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 Basis for engineering/administrative controls/PPE Timely feedback to workers Improved productivity Movement of Materials Personnel efficiency 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 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.
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