Outline of dissertation defense

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A presentation in defense of the dissertation entitled ANALYSIS OF FACTORS THAT AFFECT ION BEAM CURRENTS FOR COSMOGENIC 10 Be AND 26 Al ANALYSIS BY ACCELERATOR MASS SPECTROMETRY (AMS)” by Adam Lewis Hunt In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy Specializing in Chemistry at the University of Vermont

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Transcript of Outline of dissertation defense

  • A presentation in defense of the dissertation entitled

    ANALYSIS OF FACTORS THAT AFFECT ION BEAM CURRENTS FOR COSMOGENIC 10Be AND 26Al ANALYSIS BY ACCELERATOR MASS SPECTROMETRY (AMS)

    by Adam Lewis Hunt

    In Partial Fulfillment of the Requirementsfor the Degree of Doctor of PhilosophySpecializing in Chemistryat the University of Vermont

  • Outline of dissertation defenseI. Introduction to the analysis of cosmogenic 10Be and 26Al

    II. Investigation of factors which affect the sensitivity of accelerator mass spectrometry (AMS) for cosmogenic 10Be and 26Al isotope analysis

    III. Metal matrices to optimize ion beam currents for accelerator mass spectrometry

    IV. Investigation of metal matrix systems for cosmogenic 26Al analysis by accelerator mass spectrometry

    V. Closing remarks

  • Strategy for isotope quantification

  • Long-lived radioisotopesPleistocene Age 1.806 Ma to 11 ka before nowLatest period of glaciation

  • 10Be and 26Al productionPrinciple sourcesCosmogenesisMeteoric or garden variety (atmospheric)In situ terrestrial substrate (< 2 m)Negative muon capture (> 2 m)RadiogenesisInterstellar protonsPrinciple mechanism

    10Be (5.2 atoms g-1 a-1)16O(n,4p3n)10Be28Si(n,6p3n)210Be 26Al (30.1 atoms g-1 a-1)28Si(n,p2n)26Al Significance

  • Dual analysis of cosmogenic nuclides(b) VariablesExposure historyErosion history(a) Constants (relatively)Nuclide half-lifeNuclide production rateSubstrate densityAttenuation length for neutronsNuclide activity is a function of:

  • 10Be- and 26Al-specific challengesData courtesy of Middleton, R. A Negative Ion Cookbook, University of Pennsylvania

    Al2O3 productcurrent (mA)AlO-20-40AlO2-4-6Al-1

  • Analysis of rare isotope abundancesConventional MSFormation of atomic and/or molecular ionsAcceleration through electrostatic potential (~kV)Separation of ions based on m/zMeasurement of ions in detectorAccelerator MSFormation of negative atomic and/or molecular ionsAcceleration through electrostatic potential (~kV)Acceleration to MeV energiesSeparation of ions based on m/zMeasurement of ions in detectorSteps of the analytical method

  • AMS block diagram

  • Center for Accelerator Mass Spectrometry (CAMS) at LLNLPhotographs courtesy of Lawrence Livermore National Laboratories(1)(2)(3)(4)(5)

  • Principles of AMS operationFormation of negative atomic and/or molecular ionsCs+ sputter sourceNegative ionsSource geometryIon SourceryAcceleration through electrostatic potential (~kV)Injector magnetLow resolution filterFast ion switching3. Acceleration to MeV energiesTandem accelerator10 MV terminalElectron stripper Molecular isobars

  • Principles of AMS operation(continued)4. Separation of ions based on m/zMagnetic analyzer (ME/q2)Electrostatic analyzer (E/q)Velocity analyzer (E/M)5. Measurement of ions in detectorGas ionization detectorIsobar-radionuclide pair with same EStopping power (Z)Electron-ion pairsE vs. DE

  • Figures of merit(26Al)19972007Sensitivity

  • Figures of merit (continued)AccuracySystematic errors (uncertainty in) Production rateLatitude/longitude scalingGeomagnetic/solar modulation (temporal)Assigned constants

    PrecisionExternal error (rep>3x)Internal error (Poisson)

    ThroughputBeO cathode ~ 10 minAl2O3 cathode ~ 30 minSignificance

  • Investigatory AimsObservations10Be analysis is typically limited by B26Al analysis is typically limited by ion beam currents

    Ultimate goalsImprove cosmogenic 10Be and 26Al analysis with better wet & analytical chemistryImprove precision for challenging samples

    Strategy to improve 10Be and 26Al AMS analysesDetermine effect of sample composition on AMS ion source behaviorCharacterize quartz extraction chemistry:Trace the fate of Be and AlTrack the movement of impuritiesIdentify problematic areas in the procedureMake blanks with better background ratios from berylProduce AMS cathodes which generate sufficient ion beam current

  • AMS ion beam currents (BeO-)Value (mA)Mean=13.1Median=13.4Minimum=1.6Maximum=25.1

  • Elemental analysis75th %

    25th %

  • Effect of elemental composition on BeO- ion beam currents Notationparameter estimatestandard errort ratioProb>t.

  • Concerning the extraction of BeO and Al2O3 from quartzOverviewEmpirical procedureTime consumingPre-treatmentAcid-digestionSeparation HazardousCleanliness (isotopic)

    Yield trace analysisClean and characterize quartzSupplement native compositionAliquot during a standard extractionElemental analysis by ICP-AESMatrix matched standardsDilute into linear dynamic range

  • Separation methods: Part I

  • Separation methods: Part II

  • Anion exchange chromatography

    Parameterscv: 20 mL Resin type: AG X18Elution rate: 1 drop/s(a) 8 M HCl(b) 1.2 M HCl

  • pH selective precipitationLow pH (3.8-4.1)

    High pH (~8.5)

  • Cation exchange chromatographyParameterscv: 10 mL resin: AG 50W-X8Rate: 1 drop/s(a) 0.5 M H2SO4(b) 1.2 M HCl(c) 3.0 M HCl(d) 6.0 M HCl

  • Key steps in quartz extractionDissolution by multi-acid digestion2H3O+ + [TiF6]2- TiO2 + 6 HFSelective distillation of HF relative to HClO4Anion exchange Good for Fe but not good for Ti separationPrecipitationsPoor reproducibilityQualitative analysisCation exchangeTriple acid elutionBoron removalDecent Ti separation

  • The matrix effect

    BackgroundConvention of mixing BeO in a metal matrix (e.g Ag or Nb) prior to AMS analysis to provide high ion beam currentsIon source design

    Experimental parametersAmount of metal mixing matrixTarget packing with respect to depthMatrix composition

    Long term goalUnderstand mechanism of matrix enhancement and predict possible matrix for 26Al

  • Matrix elemental propertiesHypothesisMatrix effectiveness is dependent upon Ion source presentationQuantitative compositionPhysicochemical characteristics of matrix

    Sheet1

    matrixelectronaffinity (eV)thermal conductivity(W/cm K)electricalresistivity(nW-cm)vaporizationenergyD Hvap (J/g)workfunction(eV)

    Ta0.320.581.314.174.10

    V0.530.311.978.984.30

    Mo0.751.380.536.154.20

    W0.821.730.534.014.55

    Nb0.890.541.527.364.30

    Ag1.304.290.162.394.70

    BeO2.102.601.E+223.40

    Sheet2

    Sheet3

    Sheet4

  • Experimental designSample preparationMeasuring: volumetric curetteMixing: BeO with metalRatio: serial dilution with mole fraction (cmatrix = 0.50 to 0.95)Packing: tamped into targetsInstrumental analysisStable BeO- beam: (10 min) instantaneous and integrated current measurementsUsual matrices: Ag, NbNovel matrices: Mo, Ta, V, W, Os1 mm2.5 mmMeyhoefer curette

  • Stability for Nb:BeO cathodes(post Ag)

    t=0-660 st=30-330 si (A)139906380rsd3.59%2.76%

  • BeO- beam currents

  • Effect of analyte: matrix ratio

  • Control of cathode presentation depthdepthCAMStargetExperimental designDepth is defined as space above target surfaceSample composition is an equimolar mixture of matrix and oxideDepth is measured with a micrometerMeasure integrated currents for a typical analysis period

  • Implications of depth effectImplicationsBeO in Nb has no depth effect BeO in Ag has a significant depth effectcurrents for samples in Ag matrix can be improved (with limited practical value)Nb and Ag exhibit a different responseIs the Nb enhancement related to the depth effect?

  • More BeO ion beam currents

  • Matrix enhancement, part 2

  • AMS counting efficiency for BeO

  • Correlation to matrix properties

  • Interpretation of matrix effectsObservationsNb is not a magic powder: all of the tested matrices provide some level of BeO signal enhancementsLow e.a. is important (and low k and f)The mixing ratio effect is important for optimizationThe presentation depth effect may be importantPractical recommendationsEffect of matrix mole ratioOptimal cNb between 0.5 and 0.65 (4:1 to 7:1 bm)Achieve high beam currents with less BeOEffect of presentation depthIn a Nb matrix, packing depth is not significant

  • Al2O3 ion beam currentscmatrix

  • More Al2O3 ion beam currents

  • Correlation to matrix properties

  • Elemental Al

  • Correlation to matrix propertiesR2=0.70R2=95

  • Future work for AlCorrelate cathode composition with current for AlSeparation of elemental AlBetter characterization of ionizationAnalysis of cathodes post-AMS analysis (physical and/or chemical)

  • AcknowledgmentsCommittee membersPetrucci groupBierman groupLLNL CAMS groupDOD-EPSCoR

  • Effect of analyte: matrix ratio

  • Titanium in the ion source

    Chart1

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    10% TiO2 impurity

    pure Al2O3

    time (s)

    ion beam current (mA)

    TiO2 impurity

    stability

    cmatrix0.500.500.500.500.500.500.500.500.500.50excluding

    check 1

    timecheck1check2check3check4check6check7check8check9check10check11meanmeanaverage

    10.00E+000.00E+000.00E+001.17E+000.00E+000.00E+001.47E+001.33E+000.00E+008.90E-014.86E-015.40E-01

    21.75E+001.62E+001.24E+001.17E+001.21E+001.47E+001.48E+001.33E+001.09E+009.00E-011.33E+001.28E+00

    31.70E+001.71E+001.31E+001.17E+001.23E+001.44E+001.48E+001.36E+001.17E+009.10E-011.35E+001.31E+00

    41.67E+001.73E+001.29E+001.17E+001.24E+001.44E+001.49E+001.39E+001.22E+009.00E-011.35E+001.32E+00

    51.73E+001.75E+001.28E+001.17E+001.26E+001.42E+001.48E+001.40E+001.25E+009.10E-011.36E+001.32E+00

    61.83E+001.70E+001.27E+001.16E+001.27E+001.44E+001.50E+001.40E+001.27E+009.10E-011.38E+001.32E+00

    71.66E+001.64E+001.26E+001.16E+001.28E+001.45E+001.51E+001.40E+001.28E+009.10E-011.35E+001.32E+00

    81.67E+001.70E+001.25E+001.16E+001.29E+001.43E+001.50E+001.41E+001.29E+009.00E-011.36E+001.33E+00

    91.69E+001.62E+001.25E+001.16E+001.30E+001.44E+001.51E+001.42E+001.14E+009.10E-011.34E+001.30E+00

    101.85E+001.77E+001.24E+001.15E+001.32E+001.40E+001.50E+001.44E+001.22E+009.00E-011.38E+001.33E+00

    111.73E+001.76E+001.23E+001.15E+001.33E+001.40E+001.51E+001.46E+001.32E+009.00E-011.38E+001.34E+00

    121.72E+001.76E+001.23E+001.14E+001.33E+001.42E+001.51E+001.46E+001.35E+008.90E-011.38E+001.34E+00

    131.83E+001.70E+001.22E+001.14E+001.34E+001.40E+001.50E+001.49E+001.35E+009.00E-011.39E+001.34E+00

    141.81E+001.83E+001.22E+001.14E+001.35E+001.39E+001.49E+001.50E+001.36E+008.90E-011.40E+001.35E+00

    151.85E+001.81E+001.22E+001.15E+001.35E+001.39E+001.49E+001.49E+001.38E+008.90E-011.40E+001.35E+00

    161.83E+001.80E+001.22E+001.15E+001.35E+001.40E+001.48E+001.50E+001.41E+009.00E-011.40E+001.36E+00

    171.80E+001.35E+001.21E+001.15E+001.36E+001.38E+001.48E+001.51E+001.42E+008.80E-011.35E+001.30E+00

    181.99E+001.83E+001.21E+001.15E+001.36E+001.38E+001.47E+001.50E+001.42E+008.80E-011.42E+001.36E+00

    191.85E+001.93E+001.21E+001.16E+001.36E+001.39E+001.47E+001.50E+001.41E+008.70E-011.41E+001.37E+00

    201.81E+001.76E+001.21E+001.16E+001.37E+001.40E+001.45E+001.51E+001.42E+008.80E-011.40E+001.35E+00

    211.83E+001.95E+001.21E+001.17E+001.38E+001.42E+001.45E+001.51E+001.41E+008.70E-011.42E+001.37E+00

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