Application of a beryllium specific resin at the Y-12 National Security Complex
YGG-01-0419
Darrin K. Mann, D.H. “Bo” Bowman, Thomas J. Oatts, and Vicki F. Belt
Analytical Chemistry OrganizationY-12 National Security Complex
P.O. Box 2009, MS 8189Oak 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
– 2nd 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
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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
3680
18511761
2444
3389
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FY 05 Monthly Be samples FY 03 Monthly Be samples FY 01 Monthly Be samples FY 00 Monthly Be samples
FY 99 Monthly Be samples FY 02 Monthly Be samples FY 04 Monthly Be samples
Breakdown of Be Smears at Y-12
Routine Large area wipes from special projects/areas (LAW5D) 5 day deadline
0.0%Rush Large area wipes from special
projects/areas (LAW24) 24 hr deadline11.6%
General housekeeping smears (HSKEEP) 3 day deadline3.7%
Movement of items from area to area (PMOVE) 24 hr deadline
0.7%
Non-routine smears (NRS) 5 day deadline16.1%
Be Site characterization smears (Be-Site) TBD deadlines
6.9%
Operations needed special attention (SPECIAL) 24 hr deadline
0.0%
Downposting of area smears, cleanup work (DNPOST) 24 hr deadline
0.2%
Respirator smears (RESP) 5 day deadline2.4%
Permanent Air filters (PA) 10 day deadline1.1%
QA Samples (daily)0.4%
Routine smears (RS) 10 day deadline11.6%
Non-routine next day smears (NRS-ND) 24 hr deadline34.2%
Others0.0%
Breathing Zone (BZ) 24 hr deadline11.2%
Basic Flow Chart for Analysisof 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
Be Lab personnel accept chain of custody of samples from ACO
Receiving
Set samples aside and notify IH technician of
problems with samples
Group samples by type
Be Lab checks COC and samples for accuracy and
completeness
Batch samples into QA files based upon priority
Prepare all necessary paperwork for sample
preparation and analysis for
Be Lab personnel obtain QA file and
label test tubes with
Fold and stuff samples into test tubes
Add H2SO4 and H2O2 to digest filter and BeO
Place samples into microwave oven and heat
for 5 minutes
Remove samples and cool
Add H2O2 to each tube and heat in microwave for additional 10 minutes
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
Analyze samples
Be conc < linear range?
Dilute sample within linear range and
rerun
Store Be result
Import data to database and create analysis
documentation
Place batched QA files and samples
into Be Buffer Area
Upload data into ESLIMS
Review and approve data in ESLIMS
File datafileNO
NO
Yes
Yes
End of operations for the day
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 HNO3 at 2 ml/min
Elute Be with 10 ml of 4M HNO3 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 Be Conc. ICP Total Be Original ICP Result ICP-MS Be Diff ICPMS Diff ICPMS Rec. ICPMS Adj ICP Rec** Removal of U(3130 line) (Column) ug (No Column) ug (No Column) ug Conc (ug) %(Percent) %(Percent) % (Percent) % (Percent)
Sample 1 0.00148 0.0296 -0.003 0.058 0.0284 48.97% 51.03% 69.72% 99.96%Sample 2 0.00198 0.0396 -0.00803 0.064 0.0244 38.13% 61.88% 84.53% 99.98%Sample 3 0.00824 0.165 0.01619 0.214 0.049 22.90% 77.10% 105.33% 99.98%Sample 4 0.00082 0.00164 -0.00234 0.025 0.02336 93.44% 6.56% 8.96% 100.00%Sample 5 0.00522 0.1044 -0.00222 0.138 0.0336 24.35% 75.65% 103.35% 99.99%Sample 6 0.00769 0.1538 0.01155 0.186 0.0322 17.31% 82.69% 112.96% 99.98%
** Adjusted recovery using ratio of 10 ppm Be std. recovery and 4 M HNO3 (7.32)
Original ColumnBe9(LR) 1.42 1.27Rb85(LR) 21.01 0.43Sr88(LR) 259.61 98.86Y89(LR) 56.22 0.59Zr90(LR) 1364.75 6.24Nb93(LR) 13.46 0.29Mo95(LR) 710.93 2.13Ru99(LR) 1.16 0.29Rh103(LR) 0.92 0.89Pd105(LR) 9.17 1.36Ag107(LR) 1037.85 13.62Cd114(LR) 227.05 244.87In115(LR) 32.44 0.51Sn118(LR) 2321.91 -0.82Sn119(LR) 2253.31 0.45Sb121(LR) 86.66 13.01Cs133(LR) 1.53 0.68Ba137(LR) 140.47 287.90La139(LR) 53.98 0.82Ce140(LR) 38.28 0.59
Original ColumnNd146(LR) 11.42 0.22Sm149(LR) 5.76 0.14Eu153(LR) 1.08 0.46Gd155(LR) 30.62 1.53Tb159(LR) 0.61 0.72Dy163(LR) 1.55 0.02Er166(LR) 39.37 0.36Tm169(LR) 0.35 0.61Yb172(LR) 0.87 0.44Lu175(LR) 0.40 0.72Hf178(LR) 22.99 0.71Ta181(LR) 1.68 0.29W182(LR) 263.55 1.64Os189(LR) 0.46 0.86Ir191(LR) 0.05 0.10Ir193(LR) 0.25 0.11Pt194(LR) 1.55 0.45Pt195(LR) 1.18 0.66Au197(LR) -0.37 -3.94Hg200(LR) 267.41 10.60
Original ColumnTl203(LR) 0.75 0.34Tl205(LR) 0.83 0.26Pb206(LR) 1412.97 1562.90Pb208(LR) 1413.20 1583.78Bi209(LR) 260.22 2.31Th232(LR) 3.52 0.39U238(LR) 81.63 0.58Al27(MR) 2654.82 1720.80Ti47(MR) 57.17 7.01V51(MR) 2.68 1.43Cr52(MR) 59.34 30.56Mn55(MR) 37.50 942.14Fe56(MR) 2614.15 -222.28Co59(MR) 7.58 1.52Ga69(MR) 0.23 -0.13Ga71(MR) 0.44 0.45K39(HR) 536.48 103.76Ge72(HR) 0.93 2.20As75(HR) 4.21 -0.43Se77(HR) 1.38 7.72
Multi-element analysis of Be resinBefore and After Column
Units of ppb
89.4% Recovery of Be using the Resin
Be recovery Conc. Before and After Be cartridgeICP Analysis Represents “Normal” Analysis
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Be9(LR) B
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Be (ICP)
Percent Recovery of Be vs. Initial ConcentrationICPMS and ICPOES Results
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Be9(LR) ICPMSBe (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%)
Recovery of IS Scandium2 mg/L standard added
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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.
Recovery of Sc IS using Post Organic Resin Cartridge
2 ug/L Sc added
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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??
