Application of a beryllium specific resin at the Y12 National Security Complex

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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

YGG-01-0419
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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

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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

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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

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Be program at Y-12 National Security Complex

• Controlled by US Dept. of Energys 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

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Overview of Y-12 Be Program

• Over 50K Samples Analyzed in 04.
• Average 53 /- 79 samples/day
• Average 2625 /- 876 samples/month
• Average turnaround time is 24 hours.

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Typical Workloads Associated with Be Program
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Breakdown of Be Smears at Y-12
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Basic Flow Chart for Analysisof Be Smear Program
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
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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 (cant handle 500
  samples/day)
• Remove/Concentrate Be

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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 lt 1 ml/min
• Sample can be re-run within a few hours.

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Vacuum System with Be cartridges and 10 ml
Reservoirs
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How clean are the Samples?
Samples after digestion
Samples after Be Column
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Comparison of Be data using Be Resin and ICPMS
Analysis

• Adjusted recovery using ratio of 10 ppm Be
  std. recovery and 4 M HNO3 (7.32)

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Multi-element analysis of Be resin Before and
After Column Units of ppb
89.4 Recovery of Be using the Resin
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Be recovery Conc. Before and After Be
cartridgeICP Analysis Represents Normal
Analysis
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Percent Recovery of Be vs. Initial
ConcentrationICPMS and ICPOES Results
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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)

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Recovery of IS Scandium2 mg/L standard added
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Why is IS Signal being Suppressed?

• Doesnt 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
• Doesnt 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.

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Recovery of Sc IS using Post Organic Resin
Cartridge2 ug/L Sc added
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Conclusion/Future Work

• Eichroms 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??