YGG-01-0419

Application of a beryllium specific resin at the Y-12 National Security Complex

Darrin K. Mann, D.H. “Bo” Bowman, Thomas J. Oatts, and Vicki F. Belt Analytical Chemistry Organization Y-12 National Security Complex P.O. Box 2009, MS 8189 Oak Ridge, TN 37831-8189

Outline

  Short review of Be and Problems associated with use Overview of Be program at Y-12 National Security Complex  Current Method – Problems with current method – – Evolution of new resin New method  Data from new method – – – Problems associated with new method Scandium Problem Post-Filter solution??

 Conclusions/Future Work

Be: Why we use it

   Discovered in 1798 – Not widely used in Industry until 1940s and 50s Lighter then Aluminum, Stiffer then Steel – 2 nd lightest metal – 6 times stiffer then steel High heat absorption – One pound absorbs as much heat as 6 pounds of copper  Be Metals, Alloys, Salts and Oxides are used for a wide variety of Industries – Structures in high-speed aircraft (space shuttle) – – – Satellite mirrors and space telescopes Golf clubs and bicycle frames Neutron moderators or reflectors in nuclear reactors

Problems Associated with Be

 Physical Problems – – Expensive Brittleness • Increases toxicity  Health Hazard – – Most Significant disadvantage for industrial use Causes Chronic Beryllium Disease (CBD) • No known cure, can only be treated – Produces scaring of lung tissue • Chronic, may take years to develop – Average latency period is 10-15 years • • 2-5 % of population Be sensitive Over 100 current and former DOE employees have CBD

Be program at Y-12 National Security Complex

 Controlled by US Dept. of Energy’s Chronic Beryllium Disease Prevention Program – – 10 CFR Part 850 Promulgated in 1999 to protect DOE workers from CBD – Requires Be surface and air monitoring to determine health risk – Rule greatly increased the need for Be analysis in the DOE complex – Current analytical methods include ICPOES and GFAA

Overview of Y-12 Be Program

7000 6000 5000 4000 3000 2000 1000 0 Oct Feb Jun FY04 FY05

 Over 50K Samples Analyzed in 04.

 Average 53

+/

- 79 samples/day  Average 2625

+/-

876 samples/month  Average turnaround time is 24 hours.

Typical Workloads Associated with Be Program

FY 2005 Beryllium Filters Analyzed 4000 3500 3000 2500 2000 1500 1000 500 0 7500 7000 6500 6000 5500 5000 4500

3680 3389 2444 1761 1851 FY 05 Monthly Be samples FY 99 Monthly Be samples FY 03 Monthly Be samples FY 02 Monthly Be samples

Month

FY 01 Monthly Be samples FY 04 Monthly Be samples FY 00 Monthly Be samples

Breakdown of Be Smears at Y-12

Be Site characterization smears (Be-Site) TBD deadlines 6.9% Routine smears (RS) 10 day deadline 11.6% Permanent Air filters (PA) 10 day deadline 1.1% Respirator smears (RESP) 5 day deadline 2.4% Others 0.0% QA Samples (daily) 0.4% Breathing Zone (BZ) 24 hr deadline 11.2% Dow nposting of area smears, cleanup w ork (DNPOST) 24 hr deadline 0.2% Non-routine next day smears (NRS-ND) 24 hr deadline 34.2% Non-routine smears (NRS) 5 day deadline 16.1% General housekeeping smears (HSKEEP) 3 day deadline 3.7% Routine Large area w ipes from special projects/areas (LAW5D) 5 day deadline 0.0% Rush Large area w ipes from special projects/areas (LAW24) 24 hr deadline 11.6% Operations needed special attention (SPECIAL) 24 hr deadline 0.0% Movement of items from area to area (PMOVE) 24 hr deadline 0.7%

Basic Flow Chart for Analysis of Be Smear Program Sample group picked up by ACO sampling personnel (1500 1600 hrs) ACO Receiving personnel receive samples into ESLIMS ACO Receiving personnel notify Be Lab of received samples Group samples by type Batch samples into QA files based upon priority Add H2SO4 and H2O2 to digest filter and BeO Place samples into microwave oven and heat for 5 minutes Add H2O2 to each tube and heat in microwave for additional 10 minutes Analyze samples Be conc < linear range?

NO Dilute sample within linear range and rerun Yes Store Be result Be Lab personnel accept chain of custody of samples from ACO Receiving Be Lab checks COC and samples for accuracy and completeness NO Set samples aside and notify IH technician of problems with samples Prepare all necessary paperwork for sample preparation and analysis for Place batched QA files and samples into Be Buffer Area Yes End of operations for the day Be Lab personnel obtain QA file and label test tubes with Fold and stuff samples into test tubes Remove samples and cool Add 10% HNO3 to nominal 10 mL volume Add 0.1 mL Sc internal standard Standardize ICP instruments daily Create autosampler file with sample and QC ID's Load autosampler with samples Import data to database and create analysis documentation Upload data into ESLIMS Review and approve data in ESLIMS File datafile ICP interferents monitored: Cr (Cr267.7), Fe (273.9), Mo (Mo 204.5), Nb (Nb 316.3), Th (Th 401.9), Ti (Ti 337.2), U (U 367.0), V (V 292.4), Zr (Zr 339.1

We are using both the 313.042 nm and 313.107 nm lines to quantitate. Interferences checked on each

The Problem?

 

The Internal Standard (IS) works great correcting interferences to a point

: – High Concentrations of Interfering Elements • Some elements are very spectral rich – Uranium » Shift depends on enrichment – Some elements overlap spectrally • Vanadium, Cesium and Zirconium are examples • Dilution not useful for these elements

Possible Solutions

– Dilution • May lose Be signal • Increase in MDL – Run samples by ICPMS • Expensive (relative to an OES) • Not as rugged as OES (can’t handle 500 samples/day) – Remove/Concentrate Be

Method using Eichrom Be resin

        Elegantly simplistic Usually use 5 ml of sample left over from ICPOES analysis Adjust sample pH to between 1-2 with 4 M Sodium Acetate 2% Crystal Violet used as indicator (3-4 drops) Load sample onto Be cartridge (usually 10 mL) and pass through at 2 ml/min Rinse cartridge with 10 ml of 0.2 M HNO 3 at 2 ml/min Elute Be with 10 ml of 4M HNO 3 at < 1 ml/min Sample can be re-run within a few hours.

Vacuum System with Be cartridges and 10 ml Reservoirs

How clean are the Samples?

Samples after digestion Samples after Be Column

Comparison of Be data using Be Resin and ICPMS Analysis

Sample Type Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Be Conc. ICP (3130 line) 0.00148

0.00198

0.00824

0.00082

0.00522

0.00769

Total Be (Column) ug 0.0296

0.0396

0.165

0.00164

0.1044

0.1538

Original ICP Result (No Column) ug -0.003

-0.00803

0.01619

-0.00234

-0.00222

0.01155

ICP-MS Be Diff ICPMS (No Column) ug Conc (ug) 0.058

0.064

0.214

0.025

0.138

0.186

0.0284

0.0244

0.049

0.02336

0.0336

0.0322

Diff ICPMS %(Percent) 48.97% 38.13% 22.90% 93.44% 24.35% 17.31%

Rec. ICPMS Adj ICP Rec** %(Percent) % (Percent) 51.03% 61.88% 77.10% 6.56% 75.65% 82.69% 69.72% 84.53% 105.33% 8.96% 103.35% 112.96%

Removal of U % (Percent) 99.96% 99.98% 99.98% 100.00% 99.99% 99.98% ** Adjusted recovery using ratio of 10 ppm Be std. recovery and 4 M HNO3 (7.32)

Be9(LR) Rb85(LR) Sr88(LR) Y89(LR) Zr90(LR) Nb93(LR) Mo95(LR) Ru99(LR) Rh103(LR) Pd105(LR) Ag107(LR) Cd114(LR) In115(LR) Sn118(LR) Sn119(LR) Sb121(LR) Cs133(LR) Ba137(LR) La139(LR) Ce140(LR) Original 1.42

21.01

259.61

56.22

1364.75

13.46

710.93

1.16

0.92

9.17

1037.85

227.05

32.44

2321.91

2253.31

86.66

1.53

140.47

53.98

38.28

Multi-element analysis of Be resin Before and After Column Units of ppb

Column 1.27

0.43

98.86

0.59

6.24

0.29

2.13

0.29

0.89

1.36

13.62

244.87

0.51

-0.82

0.45

13.01

0.68

287.90

0.82

0.59

Nd146(LR) Sm149(LR) Eu153(LR) Gd155(LR) Tb159(LR) Dy163(LR) Er166(LR) Tm169(LR) Yb172(LR) Lu175(LR) Hf178(LR) Ta181(LR) W182(LR) Os189(LR) Ir191(LR) Ir193(LR) Pt194(LR) Pt195(LR) Au197(LR) Hg200(LR) Original 11.42

5.76

1.08

30.62

0.61

1.55

39.37

0.35

0.87

0.40

22.99

1.68

263.55

0.46

0.05

0.25

1.55

1.18

-0.37

267.41

Column 0.22

0.14

0.46

1.53

0.72

0.02

0.36

0.61

0.44

0.72

0.71

0.29

1.64

0.86

0.10

0.11

0.45

0.66

-3.94

10.60

Tl203(LR) Tl205(LR) Pb206(LR) Pb208(LR) Bi209(LR) Th232(LR) U238(LR) Al27(MR) Ti47(MR) V51(MR) Cr52(MR) Mn55(MR) Fe56(MR) Co59(MR) Ga69(MR) Ga71(MR) K39(HR) Ge72(HR) As75(HR) Se77(HR) Original 0.75

0.83

1412.97

1413.20

260.22

3.52

81.63

2654.82

57.17

2.68

59.34

37.50

2614.15

7.58

0.23

0.44

536.48

0.93

4.21

1.38

Column 0.34

0.26

1562.90

1583.78

2.31

0.39

0.58

1720.80

7.01

1.43

30.56

942.14

-222.28

1.52

-0.13

0.45

103.76

2.20

-0.43

7.72

89.4% Recovery of Be using the Resin

Be recovery Conc. Before and After Be cartridge ICP Analysis Represents “Normal” Analysis 15 10 5 0 40 35 30 25 20 Be9(LR) B Be9(LR) A Be (ICP)

Percent Recovery of Be vs. Initial Concentration ICPMS and ICPOES Results 100 90 80 70 60 50 40 30 20 10 0 Be9(LR) ICPMS Be (ICP)

So Where is the Be Going?

    ICPMS data appears acceptable, so Be is there.

Recovery of Be in ICV and CCV is fine Colored samples may cause pH problem – Yellow Samples are a particular problem Answer may lie in looking at IS Scandium – – Signal is being suppressed RSD is very poor (5-10%)

120 100 80 60 40 20 0

Recovery of IS Scandium

2 mg/L standard added Be Samples

Why is IS Signal being Suppressed?

      Doesn’t seem to correct in same ratio as Be Very large suppression at times, up to 75% of signal.

Only source of suppression can come from column Doesn’t seem to be acid concentration based An organic from the resin may be complexing with Sc and pulling it out of solution Need to remove organic after it passes through initial column.

120 100 80 60 40 20 0 Recovery of Sc IS using Post Organic Resin Cartridge 2 ug/L Sc added Be Samples

Conclusion/Future Work

    Eichrom’s Be resin seems to be a fast and reliable method to remove spectral interferences from samples when analyzing for Beryllium Need to better understand the effects of residual organics on the recovery of Internal Standards such as Sc. – A post organic filter seems to solve the problem Filter could be used to Lower MDL – ACGIH has recently issued a Notice of Intended Change (NIC) to lower the Threshold Limit Value (TLV) for airborne beryllium to 0.02 micrograms per cubic meter, or one-tenth of the current DOE action level. – Concentrate sample onto column, elate with smaller volume Need to quicken the process – Reduce number of sample • Customer knowledge??