The Determination of Be in an Enriched Uranium Matrix

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, or why we use it

Problems associated with handling of Be– Physical

– Health

Be program at Y-12 national Security Complex

Current Method– Problems with current method

– New method

Data from new method

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– Nuclear Weapons components

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

0

1000

2000

3000

4000

5000

6000

Oct Feb June

FY03FY04

Almost 40K samples analyzed in 03.

Averaging 50% more samples in 04

Some months topping 5000 SAMPLES

Average turnaround time is 24 hours.

Typical Workloads Associated with Be Program

FY 2004 Beryllium Filters Analyzed

5070

3585

4968

3510

4244

2725

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

6500

7000

7500

Oct

No

v

Dec

Jan

Feb

Mar

Ap

r

May

Jun

Jul

Au

g

Sep

Month

# o

f sa

mp

les

FY 04 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

Breakdown of Be Smears at Y-12

Breathing Zone (BZ) 24 hr deadline12.5%

Routine Large area wipes from special projects/areas (LAW5D) 5

day deadline15.9%

Rush Large area wipes from special projects/areas (LAW24) 24

hr deadline7.0%

General housekeeping smears (HSKEEP) 3 day deadline

6.0%

Movement of items from area to area (PMOVE) 24 hr deadline

2.4%

Non-routine smears (NRS) 5 day deadline

23.9%

Be Site characterization smears (Be-Site) TBD deadlines

1.2%

Operations needed special attention (SPECIAL) 24 hr deadline

0.1%

Downposting of area smears, cleanup work (DNPOST) 24 hr

deadline0.5%

Respirator smears (RESP) 5 day deadline

1.2%

Permanent Air filters (PA) 10 day deadline

1.3%

QA Samples (daily)0.3%

Routine smears (RS) 10 day deadline

11.6%

Non-routine next day smears (NRS-ND) 24 hr deadline

16.2%

Others0.0%

Current Method for Be Analysis

Microwave Digest samples– H2SO4 and H2O2

– Diluted to volume with HNO3

– Final solution is 10% HNO3/6% H2SO4

Samples counted using ICPOES– Use Scandium as Internal Standard

– Look at 313.107 and 313.034 lines

Interfering lines corrected using Inter Element Correction or IEC– Corrects for most spectral interferences, such as Uranium

The Problem? The IEC works great correcting for uranium, to a point:

– High Concentrations of Natural Uranium• Uranium very spectral rich• Require Dilution for Be Quantitation

– Enriched Uranium causes spectral shift• Dependent on Enrichment

Possible Solutions– Dilution

• May lose Be signal• Increase in MDL

– Determine Enrichment for all Samples• Expensive• Time consuming

– Remove/Concentrate Be– Remove Uranium

Method using Eichrom UTEVA

Elegantly simplistic

Prepare column with 10% HNO3/6% H2SO4

Load sample onto column (usually 10 mL)

Collect sample– No rinsing, we do not want to dilute solution

Internal Scandium Standard adjusts for any loss

Sample re-run within the hour

Spiked Sample Recovery0.0005 mg/L Be and 500 mg/L U

Average RSD 7.4%

0

20

40

60

80

100

120

140

160

1 2 3 4 5 6 7 Avg

Samples

Be

reco

vere

d (%

)

Be3130a Be3130b

Decontamination of U0.0005 mg/L Be and 500 mg/L U

>99% Uranium Removal

80

85

90

95

100

105

1 2 3 4 5 6 7

Samples

U R

emov

ed (

% o

f T

otal

)

U367a U367b U367c

So Where is the “REAL” Data

Real Samples yet to be processed– Sample Backlog

– Procedure Approval

Sample will be split

Analysis to be done by ICP-MS and Eichrom Extraction Method

Expect data to statistically be the same

Conclusion/Future Work

UTEVA seems to be fast and reliable method to remove the enriched uranium interference from samples when analyzing for Be

Can also be used to remove high levels of natural uranium from samples

Need to quicken the process– Vacuum Box– Prepacked column– Reduce number of sample

• Customer knowledge??