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

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

Typical Workloads Associated with Be Program

Breakdown of Be Smears at Y-12

Basic Flow Chart for Analysis of 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 We are using both the nm and 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 ** Adjusted recovery using ratio of 10 ppm Be std. recovery and 4 M HNO3 (7.32) ** Adjusted using ratio of 10 ppm Be std. recovery and 4 M HNO3 (7.32)

Multi-element analysis of Be resin Before and After Column Units of ppb 89.4% Recovery of Be using the Resin

Be recovery Conc. Before and After Be cartridge ICP Analysis Represents “Normal” Analysis

Percent Recovery of Be vs. Initial Concentration ICPMS and ICPOES Results

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 Scandium 2 mg/L standard added

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

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??