NBL Nuclear Reference Materials · NBL’s suite of reference materials and samples dates from 1944 –present Every significant uranium, thorium, or plutonium measurement (assay

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


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


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)


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


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


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 (#)


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)


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


NBL SRM 949f Pu Metal Standard

NBL Nuclear CRMs


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


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


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


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


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


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


NBL Nuclear CRMs

24

Production of Exercise Test Materials

Sample in reactor irradiation vessel

Glass debris sample


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


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


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


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


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


Documents

NBL Nuclear Reference Materials · NBL’s suite of reference materials and samples dates from 1944 –present Every significant uranium, thorium, or plutonium measurement (assay