nbl nuclear reference materials · nbl’s suite of reference materials and samples dates from 1944...
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September General Staff Meeting
May 25, 2011 1
NBL Nuclear Reference Materials
Jon W. Neuhoff, DirectorNew Brunswick Laboratory
CETAMA Seminar - Nuclear Analytical Chemistry
NBL Nuclear CRMs
NBL Cooperation with CEA/CETAMA/IndustrySafeguards Analytical Laboratory
Evaluation (SALE)LaHague, Pierrelatte, Grenoble, Saclay,
Narbonne, Romans, Fontenay‐aux‐Roses
EQRAIN/SME Participation
Last 10 years, 148 NBL CRMs shipped to 19 French fuel cycle facilities
Environmental sampling support
Expanding cooperation Analytical procedures/technical exchange
U standards; Pu metal standards (MP‐2/4 – CRM 126‐A)
May 25, 2011 CETAMA Seminar - Nuclear Analytical Chemistry 2
CEA Visitors for Environmental Sampling Tours of NBL
NBL Nuclear CRMs
Nuclear Certified Reference Material Uses
1.
Development and validation of
accurate methods of analysis
2.
Verify that methods in current use
are performing at validated performance levels
3.
Calibrate measurement systems
4.
Test materials for inter‐laboratory
comparisons
5.
Assure traceability in the production
of working reference materials
May 25, 2011 CETAMA Seminar - Nuclear Analytical Chemistry 3
NBL Nuclear CRMs
Nuclear CRMs – Safeguards Link
In a robust safeguards system, nuclear CRMs are of fundamental importance
Measurements made for declared material, proliferation detection, attribution/forensics
Good destructive analysis (DA) nuclear material measurements, for element assay and
determination of isotopic composition, require sufficient and appropriate CRMs to meet material
control and accountability, measurement quality control, and nuclear safeguards “confidence”
May 25, 2011CETAMA Seminar - Nuclear Analytical
Chemistry 4
NBL Nuclear CRMs
Nuclear CRMs Cover the Nuclear Fuel Cycle
May 25, 2011 CETAMA Seminar - Nuclear Analytical Chemistry 5
NBL Nuclear CRMs
New Brunswick Laboratory’s Role in RM Production
NBL is a U.S. Department of Energy (DOE) laboratory with an enduring mission to
improve, build confidence, and strengthen the effectiveness and efficiency of nuclear
material measurements in support of DOE and national needs
To achieve the mission, we provide unique, metrological science and technology in:
Reference MaterialsMeasurement EvaluationMeasurement DevelopmentMeasurement ServicesNuclear ForensicsSafeguards, Nonproliferation, and
National Security Assistance
May 25, 2011 6
NBL Modified Davies and Gray/High Precision
Titration Method (Uranium Assay Analysis)
NBL Plutonium Cleanroom Chemistry (Low‐Level
Plutonium Work)
CETAMA Seminar - Nuclear Analytical Chemistry
NBL Nuclear CRMs
May 25, 2011 7
United States Nuclear Measurement System
SI System
U.S. National System of Physical & Chemical Measurements
NBL: CRMs for Chemical Composition, Isotopic
Composition, NDANIST: SRMs for Radioactivity,
Oxidimetry, Reductometry
Definitive Methods
Reference Methods
Consensus Standard Methods
Measurement /Method Evaluation,
Safeguards (MC&A), QAWorking
Reference Material
Voluntary Consensus Standards Organizations:
ASTM, ANSI, etc.
Field Methods
Certified Reference Materials
CETAMA Seminar - Nuclear Analytical Chemistry
NBL Nuclear CRMs
NBL Reference Materials ProgramNBL is the only facility in the U.S. (U.S.
Government’s Certifying Authority) responsible for preparing, certifying, and
disseminating nuclear Certified Reference Materials (CRMs)
Supports the nuclear fuel/weapons cycle (mining, milling, conversion, enrichment, fuel/weapon fabrication)
NBL’s suite of reference materials and samples dates from 1944 – present
Every significant uranium, thorium, or plutonium measurement (assay or isotopic)
in the U.S. is traceable to an NBL standard (through DOE and NRC directives)
May 25, 2011 8
NBL CRM 112‐A Uranium (Normal) Metal Assay Standard
NBL CRM 129‐A Uranium Oxide (Normal) Assay and Isotopic Standard
NBL CRM 126‐A Plutonium Metal Standard
CETAMA Seminar - Nuclear Analytical Chemistry
NBL Nuclear CRMs
NBL CRM Usage – Worldwide 2000‐2010
May 25, 2011 9CETAMA Seminar - Nuclear Analytical Chemistry
NBL Nuclear CRMs
May 25, 2011 10
Units Sold (#)
CETAMA Seminar - Nuclear Analytical Chemistry
NBL Nuclear CRMs
NBL Certified Reference Materials
62 CRM’s within the following categories:
• U and Pu Assay CRMs (9)
• U and Th Impurity CRMs (18, 22, & 24 elements) (3)
• U and Pu Isotopic CRMs (29)
• U NDA CRMs (LEU, HEU) (3)
• U and Th Ore CRMs (14)
• 233U, 239 Pu, 242Pu, 244Pu spikes (4)
May 25, 2011 CETAMA Seminar - Nuclear Analytical Chemistry 11
NBL CRMs in oxides, metals, nitrates, hexafluoride, fuel
pellets, solutions, sulfates, and ore
NBL Nuclear CRMs
NBL Plutonium CRMs
May 25, 2011 12
NBL has conducted plutonium measurements since 1959
Developed analytical methods
Supported fuels research
Produced counting and other standards from pure Pu
NBL has prepared the primary plutonium metal assay standards
in coordination with LANLSRM 949 (1962)
SRM 949d
(1972)
SRM 949a (1964)
SRM 949e
(1975)
SRM 949b (1967)
SRM 949f
(1982)
SRM 949c (1969)
SRM 949g
NBL Developed the Plutonium
Controlled‐Potential Coulometry
Method
NBL Plutonium Mass Spectrometer for Isotopic Analysis
NBL Plutonium Gloveboxes
CETAMA Seminar - Nuclear Analytical Chemistry
NBL SRM 949f Pu Metal Standard
NBL Nuclear CRMs
May 25, 2011 CETAMA Seminar - Nuclear Analytical Chemistry 13
NBL Pu Metal CRM (CRM 126‐A)
Source material prepared by LANL
Highly pure plutonium metal (99.9 wt%) with low levels of Th, Ga, Np, Am, U, and Fe
1,200 units made with a batch extrusion process under elevated temp., high pressure, and inert atmosphere
•
Plutonium metal was double‐electrorefined and recast into rods and then machined into plugs
•
Plugs were placed through specially‐designed extrusion die and came out as 5/32”
diameter wire
•
Wire was cut into 1 gram pieces which were then placed in glass ampoules under argon atmosphere
NBL Nuclear CRMs
CRM’s 136 (SRM 946), 137 (SRM 947), and 138 (SRM 948)
SRMs 946 and 947 made to represent fuel‐grade materialsNFS West Valley produced a total of 1530 kg of separated Pu, 895
kg
from commercial fuel that was sold back to AEC
•
Of the 895 kg of separated Pu purchased by AEC from the utilities,
436 kg was from Yankee Rowe, 285 kg from Dresden, and rest from
Big Rock Point, Pathfinder and Indian Point reactors
SRM 948 made to represent weapons‐grade materialSource of SRM 948 plutonium is a high‐purity metal from the Rocky Flats
plant, likely originated in a Hanford (1944) or SRS reactor (1955)
Evaluated chemical forms for suitability, stoichiometry and stability – sulfate, sulfate tetrahydrate, dicesium tetrachloride double salt
Sulfate tetrahydrate found suitable for primary standards
Plans to recertify these CRMs to reduce uncertainty
14May 25, 2011CETAMA Seminar - Nuclear Analytical
Chemistry
NBL Nuclear CRMs
CRMs 136, 137, 138 – Pu Isotopic Standards
15
CRM 138/SRM 948 CRM 136/SRM 946 CRM 137/SRM 947Isotope 1966 2010 1971 2010 1971 2010Pu-238 0.010 0.010 0.25 0.18 0.29 0.22Pu-239 91.4 91.3 83.1 83.0 75.6 75.6Pu-240 7.9 7.9 12.1 12.0 18.3 18.2Pu-241 0.63 0.08 4.02 0.65 4.60 0.74Pu-242 0.03 0.03 0.57 0.56 1.20 1.18Am-241 - 0.5 - 3.2 - 3.7U-234 - 0.0 - 0.1 - 0.1U-235 - 0.1 - 0.1 - 0.1U-236 - 0.0 - 0.1 - 0.1U-238 - 0.0 - 0.0 - 0.0Np-237 - 0.0 - 0.1 - 0.1
Weight percent; 2010 data decayed only, not measured
May 25, 2011CETAMA Seminar - Nuclear Analytical
Chemistry
NBL Nuclear CRMs
May 25, 2011 CETAMA Seminar - Nuclear Analytical Chemistry 16
CALEX I and II Standards
NBL took over the Calorimetry Exchange Program from Mound in 1996
Calorimetry Exchange (CALEX) standards are suitable for quality control of gamma spectrometric and calorimetric measurements; investigating
suitability for neutron measurements
CALEX I – not a CRM, but a well‐characterized RMEach exchange sample contains about 455 g of PuO2
, giving about 400 g of PuHeat output is about 1 wattPu‐240 content is about 6% of the total Pu
CALEX‐II ‐
CRMEach exchange standard contains about 2kg of PuO2
Heat output is about 6 wattsPu‐240 content is about 12% of the total Pu
NBL Nuclear CRMs
May 25, 2011 17
Future NBL CRMs ‐
UraniumCRM 112‐A (Uranium (Normal) Metal Assay and Isotopic
Standard) –
completed in 2010 the isotopic certification
CRM 115‐A (Uranium (Depleted) Metal Assay and Isotopic Standard) –
completed in 2011 the isotopic certification
CRM 116 (Enriched Uranium Metal Standard, 93% Enriched)CRM U0002‐A (Uranium Isotopic Standard, 0.2% Enriched)CRM U005‐B (Uranium Isotopic Standard, 0.5% Enriched)CRM U010‐A (Uranium Isotopic Standard, 1% Enriched) CRM 17‐B (Normal Uranium Tetrafluoride Assay Standard)Uranium Isotope Calibration Mixes (U‐233, U‐234, U‐235, U‐
236, U‐238) – various mixtures in 1:1
Uranium impurity standardsCETAMA Seminar - Nuclear Analytical Chemistry
NBL Nuclear CRMs
May 25, 2011 18
Future NBL CRMs –
PlutoniumCRM 122‐A (Plutonium Oxide Assay and Isotopic Standard)New CRM made from CRM 126‐A
Solutions or dried nitrates of 10‐100 mg sample sizesCRM 136‐A (Plutonium Isotopic Standard) – 1 mg dried nitrateCRM 137‐A (Plutonium Isotopic Standard) – 1mg dried nitrateCRM 138‐A (Plutonium Isotopic Standard) – 1 mg dried nitrateCRMs 140‐142 (Plutonium Isotopic Spikes) – Pu‐240, Pu‐242, Pu‐244CRM 143 (Plutonium Double Atom Spike) – Pu‐242/Pu‐244CRM 144 (Plutonium Triple Atom Spike) – Pu‐240/Pu‐242/Pu‐244
2 mg dried nitratePlutonium Impurity Standards – Pu metal matrix containing
metallic/non‐metallic impuritiesPlutonium NDA Standards –
Weapons grade and reactor grade Pu
standards in metal and oxide form; high burn‐up; 3013
CETAMA Seminar - Nuclear Analytical Chemistry
NBL Nuclear CRMs
May 25, 2011 19
Future NBL CRMs ‐
Other
Mixed Oxide (MOX) Standard (U and Pu assay and isotopics with five levels of impurities)
CRM 66 (Thorium Oxide Impurity Standard)Mostly Th‐232 with 22 impurities
Np standards/spikes (Np‐236, Np‐237)Am standards/spikes (Am‐241, Am‐243)Radiochronometry standards – age dating/forensics
CETAMA Seminar - Nuclear Analytical Chemistry
NBL Nuclear CRMs
Looking Forward…Developments in nuclear CRMs continue and require a
sustained and focused effort, including increased international cooperation, to ensure appropriate availability
of nuclear CRMs
Next Generation Safeguards Initiative (NGSI) and Materials Protection Accounting and Control for Transmutation
(MPACT)NGSI’s purpose is to strengthen U.S. domestic policies,
technologies, and expertise related to the application of
safeguards while also strengthening the international
infrastructure to support the international safeguards system
as it evolves over the next 25 years
MPACT is developing innovative technologies and analysis tools
to enable next‐generation nuclear materials management for
future U.S. nuclear energy systems (Gen III and Gen IV)
Micro‐analysis/reduction in CRM sizes
May 25, 2011 CETAMA Seminar - Nuclear Analytical Chemistry 20
NBL Nuclear CRMs
Looking Forward…With the further adoption of nuclear energy,
the need for reference materials,
measurement evaluation, and related
services is expected to significantly grow in
terms of customers and materials
Significant expansion in the uranium ore
mining, processing, conversion, and recovery
facilities ‐
increased reference materials
Growth in uranium enrichment services
(centrifuge and laser enrichment) ‐
increased reference materials and
measurements
May 25, 2011 CETAMA Seminar - Nuclear Analytical Chemistry 21
URENCO National Enrichment Facility ‐
New Mexico
USEC American Centrifuge Enrichment Plant – Ohio
AREVA Eagle Rock Centrifuge Enrichment Plant –
Idaho
NBL Nuclear CRMs
22
Nuclear Forensics – New Area for CRMs
Nuclear Forensics: Analysis and characterization of pre-and post- detonation radiological and nuclear materials, devices, and debris, as well as other effects from a nuclear detonation.
Nuclear Forensics
Acquisitionof Samples
Analysisof Samples Evaluation
Ground Debris;Atmospheric
Radiochemistry;Chem & phys analysis;
Traditional forensics
Comparison to known signatures;
Databases
May 25, 2011 CETAMA Seminar - Nuclear Analytical Chemistry
NBL Nuclear CRMs
23
Origins of Nuclear Forensics – The Manhattan Project
Albert Ghiorso and A.H. Jaffey with pulse analyzer in Metallurgical Laboratory counting room, University of Chicago(source: LBNL Image Library; "Life Magazine – Fritz Goro Estate" )
Nuclear Forensics leverages heavily on fuel cycle/nuclear material production expertise
May 25, 2011 CETAMA Seminar - Nuclear Analytical Chemistry
NBL Nuclear CRMs
24
Production of Exercise Test Materials
Sample in reactor irradiation vessel
Glass debris sample
May 25, 2011 CETAMA Seminar - Nuclear Analytical Chemistry
NBL Nuclear CRMs
25
Radiochronometry Reference Materials
Reference materials certified for time elapsed since last purification
• 234U – 230Th• 235U – 231Pa• 241Pu – 241Am• 137Cs – 137Ba
Certify for age0 20 40 60 80 100
1E-6
1E-5
1E-4
1E-3
0.01
0 years 10 years 20 years 30 years 40 years 50 years 60 years
Act
ivity
Rat
io
Time [y]
230Th/234UDaughter/Parent Activity Ratio
May 25, 2011 CETAMA Seminar - Nuclear Analytical Chemistry
NBL Nuclear CRMs
26
Cs-137 Reference Material
Cs-137 is a potentially significant RDD materialProduction of a Cs/Ba radiochronology standard is in progressProduction of a Ba spike is in progress
May 25, 2011 CETAMA Seminar - Nuclear Analytical Chemistry
NBL Nuclear CRMs
27
Test Material Production
NBL provides the oversight for production of reference and test materials
RADIOACTIVE TEST SAMPLES (Actinides + Fission Products)Glass cylinders
Artifacts that Mimic Fused
Material from a Blast Crater
May 25, 2011 CETAMA Seminar - Nuclear Analytical Chemistry
NBL Nuclear CRMs
Future Challenges: Training, Education, and Infrastructure
To ensure quality nuclear CRMs for the
future, overarching challenge is the
recognition that we are dependent
upon the availability of well‐trained
analytical chemists and scientists, using
suitable measurement equipment,
within a well‐maintained infrastructure
Increased emphasis on enhancing
education initiatives (NGSI), training
(post‐docs/mentoring), and
infrastructure (lab/equipment
upgrades) activities
More international cooperation is vital
May 25, 2011 CETAMA Seminar - Nuclear Analytical Chemistry 28
NBL Nuclear CRMs
Summary and Conclusions
Expanding cooperation with CETAMA
NBL is the only facility in the U.S. (U.S. Government’s Certifying Authority) responsible for preparing, certifying, and disseminating
nuclear Certified Reference Materials (CRMs) – currently 62
New NBL reference materials planned and will come out on an increasing frequency – more international collaboration, micro‐ analysis and reduced size
NGSI, MPACT, new facilities, and the overall (hoped for) expansion of nuclear facilities will require increased reference materials and
safeguards measurements
Training, education, and infrastructure should continue to be emphasized for ensure good CRMs
for the future
May 25, 2011 CETAMA Seminar - Nuclear Analytical Chemistry 29