High Sensitivity EPMA: Past, Present and Future

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High Sensitivity EPMA: Past, Present and Future. John Donovan CAMCOR University of Oregon. (541) 346-4632 donovan@uoregon.edu camcor.uoregon.edu. The Past: EPMA/SEM (from Goldstein, et. al. 1988) :. Comparison of EDS to WDS, Equal Beam Current, pure Si and Fe, 10 -11 A (0.01 nA), 25 keV. - PowerPoint PPT Presentation

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  • High Sensitivity EPMA:Past, Present and FutureJohn DonovanCAMCORUniversity of Oregon (541) 346-4632donovan@uoregon.educamcor.uoregon.edu

  • The Past: EPMA/SEM (from Goldstein, et. al. 1988):Comparison of EDS to WDS, Equal Beam Current, pure Si and Fe, 10-11 A (0.01 nA), 25 keVComparison of EDS to WDS, Optimized Conditions, 15 keV, 180 seconds counting time:EDS : 2 x 10-9 A (2 nA) to give 2K cps spectrum to avoid sum peaksWDS : 3 x 10 -8 A (30 nA) to give 13K cps on Si spectrometer (< 1 % dt)

    60 sec

    P (cps/10-8 A)

    P/B

    CDL(ppm)

    Si K

    EDS

    5400

    97

    580

    WDS

    40

    1513

    1,710

    Fe K

    EDS

    3000

    57

    1,000

    WDS

    12

    614

    4,900

    Peak cps

    P/B

    CDL(ppm)

    EDS

    Na K

    32.2

    2.8

    1,950

    Mg K

    111.6

    6.4

    1,020

    Al K

    103.9

    5.7

    690

    Si K

    623.5

    22.8

    720

    Ca K

    169.5

    8.5

    850

    WDS

    Na K

    549

    83

    210

    Mg K

    2183

    135

    120

    Al K

    2063

    128

    80

    Si K

    13390

    362

    90

    Ca K

    2415

    295

    90

  • More recent data for EPMA/SEM:

  • The detection limit cannot be reduced indefinitely by accumulating more counts, however, because systematic errors in the background correction eventually become significant.- Stephen Reed*Accuracy (not precision) in characterizing the continuum becomes the limiting factor...

  • Other Artifacts: Holes in the Continuum

  • Reality Check: Accuracy at the 400 PPM Level?Note: Blank level (Clevel) can be non-zero

  • PETLPET5 SpectrometersStill We Need to Improve Sensitivity as well..

  • (normal PET crystal)

  • WDS Analysis of Hg (polymer door frames from suspected Mexican facility)990 PPM of Hg easily detected, with 48 PPM sensitivityChecked with EDS-count 200 sec- several nA -no Hg found

    Checked with WDS- count 20 sec- 50 nA- Hg found

    Why?

  • Polymer door frames (2000s) from suspected Mexican facility, Check with EDS for 100 sec, 20 keV, 50 nA... nothing...100 sec counting time

  • Still nothing...500 sec counting time

  • Hg peaks barely visible1000 sec counting time, with Be window inserted (to remove C and O)

  • So what exactly can WDS do on a typical quantitative analysis?

  • 15 keV, 200nA, 300 sec on-peak, 300 second off peak, Zr La, LPET + PET (aggregate intensities)

    Zr % error

    2.45414112.224.20711-16.138

    3.77006-1423.38401-23.829

    3.0663174.5523.25998-87.597

    5.03789-31.4157.05755-39.839

    5.0751654.696417.0645-21.939

    2.323565.19296-28.489

    3.954233.87978-17.802

    2.6410823.2263.53795-74.642

    3.00645823.9834.91528-17.272

    2.14855-93.6273.32091-26.395

    2.32732-28.992-111.49

    -115.02-57.084

    12.0121-69.023

    4.194346.52788-21.727

    2.0894-38.1123.84449-38.863

    3.60473204.438.60921-50.613

    1.66735-17.12111.8739-51.375

    2.03245-29.895.95443-50.168

    1.82315-96.4075.12635-29.754

    2.625663.55027-13.403

    2.815515.08564-27.961

    1.79739125.948-19.565

    2.03965-79.784-18.017

    -59.8945.70163-21.662

    192.6430.9924-19.376

    1.5391810.173-22.467

    1.32678.07822-45.869

    1.39201-25.0222.38321-60.949

    1.3246-39.0281.68711-46.809

    1.6426546.62172.40297-45.088

    1.12111-90.1445.89964

    -16.624

    3.5550717.9056

    3.812145.31864

    3.235444.39757

    4.352266.26956

    4.44684240.926

    5.527259.3965

    2.2927527.1871

    3.9968512.9092

    10.107

    1.78624

    2.1872548.1402

    1.7400112.7279

    1.3633811.147

    1.5500412.5728

    1.61243

    609.187

    16.092313.1198

    6.8294717.935

    5.7596813.9328

    6.2032383.933

    7.94528

    10.3349

    5.7923712.3808

    48.028613.4108

    -20.16212.7107

    196.72617.8705

    8.610797.29383

    6.894215.17598

    10.05477.48527

    16.248619.9283

    10.069415.2156

    17.353612.0635

    4.94547

    3.93713

    3.828897.97134

    3.107878.97952

    3.882148.89792

    11.45828.99306

    4.17859

    44.0921

    18.87732.43312

    3.480521.45028

    2.77358

    2.01642

    2.242685.53781

    2.157525.49977

    2.281085.26589

    2.257495.16125

    2.341754.15169

    2.307914.61249

    -87.219

    2.7362

    2.240998.23064

    7.29648

    6.38902

    10.26865.48005

    6.03195.95104

    7.486148.49436

    9.2333

    7.17946

    9.306760.710282

    9.971420.664616

    1.0099

    1.53718

    2.05088.02876

    2.3730510.8899

    1.741189.0448

    2.1071

    7.13035

    29.61683.97308

    -28.8833.5602

    2.881054.51049

    2.643815.50171

    4.286254.70686

    2.34673

    2.12831

    4.8406

    3.66308

    1.135684.85733

    1.189163.95119

    0.7723084.21458

    1.022064.17452

    1.16232

    1.15759

    1.087561.48966

    1.366591.45932

    1.362331.48695

    1.425881.52413

    2.162881.5412

    1.67205

    20.3926

    6.64225-87.895

    5.57003-15.555

    3.45413-20.025

    2.8039981.8312

    2.93779-139.69

    3.64922

    4.63047

    4.99909153.328

    4.9296351.3367

    12.5123

    26.8773

    1.655897.12299

    1.50912

    1.88244

    1.7376520.9577

    1.8194610.8593

    36.403

    16.4706

    1.5511712.83

    1.50807-79.994

    1.3986

    1.40667

    1.513955.40645

    1.463422.40225

    1.33033.72893

    1.361416.68564

    1.655795.34898

    1.702733.64481

    1.366124.25621

    1.327163.9483

    2.0549

    1.29361

    2.73913

    4.18999

    0.9232114.04195

    0.9348142.91542

    0.9288384.17208

    0.906714.15191

    1.75775

    1.1231

    0.9070076.58824

    0.9886847.11938

    0.9061016.4707

    0.948366

    0.92073

    1.009732.48168

    1.98595

    2.19771

    0.8827422.41917

    0.8797132.02972

    0.897385

    0.894113

    0.8615141.87359

    0.9107222.19539

    4.147772.33685

    6.193941.75086

    0.818041.63717

    2.89646

    0.859055

    1.224431.62358

    0.9586081.6556

    2.381881.59087

    1.76994

    1.69116

    7.28976

    -93.526

    11.10381.26819

    165.9221.20326

    39.4281.36976

    -132.961.33102

    -28.5861.56803

    639.5831.42195

    -30.4551.25353

    44.97641.23419

    -4.70291.39057

    -34.257

    2.17844

    4.906931.55253

    9.859721.80053

    7.802511.77139

    8.341971.48728

    8.162161.40694

    9.21971.47558

    10.66871.60609

    -523.941.64389

    16.5914

    20.1878

    20.369318.6775

    6.534519.45581

    19.34246.13594

    17.723712.3209

    1.875291.97967

    1.923381.70972

    1.912881.92603

    2.189122.23902

    2.308182.16064

    2.17325

    1.25925

    2.350971.11324

    1.83551.87204

    2.47541.46288

    1.948022.48796

    2.022420.790922

    2.382521.26226

    2.37619

    2.14849

    1.965021.28198

    1.419751.09289

    5.656451.08679

    1.780311.16339

    2.365020.990416

    3.016931.15401

    1.548351.50585

    1.625161.61489

    1.591511.53818

    1.874571.42829

    1.59341.58403

    1.557711.63399

    1.57279

    1.53297

    1.652891.53301

    1.6054

    1.45084

    0.754056

    0.99792

    1.33418

    1.22401

    1.27073

    1.65137

    2.72972

    1.59388

    1.74326

    2.68501

    2.55225

    2.39605

    3.67412

    2.47548

    2.23822

    7.95105

    6.77329

    8.51263

    9.27195

    8.21363

    14.7215

    0.663958

    1.05195

    0.806815

    1.14258

    0.895579

    1.19125

    2.33224

    1.76765

    2.22796

    1.86624

    4.00536

    8.33217

    8/20/2008 unk

    8-20-08 synth

    10/1/2008 unk

    10-1-08 synth

    wt% Zr in rutile

    Zr % error

    Mercer- Butte Zr % error

    8-20-08

    C:\Documents and Settings\Celeste\My Documents\School\Lab\EPMA\probeDATA\new probe_SX100\2008-Aug\Zr in rutile 8-20-08.dat

    C:\Documents and Settings\Celeste\My Documents\School\Lab\EPMA\probeDATA\new probe_SX100\2008-Aug\Zr in rutile 8-20-08.mdb

    Celeste Mercer

    Butte quartz

    Zr in rutile for geothermometeralso Nb, Ta, Fe

    Nominal Beam: 30

    Un 2 TiO2 synthetic

    LINEZr WT%Zr WT%Fe WT%Ta WT%Nb WT%Ti WT%O WT%Zr CDL99Zr CDL99Fe CDL99Ta CDL99Nb CDL99Zr %ERRZr %ERRFe %ERRTa %ERRNb %ERR

    1300.0004280-0.00084-0.000550.00218759.948840.050.00101900.0020390.0031020.004995112.220-114.49-264.16108.044

    131-0.000340-0.00013-0.00087-0.0007759.951640.05050.00101900.002030.0030990.005053-1420-745.32-167.4-308.59

    1320.0006470-0.000340.0003140.00097759.948640.04980.00102100.002030.0030970.00500874.5520-284.97464.509242.13

    133-0.0015300.0008310.000751-0.0009759.950840.05010.00102500.0020270.0030910.005002-31.4150115.079194.223-241.49

    1340.00087600.0004710.000356-0.0012659.949740.04990.00101500.0020280.0031040.00501954.69640202.941411.302-187.74

    Un 11 TiO2 synthetic as unknown

    2170.0020480-0.00075-0.00005-0.0003859.949240.04990.00100400.0020530.0030870.00502723.2260-129.33-2937-628.64

    2180.0000580-0.000190.000234-0.0003659.950240.05010.00101600.002060.0030970.005047823.9830-517.98624.613-652.13

    219-0.000510-0.00078-0.00125-0.0020259.953640.0510.00101900.0020690.0031020.005075-93.6270-125.46-116.99-117.84

    220-0.0016500.000102-0.001440.00292759.949740.05030.00102200.002060.0031050.004983-28.9920952.252-101.6180.6338

    221-0.000420-0.0012-0.001010.00187359.950340.05040.00101700.0020670.0031070.004949-115.020-81.306-144.24124.982

    Un 17 TiO2 synthetic as unknown2

    266-0.0012700.000164-0.00011-0.0040959.954440.05090.00102800.002070.0031030.005125-38.1120595.502-1324.3-58.706

    2670.00001500.0015820.000695-0.0002559.948440.04950.00102100.0020650.0031170.0049753204.43061.6752211.398-922.07

    268-0.0028200.0014-0.002420.00045659.952540.05090.00103100.0020690.0031150.005029-17.121069.8132-60.645520.755

    269-0.00160-0.001580.00021-0.0022959.954340.0510.00102100.0020740.0031070.005069-29.890-61.776699.134-104.03

    270-0.00050-0.001140.0003380.00253659.948840.050.00101800.0020720.0031080.004996-96.4070-85.208433.98193.2363

    Un 24 TiO2 synth as unk 3

    3470.000390-0.001490.0020980.00211959.947440.04950.00104200.0021780.0031640.005231125.9480-68.99471.2286116.748

    348-0.0006200.0004740.001612-0.0001859.94940.04970.00104500.002170.0031670.005224-79.7840215.93392.7267-1331.2

    349-0.000820-0.002880.0001440.00119459.951740.05070.00104700.0021810.0031640.005193-59.8940-35.5231036.58205.342

    3500.0002550-0.00003-0.0002-0.0029359.952440.05050.00104300.0021780.0031710.005257192.6430-3047.9-736.38-84.062

    Un 30 TiO2 synth as unk 4

    448-0.002010-0.00058-0.00071-0.0008159.953240.05090.0010700.0022370.0033350.005599-25.0220-181.26-220.9-326.3

    449-0.0012900.000035-0.00215-0.0002959.952840.05090.00106900.0022370.0033490.005532-39.02802974.8-73.254-896.96

    4500.00106200.000117-0.000970.0001659.949640.05010.00104700.0022370.0033310.00553446.62170899.704-161.471634.31

    451-0.000550-0.001210.0021970.00167359.948340.04960.00105500.0022350.003330.005535-90.1440-87.23671.5862156.35

    452-0.002990-0.001410.001804-0.0047959.956240.05120.00106400.0022380.0033330.005602-16.6240-74.61687.2369-54.709

    Un 3 11135-2470_blockyrutile3

    1350.02091101.220380.0115980.30360958.722939.72060.00103900.0021570.0032870.0051572.4541400.17216613.48371.12123

    1360.01314600.6268250.0024150.06720859.396439.8940.00101900.002080.0031610.0050823.7700600.26196161.84173.93477

    1370.01647700.783332-0.003290.04409359.29739.86230.00103200.0021050.0032080.0050883.0663100.226768-45.8285.81588

    1380.00979900.448330.0015040.00517359.590739.94450.00102300.0020590.0031330.0049685.0378900.32974798.345745.6711

    1390.00976300.5413260.0005020.00307259.521539.92380.00102700.0020670.0031430.0050345.0751600.289225295.26877.6332

    1400.02206500.9644740.0021310.04451559.148539.81830.00103500.0021240.0032410.005072.3235600.19865171.83525.74526

    1410.01261800.406671-0.000860.00199459.62539.95460.00102800.0020750.0031520.0050333.9542300.355112-172.9119.37

    1420.01921100.780080.0027230.04281359.29439.86110.0010300.0021140.0032130.0051412.6410800.22780555.75566.03377

    1430.01669900.5030490.0089120.13126359.429339.91070.00102500.0020840.0031880.0050053.0064500.305316.99242.15627

    1440.02396401.03216-0.008230.02338559.120439.80830.00103500.0021580.0033130.005122.1485500.191133-18.85710.7006

    1450.02211701.30594-0.013750.00612658.929639.74990.00103900.0021710.003340.0050882.3273200.165224-11.32239.543

    Un 4 11135-2470_blockyrutile2

    1460.01194801.13823-0.00387-0.0014759.066539.78870.00103400.0021190.0032130.0051624.1943400.179201-38.996-164.59

    1470.02481101.51036-0.017840.0053558.773439.70390.00104100.0021810.0033450.0051692.089400.151606-8.715245.9206

    1480.01379900.6837280.0025120.0319859.382239.88580.00102200.0020760.0031280.0050483.604700.24711258.83317.82244

    1490.03141401.29204-0.007090.10012658.847339.73620.00103700.0021510.0032680.0051361.6673500.166125-21.6122.77598

    1500.02527500.807838-0.000670.09439659.22639.84720.0010300.0021110.0031920.0050292.0324500.222278-222.922.8765

    1510.02874700.9644420.0016560.1881959.020239.79670.00104400.0021330.0032360.0050431.8231500.19922692.26011.60858

    1520.01927800.7313420.0032940.1596559.230939.85550.00102700.0021010.0031850.0050482.6256600.23741945.69821.84122

    1530.01789800.6177140.0049550.1184759.353839.88720.00102600.0020830.0031450.0049992.8155100.26498830.05032.35138

    1540.02935801.274680.0064350.27985258.698339.71130.00105100.0021750.003310.0050631.7973900.16808724.37271.18059

    1550.02523100.7572720.0007220.14331359.22239.85140.00103100.0021140.0031910.0050252.0396500.232629208.6242.00896

    Un 5 11135-2470_rutile_zircon-prism-area

    1560.03377100.5871070.0092770.49380259.039539.83650.00102200.0020750.0031290.0050671.5391800.27398816.02970.781619

    1570.03949500.6507360.0103270.57224758.917739.80940.00101800.0020810.0031490.0051071.326700.25577314.50280.708802

    1580.03737100.7617670.0062330.55537158.851339.7880.00101500.0020910.0031580.0050481.3920100.23033124.01240.719254

    1590.03967900.718520.0167110.61648858.822739.78590.00102100.0020890.0031340.0050921.324600.2396068.97210.673261

    1600.03153200.5845070.0074740.5234259.019239.83380.00102400.0020750.0031250.0050661.6426500.27480719.84280.750595

    1610.04736700.6808710.0158260.70257158.772339.7810.00101500.0020930.0031330.0051271.1211100.2485169.46210.618807

    Un 6 11135-2470_blockyrutile

    1620.01382900.4861180.0023480.00700659.556139.93460.00100900.0020630.003110.0050273.5550700.31152362.559434.2127

    1630.01312601.01794-0.001860.05253259.110539.80770.0010300.0021180.0032120.0050373.8121400.19198-81.2364.89528

    1640.01558401.110020.0248240.6990258.463639.6870.00103200.0021280.0031920.0051233.2354400.1820776.188910.620569

    1650.01145500.817020.0007030.05623859.261839.85280.0010300.0021050.0031880.0050584.3522600.220868213.9624.61319

    1660.01114500.6237420.002470.02944459.432839.90040.00102400.0020980.0031530.0050094.4468400.26401460.30838.40325

    1670.00884300.537421-0.000910.01958959.512239.92290.00101500.0020820.0031410.0050465.5272500.291612-162.2712.527

    1680.02249401.65394-0.001020.16208958.517839.64460.00104100.0022120.0034150.0050452.2927500.144276-157.891.81761

    1690.01239100.4439060.0029870.00475359.591339.94470.0010200.0020780.0031160.0050233.9968500.33394649.307550.2083

    Un 7 11135-2470_blockyrutile4

    1700.02879700.7854760.0312880.75445258.650939.74910.00102200.0020990.0031550.0051091.7862400.2266424.882490.590611

    1710.02325400.6685360.0286080.78301558.72339.77360.00102300.0020790.0031350.0050792.1872500.2511475.29460.575037

    1720.02941400.5505580.0095970.39976659.151639.8590.00101500.0020840.0031290.0050781.7400100.28698315.49750.907132

    1730.0386700.7769320.0239010.58127358.803439.77580.00102700.0021090.0031630.005121.3633800.2286246.367950.701927

    1740.03369200.7475550.0125720.50725458.901939.79710.00102800.00210.0031610.0051171.5500400.23416311.98030.770009

    1750.03223800.8574750.0261650.81635358.543239.72450.00102600.0020980.0031240.0051061.6124300.2141495.758710.561401

    Un 8 11185-3771_rutile

    1760.00275500.4461060.1387020.10617459.411139.89520.00093300.0019270.0036530.0044116.092300.3226441.349432.36396

    1770.00700.4935120.0158860.1663559.409439.90790.00099700.0020820.0031850.0050046.8294700.3101229.579611.76904

    1780.008400.4819830.0217610.2004759.383539.90380.00100500.0020780.0031520.0050615.7596800.3151536.957421.53136

    1790.007700.4785770.0085010.14855359.44139.91570.00099400.0020830.0032090.0050486.2032300.31729817.92331.95498

    1800.00596400.4807260.0078890.15447659.436139.91490.0009900.0020790.003230.0050587.9452800.31609619.43031.89499

    1810.00457400.4811780.0078980.17671359.417839.91180.00099100.0020830.0032350.00499810.334900.31611619.4351.68325

    1820.00852900.4872280.0069880.17921559.408439.90960.00102700.0020630.0030870.0049435.7923700.31230120.961.65328

    1830.00089900.376770.1123630.10800459.483739.91820.00091300.00190.0035820.00437348.028600.3618071.613542.31726

    184-0.0021100.3454520.1354440.0988459.501339.92110.00090600.0018790.0037170.004271-20.16200.3832091....

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