The Search for a Portable Method for Rapid Airborne Beryllium

The Search for a Portable Method
for Rapid Airborne Beryllium
Measurement:
The Current State of the Science
Kathryn Creek, MS, CIH
AIHCE, May 11, 2004
Overview
™Background
™Methods
™Wish
list (in search of the perfect
method)
™Future direction
Background
Beryllium exposure causes Chronic Beryllium
Disease, a chronic debilitating lung disease
™ The DOE Chronic Beryllium Disease Prevention
Program Rule, 10 CFR Part 850, requires
beryllium surface and air monitoring to determine
health risk and the effectiveness of mechanisms
used to minimize or eliminate that risk.
™ Current analytical techniques involve substantial
delays and costs.
™
Current gold standard-ICP
LAGGING MEASURE
Symposium hosted by Network of
Senior Scientists and Engineers (NSSE)
and Los Alamos National Laboratory
™ Beryllium Advanced Technology
Assessment Team (BeATAT) formed as
a result of information learned at
symposium
™
Be ATAT Members
Kathy Creek, Chair, LANL
™ Mike Brisson, WSRS
™ Mark Hoover, NIOSH
™ Dave Weitzman, DOE EH
™ Bret Clausen, RFETS
™ Ken Meyer, PX
™ Bill Frede, KC
™ Ed Kahal, WSRS
™
Sam Robinson, Y-12
™ Larry Jones, DOE Y-12
™ George Fulton, LLNL
™ John Lemming, PX
™ Greg Day, NIOSH
™ Dave Hamel, OSHA
™ John Bishop, NERL,Navy
™ Ron Staubly, NETL
™ Murray Moore, LANL
™
Objectives of beryllium real-time
monitoring
™ Improved
worker and public protection
Œ Basis for engineering/administrative controls/PPE
Œ Timely feedback to workers
™ Improved
productivity
Œ Movement of Materials
Œ Personnel efficiency
Œ Reduced analytical laboratory costs
™ Characterize
contamination migration
™ Evaluate legacy areas
Laser induced breakdown
spectroscopy
LENS
LASER
PLASMA SPARK
DETECTOR
SPECTROGRAPH
FIBER OPTIC
CABLE
COMPUTER
LIBS
Aerosol-Focusing Laser-Induced-Breakdown
Spectroscopy
Portable unit enables in-situ
measurement of the elemental
composition of airborne particulate
matter in near-real time.
Instrument has a
capability for the
simultaneous, multielement analysis of
airborne particles.
Microwave Induced Plasma
Spectroscopy
Plasma
Optical
Detection
System
Excited
Elements
Microwave
Generator
.01
Compounds
& Elements
Amzil BAM System
•
•
•
•
•
•
•
•
•
High Sensitivity
High Sampling Rate
Complete Particulate Volatilization
Air Cooled
Operates on Electricity & Air
Robust Cart Mounted Package
Completely Automatic
Simple Touch Screen Interface
Full Gear Operation
MIPS
Adsorptive Stripping Voltametry Analysis of
Beryllium in Dusts and Air Samples
‹
‹
‹
Ultrasonic extraction
Adsorption of
beryllium/ligand
complex
Anodic stripping
ATOFMS (Aerosol Time of Flight Mass Spectrometer)
The Model 3800 ATOFMS
Aerosol In
Ellipsoidal Mirrors
Roughing Pump
Diode-Pumped Solid State
Lasers (532 nm) (Sizing Lasers)
Photo Multiplier
Tubes (PMT)
Split-Flow TurboMolecular Pump
Particle Sampling Region
1st stage: 2x100 Torr
2nd stage: 10-1 Torr
Particle Sizing Region
10-4 Torr
Negative Ions
Positive Ions
Mass Spectrometry
Region
2x10-7 Torr
Reflectron
(“Ion Mirror”)
Flight Tube
Nd:YAG Laser (266 nm)
Desorption/Ionization Laser
Microchannel Plate
Ion Detectors
200
180
160
140
120
100
Unclassified
Calcium-Aluminum containing
Magnesium containing
organic
Titanium containing
Potassium rich
NaCl containing
Iron containing
80
60
40
20
3.96
3.62
"118"
3.30
2.98
2.68
2.39
2.12
1.85
Zink containing
1.60
1.36
1.13
0.91
0.70
chrome containing
0.51
0.33
0.15
0
Colorimetric
Fluorometric
Status of non-lab analysis/detection
techniques (airborne & surface)
™ Fifteen
instruments/methods
¾Technology development-5
¾Prototype – 5
¾Out of business – 1
¾Commercial instruments -4
Œ One only qualitative, one never tested with
beryllium, two over $300k and very large
™ Nothing
validated to date
WHAT ARE WE LOOKING FOR?
Let’s talk about exposure risk.
Comparison of locations by deposited Be particle number
and average Be mass concentration
Deposited Be
Particles / cc
Oxide furnace area
Fluoride furnace area (Average)
Cast shop
Hydrolysis / filling area
Wet plant (Processing Facility)
Reduction furnace area
Bulk pickle in strip mill
Ball mill (Processing Facility)
Beryl ore mine
Ore crusher
Milling operation
Administration and shipping
9900
9700
3700
1800
1400
300
200
100
9
5
3
1
Average Be
Mass µg / m3
0.015
0.25
0.036
0.19
0.058
0.059
0.075
0.074
0.24
0.077
0.004
0.001
Michael McCawley, et al.
Lung Deposition Curve
1
0.9
IMPACTION
SEDIMENTATION
INTERCEPTION
DIFFUSION
Efficiency (%)
0.8
0.7
0.6
Gas Exchange Region Deposition
0.5
Tracheobronchial Deposition
0.4
0.3
0.2
0.1
0
0.01
0.1
1
10
Particle Diameter (micrometers)
100
Particle size data by operation
1.8
1.8
1.6
1.6
1.4
1.4
1.2
1.2
1
1
0.8
0.8
0.6
0.6
0.4
0.4
0.2
0.2
0
0
10
10
100
100
1000
1000
DIAMETER (nm)
R
R 88
88
ZZ- Mill
Mill
R
R 31&
31& R
R 35
35
Roll
Roll 696
696
78.001
78.001
Slitter
Slitter
7301
7301
Annealing
Annealing 611
611
Preliminary conclusions on beryllium
health
™ Dose
response relationships for beryllium
sensitization and beryllium disease have not
previously been clearly established
™ Risk may be particle size and particle
number dependent
™ Skin contamination may be a route of
sensitization
™ Particle number may possibly be a good
metric for inhalation exposure risk
In search of the perfect method
Real-time
™ Low detection limit (<10ng)
™ Ability to speciate (natural vs man-made)
™ Non-destructive
™ Measures number, surface area and possibly particle
size of airborne particles
™ Proven to assess exposure risk
™ Small (can hang device on a person)
™ Inexpensive
™ Rugged
™ Validated in laboratory and workplace setting
™
Future direction (from BeATAT)
™ Complete
instrument criteria and
validation procedures
™ Select/fund 3-4 technologies to final
development
™ Develop beryllium aerosol laboratory
for evaluation and validation
™ Validate instruments with established
criteria
Conclusions
™ Many
methods developed yet none have
been validated
™ Research needs to be continued to
¾reduce cost and time
¾allow for increase in sample throughput,
¾ provide workplace risk determination for
surface and airborne exposure
™ Need
final development and validation of
instrumentation
Acknowledgements
™ Science
& Engineering Associates, Inc.
™ Y12 National Security Complex
™ Oak Ridge National Laboratory
™ ADA Technologies, Inc.
™ Amzil, Inc.
™ Los Alamos National Laboratory
™ ELS Technology, Inc.
™ TSI Inc.