Epstein, R.D. Reeves, and J.D.Winefordner, Anal. Chem., Vol 51, p.1521(1979).

56. "FLUORESCENCE RATIO OF THE TWO D SODIUM LINES IN FLAMES FOR D1AND D2 EXCITATION", N. Omenetto, 1M.S. Epstein, J.D. Bradshaw,

S. Bayer, J.J. Horvath, and J.D. Winefordner, JQSRT, submitted.

57. "A NEW, INEXPENSIVE, NITROGEN PUMPED DYE LASER WITH SUBNANOSECONDPULSES", G.L. Walden, J.D. Bradshaw, and J.D. Winefordner,Appl. Phys. Lett., submitted.

58. "PRECTSION AND LINEARITY OF DETERMINATIONS AT HIGH CONCENTRATIONSIN ATOMIC ABSORPTION SPECTROMETRY", M.S. Epstein and J.D. Wine-fordner, Talanta, submitted.

59. "LASER INDUCED FLUORESCENCE IN KEROSENE/AIR AND GASOLINE/AIR FLAMES",K. Fujiwara, N. Omenetto, J.B. Bradshaw, J.N. Bower, and J.D.Winefordner, Combustion and Flame, submitted.

60. "A COMPARISON OF TRACE ELEMENT CONTENT OF FLORIDA AND BRAZIL

ORANGE JUICE", J.A. Mcllard, S.F. Foulk, and J.D. Winefordner,J . F Food Chem ., submitted.

61. "APPLICATIONS OF AN INDUCTIVELY-COUPLED ARGON PLASIMA AS ANEXCITATION SOURCE FOR FLAME ATOMIC FLUORESCENCE SPECTROMETRY",M.S. Epstein, S. Nikdel, N. Omenetto, R. Reeves, J. Bradshaw,and J.D. Winefordncr, Anal. Chemi., submitted.

62. "LASER INDUCED MOLECULAR BACKGROUND FLUORESCENCE IN FLAMES",by K. Fujiwara, N. Omenetto, J.B. Bradshaw, J.N. Bower, S. Nikdel,and J.D. Wincfordner, Spectrochim. Acta. B., submitted.

63. "APPLICATION OF LASER-EXCITED ATOMIC FLUORESCNECE SPECTROMETRYTO THE DETERMINATION OF IRON", M.S. Epstein, S. Bayer, J. Bradshaw,E. Voigtman, and J.D. Winefordncr, Spectrochim. Acta B., submitted.

64. "EVALUATION OF SELECTIVITY IN ATOMIC ABSORPTION AND ATOMICEMISSION SPECTROMETRY", Kitao Fujiwara, J.A. McHard, S.J. Foulk,S. Bayer, and J.D. Winefordner, Canadian Journal of Spectrosc.,submitted.

65. "APPLICATION OF LASER-EXCITED ATOMIC FLUORESCENCE SPECTROMETRYTO THE DETERMINATION OF NICKEL AND TIN", M.S. Epstein, J. Bradshaw,S. Bayer, J. Bower, E. Voigtinan, and J.D. Winefordner, Appl.Spectrosc.

66. "SOME EXAMPLES OF THE VERSATILITY OF THE INDUCTIVELY-COUPLED ARGONPLASMA AS AN EXCITATION SOURCE FOR FLAME ATOMIC FLUORESCENCESPECTROMETRY", M.S. Epstein, N. Omenetto, S. Nikdel, J. Bradshaw,and J.D. Winefordner, Anal. Chem., submitted.

67. "FURTHER IMPROVEMENTS IN DETECTION LIMITS IN LASER EXCITED ATOMICFLUORESCENCE SPECTROMETRY", J.N. Bower, J. Bradshaw, J.J. Horvath,and J.D. 11inefordner,

68. "ATOMIC AND IONIC FLUORESCENCE SPECTROMETRY USING PULSED DYELASER EXCITATION IN THE INDUCTIVELY COUPLED PLASMA", M.S. Epstein,S. Nikdel, J.D. Bradshaw, M.A. Kosinski, J.N. Bower, and J.D.Winefordner, Analytica Chimica Acta, submitted.

69. "LASERS IN ANALYTICAL SPECTROSCOPY". N. Omenetto and J.D. Winefordner,CRC Crit. Rev, in Anal. Chem., submitted.

70. "MOLECULAR EMISSION SPECTRA IN THE RF-EXCITED INDUCTIVELY COUPLEARGON PLASMA", R .D. Reeves, S. Nikdel, and J.D. Winefordner,Appi. Spectrosc., submitted.

71. "RELATIVE SPATIAL PROFILES OF BARIUM ]ON AND ATOM,1 IN THE ARGONINDUCTIVELY COUPLED PLASMA AS OBTAINED) BY LASER EXCITED FLUORESCENCE",N. Omentto, S. Nikdcl, R.D. Reeves, J.B. Bradshaw, J.N. Bower,and J.I). Winefordner, Spectrochim. Acta B., submitted.

72. "A REVIEW ANI) TUTORIAL D)ISCUSSION OF NOISE AND SIGNAL-TO-NOISERATIOS IN ANALYTI CAL SPECFROMETMX-II I. MULTI Iiil CATIVI3 NOISES'',C.Th.J. Alkemnade, IV. Snellemamn, G.fl. Boutilier, and J.D. 'Winefordner,Spectrochim. Acta B., submitted

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"DETERMINATION OF FLAME AND PLASMA TEMPERATURES AND DENSITYPROFILES BY MEANS OF LASER EXCITED FLUORESCENCE", J. Bradshaw,S. Nikdel, R. Reeves, J. Bower, N. Omenetto, and J.D. WinefordnerT,ACS Symposium Monograph on "Laser Probes of Combustion Chemistry".

9. ABSTRACT OF OBJECTIVES AND ACCOMPLISHMENTS

The research completed during the past four years can be generallydivided into combustion diagnostics and analytical , s phaseatomic and molecular spectrometry. Significant adv ices have beenmade in both areas. New and improved techniques to spatiallyand temporally measure flame gas temperatures and species havebeen and are being developed. These techniques are all based uponfluorescence detection. Earlier studies involved the use of aconventional xenon arc lamp source, whereas recent studies in-volve the use of a pulsed, high peak power tunable dye lasers.By measuring the ratio of two fluorescence transitions (in a probe,such as indium) excited with two different wavelengths, the flametemperature can be measured with a precision and accuracy betterthan 50 K. The two main temperature techniques developed dependupon either the linear relationship between fluorescence and theexcitation flux on the approach to saturation of the fluorescencewith high excitation fluxes. The measurement of total speciesconcentrations in flames and fluorescence quantum efficienciesis readily performed by measurement of the absolute fluorescenceflux reaching a calibrated detector as a function of absolutelaser flux. A rather simple graphical method allows both speciesconcentration and species fluorescence quantum efficiencies tobe measured. Using these approaches, both flame temperatureand spccies concentration spatial profiles in a variety oflaboratory flames (acetylene/air, acetylene/N 20, H2 /air, H2/O2/Ar,etc.) have been measured.

Analytical gas phase spectrometric studies have spanned a consider-able breadth. Theoretical calculations of signal-to-noise ratiohave been made to obtain: approaches to the optimization of spec-tral measurement systems (linear spectral scan spectrometersvs sequential slow scan spectrometers vs multiple detector spectro-meters vs multiplex spectrometers, sucl-as Hladamard Transformand Fou-i-er Transform); approaches to the optimization of conven-tional and time resolution of luminescent components (cw source-cw detection, pulsed source-gated detection with no time resolu-tion, and pulsed source-gated detection with time resolution);approaches to the optimization of atomic and molecular analyticalmethods (absorption vs emission vs fluorescence vs Raman and theuse of optogalvanic and optoacoustic detection as well as the useof non-linear methods involving more than one photon processes);and finally approaches to the optimization and use of image detectors(vidicons, SIT, ISIT, diode 3rrays, etc.) over photomultiplierdetectors for optical spectroscopy.

Experimental analytical gas phase spectrometric studies haveinvolved: the development and refinement of pulsed (and cw)tunable dye laser excitation of ,toms produced by spraying aerosols

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into combustion flames, furnaces, and inductively coupled plasmas;the development and refinement of an E.J1MAC xenon arc source-flame-slew scan atomic fluorescence spectrometer for multielement analy-sis in real samples, such as engine oils, biological materials,etc.; the development and refinement of an innovative source foratomic fluorescence flame spectrometry, namely the use of anICP source which has the benefits of both a continuum source interms of wavelength selectivity and line sources in terms ofintense narrow line output; and development, of chemiluminesccnceproduced above a furnace (into which samples are nebulized) as ananalytical method. By means of these approaches, considerableselectivity (near specificity in several cases) is obtained withdetection limits in the picograms per milliliter in most casesand with precisions (%RSD) of the order of 5% or better. The abovetechniques have been applied to the selective measurement ofultratrace elements in real samples, such as elements in riverwater and the selective measurement of trace elements in sampleswith complex matrices, such as zinc in copper alloys, trace elementsin orange juice, and trace elements in fly ash.

Other analytical and diagnostical studies performed include: acomparison of wavelength vs amplitude modulation in optical spectro-scopy; use of a continuum source, resonance monochromator foratomic absorption flame spectrometry; identification of the mole-cular fluorescence components of unseec-d and seeded flames;identification of the major spectral noise peaks in flame emissionand fluorescence spectrometry; a tutorial and definitive reporton additive and multiplicative noises in optical emission andfluorescence spectrometry; an evalu,-.tion of commercial RF-electrodeless discharge lamps and the design of an experimentalapproach to prepare and evaluate microwave electrodeless dischargelamps for atomic fluorescence flame spectrometry; and an evaluationof several multiplex (including the Hadamard spectrometer) approachesand image devices for multiple element measurements in atomicemission and fluorescence spectrometry.

In summary, the past 4 years have been fruitful in the developmentof combustion diagnostical approaches which will have considerableuse in evaluating large flames (as in combustors) and in develop-ing selective, sensitive approaches to trace element measurements.

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10. REVIEW OF PROGRESS IN PAST FOUR YEARS

Fundamental and Diagnostical Studies

Flame Temperature Measurements. Two basic approaches have beendevelopcd and have been or are being evaluated. These approachesinvolve either the measurement of the fluorescence intensity ratioof direct line fluorescences (with excitation of the resonancelevel via the ground state or via the metastable state and measur-ing the resulting direct line fluorescence)in an indium type atom(In, Ga, TI, Pb, etc.) or the measurement of the ratio of resonancefluorescence intensity resulting when excitation is via the reson-ance absorption process or via the metastable state [refer to theAPPENDIX]. In the former case, the excitation must be on thelinear portimof the fluorescence intensity vs source intensitycurve and in the latter case; saturation musf-be approached. Inthe former case, conventional xenon arc sources can be used whereasin the latter, a high peak power laser must be used since thesaturation spectral irradiances of transitions of atoms in hydro-carbon flames are very large. In both cases, steady state condi-tions must be met and the sources must not cause disequilibriumto occur. By means of these approaches, temperature spatial pro-files in a number of laboratory flames have been determined. Thespatial resolution of the former method with an EIMAC xenon arcsourse is %5 mm3 _whereas for the latter with a pulsed tunable dyelaser is "-0.2 mm3. The former technique could, of course, be donewith a pulsed tunable or cw tunable dye laser using neutral den-sity filters to minimize saturation and to obtain %0.2 mm° spatialresolution. By means of pulsed tunable dye lasers, it is possiblealso to obtain temporal resolution, e.g., temperature values withina 20-30 ns period 100 times a second.

Species Concentration and Quantum Efficiency Measurements. For a2-level atom (or molecule), it can be shown that tliefluorescenceradiance, BF is related to the laser excitation flux, 0, by

1 _ 12B F +nT

where K. is a constant containing the laser excitation bandpassand area and K1 and K2 are constants containing known parametersas the transition probability, statistical wieght, gas path lengthover which fluorescenceis measured, and energy of the emittedphoton. By measuring the absolute laser flux, area, and bandpass,the fluorescence radiance, and the fluorescence path length, it ispossible to determine both absolute values nT (the total concen-tration of species) and Y (the quantum efficiency of the fluorescenceprocess) from the intercept and slope. The former is valuablein combustor modelling and in absolute analysis and the latter isvaluable in understanding the deactivation processes in gases andplasmas.

For a three level (or greater number of levels), the relationship

LI-J

between BF, 4, nT, and Y is quite similar to the 2 level case butmore complex in that now radiationless rate constants must beknown (or negligible) to evaluate nT and Y from the intercept andslope of the 1 vs 1. Under certain experimental conditions, it

is possible to approximate the terms containing the radiationlessrate constants. Work is currently in progress demonstrating thepotential use of this approach for evaluation of atomic andmolecular species concentrations in laboratory type flames. Thisapproach should also be useful for evaluating the species concen-trations in combustors; obviously here extremely high peak powerlasers will be needed. Also it is feasible to obtain both spatialand temporal profiles by using high peak power pulsed, tunabledye lasers.

During the past 2 years, we have verified the validity of theabove theoretical approach with accurate experimental measurements.

During the past year, we have used the pulsed tunable dye laserapproach to spatially profile seeds (Ba, Sr, In, etc.) sprayedinto laboratory flames (H2 and C2H2 -based flames). Although thepossibility of temporal profiles exists, only initial measurementshave so far been performed.

Signal-to-Noise Ratio Calculations

Signal-to-noise is perhaps the most important of all spectrometricfigures of merit. The signal-to-noise ratio influences the pre-cision (%RSD) and the detection limit (LOD) of an analyticalmeasurement. A tutorial approach was recently published in whichadditive noises were considered in both emission and luminescencestudies. More recently, a similar approach has been prepared onmultiplicative noises which unfortunately are also intimatelyrelated to the signal level. In these studies, the influenceof sampling time (related to measurement time), instrument responsetime or integration time, and modulation with ac detection wereconsidered with respect to their effects on the SNR. Some ratherapparent but basic conclusions are that all methods are affectedby white noise, that modulation and ac detection is useful onlyif the noise source is not modulated, that additive flicker noisescan be minimized by proper choice of response and sampling times,that multiplicative flicker noise can be minimized only by useor an ideal internal standard, and that proportional (whistle)-noises can be avoided by proper choice of modulation frequency.

In a separate report, wavelength, amplitude, and sample modulationwere compared. Theoretically sample-blank-standard modulation isan ideal analytical approach but experimentally it is difficultto perform with a sufficient modulation frequency to minimizeflicker noises. Therefore, the best, current experimental approachis to wavelength modulate to minimize drift (flicker) in the back-ground (in emission or lumincscnece studies.) Amplitude'modula-tion is the simplest to perform but more susceptible to driftproblems. If white noise is dominant, then the best approach is

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to use dc detection.

In other separate studies, multiplex (Hadamard and Fourier TransformSpectrometers) systems, multiple photodetector systems (directreaders), sequential slew scan spectrometers, and sequentiallinear scan methods were compared for optical (UV-VIS) spectroscopywith the following general conclusions: based on SNR calculations,the multiplex systems will have little use in high or even moder-ate background cases, such as flame emission, or in molecularabsorption with a continuum background source; the multiplephotodetector spectrometer is the best if one knows which spectraltransitions to measure and if there is little need to even changeto other transitions; the sequential slew scan (computer programmed)spectrometer is the most versatile and best if 10 or fewer transi-tions are to be measured or if initial cost is the most criticalfactor; the linear sequential scan spectrometer is of littlequantitative use but is a reliable qualitative analysis tool.Experimental studies by us and others have verified these theore-tical predications.

In another st:dy, it was shown that (based on SNR) the imagedetectors are at best poorer than photomultiplier detectors foratomic spectrometry. For molecular spectrometry, particularly whenabsorption or luminescence detection of gas or liquid chromato-graphic effluents is used, the image devices are generally superiorto photomultipliers in terms of SNR for a given measurement timeand for a large range of spectral components. Experimental veri-fication of these theoretical concepts have also been carried out.

Finally, it was shown that a pulsed source-gated detector withtime resolution has considerable advantage for luminescencespectrometry (compared with pulsed-source-gated detection with notime resolution, modulated source with averaging detection, andcw source with cw detection) if the spectral interferent has ashorter lifetime than the analyte. If this is not the case thenthe more conventional approaches (modulation or cw) are simplerand at least as good (based.on SNR). Experimental verificationof these theoretical concepts have also been carried.

Analytical Gas Phase Spectrometric Studies

Laser Excited Atomic Fluorescence Spectrometry. At this point intime, it is apparent that laser excited atomic fluorescencespectrometry (LEAFS) has very specific and specialized uses, i e.,

it is not yet a routine analytical tool primarily because of thehigh initial cost, the complexity and cost of operating many lasers,and the applicability of tunable dye lasers to only a singleexcitation transition within a short time period (say 5 min), i.e.,tunable dye lasers can not yet be slew scanned reliably to a widerante of wavelengths. Nevertheless, we have shown that LEAFS(see Figure 1) has tremendous potential for certain applications,namely where extremely low detection limits are needed and wherehigh spectral selectivity is riceded. It should be mentioned thatdespite the inert atmosphere of the inductively coupled plasma,

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relatively poor limits of detection (see Table I) were obtainedwith pulsed dye or cw dye laser excitation; the high plasmabackground noise prevented improvements compared to the flameatomizer system. In Table IA, we have given detection limits(LODs) obtained by LEAFS in the past 4 years. These values rivalor exceed the best LODs reported by others by similar and differentmethods. We have also applied LEAFS to the measurement of trace

-elements in a variety of samples, difficult or impossible tomeasure by any other method (see Tables II and III for typicalexamples). In addition to the excellent LODs, the linear dynamic-ranges of most elements is 105X to 107X and the %RSD %5%.

Inductively Coupled Plasma Atomic Flame Fluorescence Spectrometry. Inthis study, high concentrations of a given element are sprayedinto the inductively coupled plasma (ICP) which is the sourceof excitation for atoms produced via spraying samples into theflame; atomic fluorescence is measured (see Figure 2). It wasshown theoretically and verified experimental that because theICP has little self absorption even at concentrations of 20,000ppm and rare self-reversal (except at high heights), it is anideal source for FAFS. The ICP source is intense and the spectrallines of atoms in the ICP are narrower than for atoms in theICP, and so by simply varying the elemental content of thesolution sprayed into the I:CP, one can have a narrow line sourcefor virtually any element. The major advantage of using an ICPas a source for FAFS rather than spraying the analyte into the ICPand using the emission of the ICP for analysis is that in the ICP-FAFS case, the flame acts as a resonance monochromator, minimizingor eliminating complex spectral interferences arising in an ICPused for emission analysis. In our case, using 20,000 ppm ofelements in the ICP, the detection limits shown in Table IV re-sulted. These values could be improved substantially (by lOOX)by (1) increasing the concentration of element in the ICP,(2) increasing the time constants on the measurement system, and(3) increasing the solid angle of collection of ICP rediationspraying on the flame. This approach also has 2 other uniqueadvantages, namely: (1) scatter can be corrected by use of anearly ICP line, such as Ar, or by making use of self absorptionin the ICP which results in a plateauing of fluorescence intensi-ties but in a corresponding increase in the scatter; and (2)measurement of high concentrations of (>1000 ppm) by spraying thesample into the ICP and a low fixed concentration of analyte intothe flame which now acts as a resonance monochromator. In TableV, typical application results of the ICP-FAFS system is given.

Detection limits obtained with the ICP-FAFS system were superiorto emission ICP values obtained with our experimental system andestimated LOD, for the same line. However, the LODs in our casewere generally 3 to 1OX poorer than the best previously given inthe literature for emission ICP.

Multielement BIMAC Atomic Fluorescence Spectrometry (MEAFS). Thissystem consisting of an EIMAC xenon arc lamp, a flame, a photo-multiplier detector, a synchronous photon counter, and a programmedcomputer for wavelength slewing and for data processing. Both

-14-

amplitude and wavelength moderation have been used. Althoughthe detection limits (see Table I) are not as good as othertechniques (those mentioned above or atomic absorption), thesystem provided reliable results for real. sample analyses for 20or fewer elements. The MEAFS system (worth less than $50,000)is easy to use, reliable, and versatile. Limits of detection inthe sub ppm range were obtained for a large number of elements anapplications were made to trace elements in biological samples,jet engine oils, standard reference materials, and metals (seeTables VI, VII, VIII).

Atomic Sectrometry in Furnances. During the past 4 years, bothcw and discrete sampling furnaces were studied. The presence ofand difficulty of interpretation of the effects of matrix materialson the emission, absorption, or fluorescence signals has led usto the following conclusion: furnaces should only be used foranalysis if the sample can not be done by a flame, an ICP, etc.,i.e., if one is sample limited or sensitivity limited. Atomicfluorescence detection with tunable dye laser excitation resultsin sub-picogram LODs but real sample analyses are plagued withinterferences difficult to interpret.

More recently, we have evaluated the potential use of chemilumines-cence of species produced in a cw furnace and reacting with anoxidant, such as N20, C12 , etc. Molecular chemiluminescencespectra result which can be used for trace measurements of speciessuch as As and Sb in our case. We intend to go to the use of F2which is a stronger oxidant and should be a useful "source" ofexcitation for a wide variety of elements.

Other Studies

By means of a continuum source of excitation, a flame for thesample introduction, and a cw furnace with analyte being contin-uously introduced and a photomultiplier detector, a highly spec-tral selective resonance monochromator system was evaluated foratomic absorption flame spectrometry. The system perfoimed asexpected but was somewhat inferior to a conventional line sourceatomic absorption flame spectrometer. Further studies arewarranted.

By means of pulsed and cw tunable dye laser excitation, molecularfluorescence of native species (C2 , CH, OH, NH, CN) and introducedspecies PO, SrOHI, CaOH, CrO, MnO, BaCl, BaOH, BaO) have beenobserved and identified. Because of the low fluorescence inten-sities of the latter species, few analytical capabilities exist;however, the fluorescence of the native and introduced speciescan lead to spectral interferences in a few specialized cases.The contributions of shot and flicker emission and fluorescencenoises to the total noise as a function of wavelength (200-800 nm)were also evaluated for a variety of laboratory flames; the sourceof excitation for fluorescence was an EIMAC xenon arc lamp. Thenoise sources in pulsed laser excited atomic fluorescence spectro-metry are currently being measured.

-15-

A theoretical and experimental comparison of optoacoustic andoptogalvanic detection with fluorescence detection is currentlyin progress; initial results indicate that optoacoustic detectionis very specialized and has few uses for UV-Visible opticalspectrometry of gases. Optogalvanic detection does not seem tobe as sensitive and certainly not as selective as fluorescencedetection.

By means of signal-to-noise ratio expressions, derived forlimiting noise cases, estimated detection limits for atomic ab-sorption (with line and continuum sources), atomic emission(flame vs ICP), and atomic fluorescence (flame and ICP atomizersand line vs continuum sources operating on the linear and satur-ated regime) was obtained. These calculated detection limitsindicate that atomic emission with an ICP is excellent but hasnearly reached its ultimate sensitivity whereas atomic fluorescencewith laser sources can theoretically be improved by severalorders of magnitude and ultimately exceed the detection power ofthe ICP-emission method by several orders of magnitude. To esti-mate solution concentrational detection limits from the gaseousatom detection limits (in terms of atoms cm-3 in Table IX), oneneeds to divide the n-values by %lOCSa where a is the free atomfraction in the hot gas for the analyte atom ( a = 1 if the speciesis 100% atomized). Actually, if the efficiency and rate of intro-duction of sample solution into the flame varies significantlyfroq the values used to estimate the 101 1 factor, then the "constant"(1011) must be charged. During the past 4 years, Hadamard spectro-metry and a modified Michelson spectrometer (interferometer) havebeen evaluated experimentally and theoretically and have beenshown to have little use for the UV-Visible Spectral region,especially for emission, fluorescence, and absorption spectrometrywhere either the cell emission and/or the source emission isintense and spectrally broad. Calculations (SNR) have similarlyshown that the conventional Michelson interferometer, the SISAMsystem, or any other modifications will also be of little use inthe UV-Visible region becaijse of a great reduction on SNR comparedto more conventional approaches.

Other studies have included: the use of information theory toevaluate analytical methods; particularly with respect to resolvingpower, the measurement of the detection limits of rare earths byICP emission; a study of the factors affecting aerosol productionin nebulizer-burners; an evaluation of a selectivity conceptbased upon II. Kaiser's approach; a deviation of radiance expressionsfor atomic fluorescence assuming continuum excitation and formolecular fluorescence and phosphorescence assuming narrow lineexcitation, a definitive report on why the ratio of the sodiumD1 and D2 fluorescence varies with excitation via the D1 or D2transition; the use of an atomic absorption inhibition release titra-tion for studying the chemical equilibria and kinetics in flames;the measurement of phosphorous via molecular fluorescence of PO inflames; and several application papers involving the measurement oflead in confection wrappers and trace elements in orange juice.

~-16-

TABLE IA

DETECTION LIMITS (AQUEOUS SOLUTION) OBTAINED BY LASER EXCITEDATOMIC FLUORESCENCE SPECTROMETRY LEAFS AND BY SEVERAL OTHER METHODS

Element Detection Limit (ng/ml) Optogalvanic 6

Line Source1 Continuum Source2 LEAFS3 AS4 AICP5 LaserMEAFS

Ag 0.1 1. 4. 2. 0.2(4)

Al 100. 200. 0.6 20. 0.4

As 100. - - 400. 2.

Au 1,000. 150. - 200. - -

Ba - - 8. 20. 0.01(0.2) -

Be 10. 15. - 2. -(0.3) -

Bi 10. - 3. 30. -(50) -

Ca 20. - (0.01)7 0.08 2. 0.0001(4) -

Cd 0.001 6. 8. 1.5 0.07**(l) -

Ce - - 500.* - 0.4(20) -

Co 5. 15. (19)7 200.* 15. 0.1**(2) -

Cr 50. 1.5 1. 3. 0.2(4) 2.

Cu 1. 1.5 1. 2. 0.04**(2) 100.

Dy - - 300.* - -(2) -

Er - 500.* -

Eu - 20.* - -(1) -

Fe 8. 10. 30. 10. 0.09(2) 2.

Ga 10. - 0.9 - 0.6(40) 0.07

Gd - 800.* - 0.5(8) -

Ge 15,000. - - - (50)

Hf - - 200. -(-)

Hg 80. - -(50)

Ho - - I00.* -

In 100. 25. 0.2 - -(40) 0.008

Li - - 0.5 1. -(3) -

LU - 3,000.* -

Mg 1. 0.1 (0.009)7 0.2 0.1 0.003(20) 0.1

Mn 6. 2. 0.4 3. 0.02(0.5) 0.3

Mo 500. 100. 12. 20. 0.4(5) -

Na 100,000. -

TABLE IA - cont.

Element Detection Limit (ng/ml) Optogalvanic 6

12 3 4 5Line Source Continuum Source LEAFS AAS AEICP Laser

MEAFS

Nb -- 1,500..* - 0.2(20)-

Nd - - 2,O00.* 10. -(10)

Ni 3. 25. 2. - 0.2(6) 8.

Os - - 150,000.* 15. -(200)

Pb 10. 50. (1,3)7 13. - 1.**(20) 0.6

Pd 1,000. 100. - - 2.(40)

Pr .- - 1,000.* - -(30)

Pt 50,000. 700. - - -(30)

Rh 3,000. 0 100. * - -(30)

Ru - - Soo.* - -(60)

Sb -- 50.* 30. -(30)

Sc - - 10.* - -(1)

Se 40. - - 250. 1.**(20) -

Si 600. - - 100. - (10)

Sm - - 100.* - -(10)

Sn 30. 150. - 70. 3.(6) 6.

Sr 30. 0.9 (0.i) 7 0.3 1. 0.003 (0.2) -

Th - - 500.* -

Te 5.-- 70. -(20)

Ti -200. 2. 80. 0.03(1) 0.2

T1 S. 6. 4. 30. -(75) 0.09

TM - - 100.* -

*V 70. 30. 30. 50. 0.06(2)

Yb - - 10.* - -

Zn 0.02 15. - 1. 0.1(2)

*1. The values come from references within J.D. Winefordner, J. Chem. Ed., 55,72(1978).

2. The values come from D.J. Johnson, F.W. Plankey, and J.D. Winefordner,Anal.-Chem., 46, 1858(1974).

3. Values from 5S.J. Weeks, If. Haraguchi, and J.D. Winefordner, Anal. Chem.,50, 360(1978), except those with * which were taken from references listedin W'inefordner, J. Chem. Ed., 55, 72(1978).

i -18-

TABLE IA - cont.

4. All values come from Perkin Elmer atomic absorption commercial literatureon the Model 460.

5. All values from P.W.J.M. Boumans and F.J. de Boer, Spectrochim. Acta, 30B,309(1975), except for those with ** and those in (). All values in ()come from commercial literatures from Jarrell-Ash Division, Fisher ScientificCo., Wlatham, MA for their 3rd generation ICP plasma Atom Comp. All valueswith ** come from K.W. Olson, W.J. Haas, and V.A. Fassel, Anal. Chem., 49,632(1977).

6. Values taken from J.C. Travis, G.C. Turk, and R.B. Green, Chapter in NewApplications of Laser to Chemistry, ACS Monograph, Vol. 85.

7. J.N. Bower, J. Bradshaw, J.J. Horvath, and J.D. Winefordner, Anal. Chem.,submitted.

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-21-

TABLE II

Determination of Iron in Standard Reference Materialsusing Laser-Excited Atomic Fluorescence Spectrometry

SAMPLE LEAFS ANALYSIS a CERTIFIED VALUEb

Trace Elements in 78 ng/g 75 ± 1 ng/gWater (SRM-1643)

Unalloyed Copper 145 ±6 Vg/g 147 ±8 pg/g(SRM-394)

Fly Ash (XRM-1633) 6.2 ± 0.2% 6.2 ±0.3%

a ± one standard deviation of analytical results, where multiple

samples were analyzed

Office of Standard Reference Materials, National Bureau of Standards,Washington, D.C. 20234

C Not certified by NBS.

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-34-

APPENDIX

REPORT

Two flame temperature measurement methods have been developed

and used for several small laboratory flames. The methods are called

Two Line Linear Fluorescence Method (TLLF) and Two Line Saturation

Fluorescence Method (TLSF). In TLLF, the ratio of two direct line

fluorescence signals under the linear fluorescence - source flux

condition are measured, i.e., the irradiance ratio EF(' 3 2)/EF(' 3 1)

is measured (EF is the fluorescence irradiance for the wavelength

X and X31) and the flame temperature Tf is calculated from

5040 V2T- ) -6 log(i. log( x 3 )log(EX13 3) (F X

where E is the source (laser) spectral irradiance at the 2 excita-

tion lines X and X13 " A diagram of the transitions are shown

below

,,

Lua-

The major assumptions are that the two cases be done close together

(within 1 vs) that steady state, linear operation occurs for each

case, and that state 2 is thermally populated at the flame temper-

ature. In our case, CASE B and CASE A occurs repetitively but

with an 30 ns delay between them. The major assumptions have been

shown to be valid. Calibration of the spectrometric system is

essential here.

In TLSF, the fluorescence irradiance at X is measured follow-

ing excitation first at X(13 E and then at X(EX delayed

by %30 ns. In this case, saturation must occur and so the spatial-

temporal characteristics of the laser beam must be monitored so that

measuremcnts only occur in the saturation domain. In addition, the

laser spot size for EX13 and E 23 excitation must be the same. The

flame temperature, Tf, is thcn calculated from

4868Tf-

33 11 33

10lo + + 0.125EF

2-3

here E is the fluorescence irradiance at X with excitation atF3-1 3

1-3

X and EF is the fluorescence irradiance at X with excitation3 12-3

at X23. Here it is not necessary to calibrate in the spectrometer

but only to know the relative fluorescence signal levels.

-36-

The experimental system for these measurements is shown

in a schematic fashion in Figure 3. Several experimental flame

temperatures as measured by the TLSF and TLLF methods are given in

Table I; in Table X, literature values are also given for the same

flames. The spatial and temporal-resolution of the TLSF and TLLF

temperature values is 1.5 mm x 0.5 mm x 3 mm and 30 ns respectively, which

falls within the required resolution for flame modeling.

The experimental system is currently being interfaced via

CAMAC units to our PDP 11/34 minicomputer to allow spatial flame

temperature measurements of a variety of flames and plasmas. A

manual horizontal temperature profile of our ICP is shown in Figure

4. The major limitations to flame temperature measurements by the

much simpler and more precise (better SNR) method is the dye laser

source spectral irradiance. Currently, the TLSF method can be used

with non-quenching flames (H2 -based) and plasmas (inductively coupled

Ar plasma), but with quenching flames (hydrocarbon based) because

of the low quantum efficiencies of the probes (In, Ga, TI, Pb, etc.),

the saturation spectral irradiance is so large as to prevent sat-

uration with our Molectron UV-14-DL-14 Dye Laser system. Calculations

show that the Lambda Physik excimer laser-Lambda Physik dye laser

system will "saturate" In, Ga, TI, Pb, etc., in hydrocarbon based

flames. We hope sufficient funds will be available in the near

future to purchase the Lambda Physik excimer laser ("435,000.);

the other laser items are already available in our laboratory.

Other related studies in progress include the measurement of

atom quantum efficiencies and total concentrations (m-3 of atoms

and molecules in flames (see Table II). The experimental equipment

for these studies is shown in Figure 5. Some typical results via

-37-

several methods are shown in Table XI and Table XII (papers describ-

ing these approaches will be forwarded to AFOSR within a month).

In addition to the flame temperature measurement methods, TLLF

and TLSF with elemental probes (In, Ga, Ti, Pb, etc.). We are

also developing similar TLLF and particularly TLSF methods with

native flame species (e.g., OH, CH, C2 , etc.). Flame fluorescence

(laser induced) background spectra have been measured; these results

indicate the potential use of TLSF and TLLF for temperature

measurements (several papers concerning flame fluorescence spectra

will be sent to AFOSR within a month).

V

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