methodology and application of automation in radiochemical ..."extraction chromatographic...
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Methodology and Application of Automation in Radiochemical Separations
and AnalysisJay W. Grate and Matthew J. O’Hara
Pacific Northwest National Laboratory
NKS Workshop on Radioanalytical Chemistry
Roskilde, Denmark, September, 2013
United States Department of Energy (DOE) Multi-program National Laboratories
Lawrence Livermore
Pacific Northwest
IdahoLawrence Berkeley
Argonne
Sandia
Los AlamosOak Ridge
Brookhaven
Office of ScienceNational Nuclear Security AdministrationOffice of Nuclear Energy, Science & Technology
Hanford Nuclear Site in Washington StateNuclear waste storage tanksContaminated earth and groundwaterNuclear waste processing facilities
Under constructionColumbia River
Radiochemical analysis is critical in several activities
CharacterizationMonitoringRemediationProcessing waste into stable waste formsLong term stewardshipNuclear archeology
Hanford Nuclear Site Facilities
PUREX PlantExtract Pu from irradiated U
N-reactor next to Columbia River
Nuclear Waste Storage Tanks
Hanford Waste Treatment Plantplannedunder construction
Drilling and seismic testing prior to construction
June 2011 aerial view
http://www.hanfordvitplant.com/gallery_view.php?id=134
Pretreatmentfacility
AnalyticalLab
HLW
LAW
Radionuclides of Interest
Fission ProductsSr-90Tc-99
Transuranic ElementsPuAmNp
Half lives, activity, mobility in the environment, biological activity…
Sr-90Tc-99 Cs-137
Sample to Analysis in Radiochemistry
Dissolution
Extraction Chromatography
Precipitation
Anion Exchange
Single Bead Methods
Mass spectrometry
SEPARATION(S)Resolve interferences
Radiometric
Matrix Adjustment
Speciation Control
SAMPLE PREPARATION
DETECTION
Other elemental methods
Separations
Mass spectrometry
SEPARATION(S)Resolve interferences
Radiometric
SAMPLE PREPARATION
DETECTION
, , spectral
Isobaric, molecular ion, spectroscopic
Fluid handling methodology
Separation chemistry
Step Analyte retention
Load sample
Strong
Wash Strong
Elute Weak or unretained
…
Contrast with high resolution chromatography separations based on migration time
Extraction Chromatography
Anion Exchange
Separations
Mass spectrometry
SEPARATION(S)Resolve interferences
Radiometric
SAMPLE PREPARATION
DETECTION
, , spectral
Isobaric, molecular ion, spectroscopic
Fluid handling methodologyFlow Injection (FI)Sequential Injection (SI)Separation-optimized SIWhatever works for the application
Laboratory automationAnalyzers for process analysis at-siteRadiochemical sensors for environmental monitoring
Fluidic system may link:Directly to detectorFraction collector
Flow Injection and Sequential Injection Analysis (FIA and SIA)
Sequential InjectionReversible fluid drive
Digital syringe pump
Holding coil to stack zones of reagentsVariable sample size controlled by software rather than fixed sampling coilScaleable fluidics architecture suitable for many applications
Sequential Injection Separation
Pump
Reagent,8M HNO3
Waste
Sample
Holding CoilMultiposition Valve
SorbentColumn
Flow‐Through
ScintillationDetector
WasteCarrier, H2O
Sequential Injection Separation of Sr-90
Sr-ResinExtraction chromatographic resin (crown ether)
Standard
Pre-processedNuclear Waste
Flow through liquid scintillation detection and quantification
Sequential Injection Separation
Sequential Injection Separation
Separation-optimized Sequential Injection
Enables rapid change from one solution composition to
another, even with large-bore holding coils
Separation-optimized Sequential Injection
Enables rapid change from one solution composition to
another, even with large-bore holding coils
Gross Actinides Separation on TRU-Resin
Load, wash, & elute
Multistep Separations of Actinides
TRU-resinCMPO in TBP
A number of actinide separations can be implementedCompatible with ICP-MS detection
Actinide Analysis by Sequential Injection Separation with ICP-MS Detection
place analyte in consistent matrixaddress interferences:
isobaric , molecular ion, and spectral interferences
Actinide separation shown addresses 241Pu/241Am, 239Pu/238UH
237Np/238U
Automated Separation with On-line Detection
Dissolution
Extraction Chromatography
Precipitation
Anion Exchange
Single Bead Methods
Mass spectrometry
SEPARATION(S)Resolve interferences
Radiometric
Matrix Adjustment
Speciation Control
SAMPLE PREPARATION
DETECTION
Separation Issues Analytical Issues
Solution and reagent conditions to obtain consistent reproducible behavior time-after-time
Nearly always find something that needs to be addressed in automated format with on-line detection
Separation recovery
Column crossover
On-column reaction chemistry
Carryover
Column reusability
Detection limit
Sample throughput
Separation efficiency
Detection efficiency
Carryover
Application specific criteria
Applications Automated Radiochemistry
Analyses enabled by automation
Process monitoring “at-site”
Radionuclide sensors for ground water “at-site” or “in situ”
Analyses made more efficent* by automation
Laboratory automationfasterreduced labor/costreduced worker exposure to radiationmore consistent procedures with less training
Automated Monitoring: At-site Process Analysis
Dissolution
Extraction Chromatography
Precipitation
Anion Exchange
Single Bead Methods
Mass spectrometry
SEPARATION(S)Resolve interferences
Radiometric
Matrix Adjustment
Speciation Control
SAMPLE PREPARATION
DETECTION
Automated Monitoring: Total Tc-99
Anion Exchange
SEPARATION(S)
Radiometric
Matrix Adjustment
Speciation Control
SAMPLE PREPARATION
DETECTION
Alkaline high salt matrixacidificationoxidation of all Tc to TcO4
-
(pertechnetate anion)
retain TcO4- in weak acid
multi-eluent wash elute TcO4
- in strong acid
flow through solid scintillator detector
beta emitter
Monitor Fluidic System
Monitor Fluidic System
Microwave-assisted Sample Preparation
Digestion cell
Reagent line Vent line
Cell cap
A
B C
D
E
Automated Tc Monitor
Monitor Fluidic System
Rapid Column Separation of TcO4-
Flow reversalHigh flow rates
Species captured on the “top”of the column are then rapidly released in reverse flowFlow rates up to 8 mL/min are effective
raw data
smoothed data
calculated peak start
calculated peak end
calculated baseline
Tc Elution and Peak Integration
Flow through solid scintillator detector
Automated Peak searchBaseline calculationSmoothIntegration
Determine net peak area countsNcts
Sample Processing-Separation-Detection
<12 minutes per sample!near real time4 samples plus one matrix spike addition per hour
Continuous operation demonstrated for 54 hours
Precision and accuracy demonstrated for variety of complex nuclear waste matrixes
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Automated Tc Monitor SuccessesFully automated monitor including on-line sample preparation
Challenging selectivity issues addressed for highly radiological, complex, variable sample matrix
Technology suitable for on-site/at-line monitoring in harsh industrial environment
Automated Separation Laboratory Platform
Dissolution
Extraction Chromatography
Anion Exchange
Mass spectrometry
SEPARATION(S)Resolve interferences
Radiometric
Matrix Adjustment
Speciation Control
SAMPLE PREPARATION
DETECTION
Automated Separation Laboratory Platform
Extraction Chromatography
Anion Exchange
SEPARATION(S)Resolve interferences
Sequential Injection SeparationsTypically
Single column separationCoupled to detectionFluidic system
Laboratory AutomationSamples in parallelSeparate containers or columns - no carryoverWorkstationsSupports:
Radiometric detectionICP-MSTIMS
Automated Separations for Multiple Detection Methods
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RadiometricICP-MSTIMS
TIMS:Very low detection limits, and precise isotopic ratiosCapable of measuring Pu at global fallout levels of ng / m2 from small mass samplesBut TIMS requires essentially pure sources
Multiple separation / purification steps in sequence, moving to smaller and smaller scales
Total SampleDissolution
Matrix Separations
Actinide Separations
SingleBead
Separations
MW-assistedDissolution
AutomatedColumn
Separations(Matrix)
AutomatedColumn
Separations(Actinides)
AcceleratedSingle Bead
Uptake
Extraction Chromatography
AnionExchange
Workstations Concepts for Sample Prep…Flexible approach applicable to various analytical challenges
Column conditionSample load and wash
Uranium elute Thorium
elutePlutonium elute
Classic Actinide Anion Exchange Separations
Am U Th Pu/Np7.2M HNO3 9M HCl 1.2M HCl
Pu-containing fraction
Matrix removalvia precipitations
Matrix Separation for ActinidesLoad sample on stacked TEVA and DGA columnsSeparate and recover actinides of interest from TEVA column
Pu/Np
Stacked columns
TEVAonly
DGAonly
Recovery and separation from soil
digestate matrix in 7.5 M HNO3
EC as matrix separation prior to Anion Exchange (AnIX)
ClassicPrecipitations
ppt contains:Precipitant.Am, LnsThPu/Np
AnIX
EC:TEVA-resin
eluent contains:....Pu/Np
AnIX
load load
AnIX
load
No separation
sample contains:MatrixUAm, LnsThPu/Np
Column-based separations suitable for automation
Manual Separation Sequence for TIMS Manual EC on Vacuum Box
ECColumn
1. Wet Ash
2. Redox Adjust
AnIXColumn
Source Preparation
AcidSample(SPIKE)
TIMS
EC (TEVA) 97 ± 3%
400 µL AnIX 89 ± 3%
Overall efficiency(244Pu)
2.7 ± 0.3%Compares to 2.78 ± 0.85%
for process using precipitations
Grate J.W.; M.J. O'Hara; A.F. Farawila; M. Douglas; M.M. Haney; S.L. Peterson; T.C. Maiti; C.L. Aardahl. "Extraction Chromatographic Methods in the Sample Preparation Sequence for Thermal Ionization Mass Spectrometric Analysis of Plutonium Isotopes",Analytical Chemistry 2011, 83, 9086-9091. ; DOI: 10.1021/ac202150v
Matrix Free
2.5 fg Pu spikes
Pu-244 Pu-242 Pu-239
EC chemical recovery at very low levels is effectiveAnIX separation downstream unimpairedTIMS bead loading and ionization efficiency unimpairedEC with wet ash compatible with TIMS detection process
Challenges for Automating Column-based Separations in Radiochemistry
Strong acid solutions2 mL column bed scale
larger than typical bioanalytical applications.Cross contamination must be preventedCustomization (no COTS fits needs)Complexity/Reliability
44
Customize Commercial Liquid HandlerX-y-z robotics
Design from scratchFluid transport via tubing
y-z fraction collector
Column Separation Automation Platforms
Customized to match actinide anion exchange process very closely
SLOWDrifting Positional Accuracy
PNX-II System (Pacific Northwest eXtraction system)
Disposables in Blue
Designed for varying column configurationsOverhead rack is adaptable to a variety of column types
2cc Column
0.1cc Column
StackedCartridges
2cc Cartridge
Sample routed manually via disposable components (side);Separation agents delivered from the top
Custom fraction collector fabricated at PNNL
Actuation with fixed stops, feedback confirms each step
2 translational directions (only 2!)
2 barriers to prevent cross-column contamination
Parts easily removed and cleaned
Waste trough and 5 vial positions
PNX-II System (Pacific Northwest eXtraction system)
X-contamination verification w/ ~37 kBq Pu-238 resulted in < MDA in vials and surface smears
Automated Separations on PNX-IIExtraction Chromatography and Anion Exchange
Demonstrations at radiotracer levels
Demonstrations at mass spectrometry levels
Chemical recoveriesOverall measurement efficiency Isotopic ratios in Standard Reference Materials
EC on PNX-II at TIMS levels
EC 85%
Chemical Yields,* Pu
2 mL AnIX 88%
*Avg of 6 samples3 digestate matrix (86.4%)3 acid – matrix free (83.7%)
TEVA
ECcolumn
2 mLAnIX
column
0.1 mLAnIX
column
transp/redox Adj**
source prep
TIMS
sample
244Pu242Pu
244Pu 242Pu 239Pu
tripletrans-pose
EC only on PNX-II
wet ash
Spiked Clean Soil Digestate– Spiked Known
239Pu
AnIX on PNX-II at TIMS levels
ppt – 2 mL AnIX 81%
Chemical Yields,* Pu
0.1 mL AnIX 84%
*Avg of 6 samples3 digestate matrix (80.8%)3 acid – matrix free (81.3%)
2 mL AnIX only on PNX-II
pptdissolveIn nitric*
2 mLAnIX
column
0.1 mLAnIX
column
source prep
sample
244Pu 242Pu 239Pu
trans-pose
Spiked Clean Soil Digestate– Spiked Known
TIMS244Pu 242Pu 239Pu
Laboratory Automation ApproachWorkstation Toolkit for Actinide Analysis
Method developmentAutomated workstationsLink workstations with
manual transfers
DissolutionAutomated
ColumnSeparations
(Matrix)
AutomatedColumn
Separations(Actinides)
AcceleratedSingle Bead
Uptake
Extraction Chromatography
AnionExchange
Sensors and Systems for Radionuclides in Water Preconcentrate and Detect
Automated Fluidic SystemCapture on a columnElute to downstream detector
Sr-90Beta emitterSr2+
SuperLig 620
Radionuclide SensorCapture on a columnDetect on the column
Tc-99Beta emitterTcO4
- (pertechnetate)Anion exchange
Anion Exchange beads &Scintillating beads mixed in a Column packing
Tc Sensing: Random Order
0
2
10
1
5 dpm
Tc-99 in Hanford Groundwater, dpm
Radionuclide Monitors on Hanford SiteTc-99 as TcO4-
Hanford groundwater Pump and Treat Plant
Outdoor groundwater well Near Columbia River
Sr-90 in ground water
Articles, Chapters, and ReviewsFall 2012
Ch18 Automated Radiochemical
Sensing Separation and Analysis
2009
Acknowledgements
DOE - National Nuclear Security Administration
Office of Nonproliferation Research and Development NA-22
U.S. Department of Energy Environmental Remediation Science ProgramEnvironmental Management Science Program
Hanford site contractors
Matthew O’HaraKaren NoyesOleg B. EgorovTravis MintonMatt DouglasSteve PetersenTapas Maiti Diana BellofattoCrystal RutherfordSamuel MorrisonBrian DockendorfAnne FarawilaStan OwsleyJohn Wacker
Extras
Microchemical Separation and Bead Source Preparation
TypicalSlow static diffusion
NewNoncontact mixing by acoustic streaming
CHALLENGESVery small volumesDiffusional limitationsReynolds number contraintsAvoid sample contamination
0 min
30 min0 min 60 min
5 min 10 min
Diffusion only:
Acoustic streaming (82 MHz/25 dB):30 min 60 min
Acoustic Streaming Results
Uptake with streaming is ~10 times faster than diffusion alone!
sorption of a strong trianionic dye, amaranth (5.510–5 M), by ~760 µm strong anion exchange resin beads
1 mm
no streaming
w/streaming
Direct comparison after 1 hour
“Big bead” in microwellsPu uptake from 7.5 M HNO3
Acceleration:5x faster uptake
Platform for Parallel Single Bead Procedures
96 transducers 384 microwell plate
Enhanced platform for parallel single bead procedures
96 piezoelectric transducers excited w/ radiofrequency powerCapable of uniform mixing across 384 microwell plate
Produces a rotating lateral vortex
DissolutionAcid digestion in beakers on hot plates
Microwave-assisted total sample dissolution in acids12 samples in parallel
Instant on, instant offProgrammable heating
Feedback on temperature and pressureANALYTICAL CHALLENGESTotal sample dissolution of soil/sediment Recovery of Pu, including refractory Pu Safety
3-Step Method1. HNO3 / HCl / HF dissolution2. Matrix reduction by evaporation
Drives off Si as SiF43. HNO3 / H3BO3 *
Dissolve metal fluoridesScavenge free F-
Pu recovery demonstrated in further experiments
Dissolution demonstrated in diverse sediments
> 99.9%
Plutonium Recovery
Sediments spiked with Pu tracers
MAPEP standards containing leachable and refractory Pu as separate isotopes
Pu determinations in standard reference soils using TIMS
Side-by-side comparisons with hot plate digestions
Acceleration:Reduce time by ca. 50% compared to hot plate beaker methods12 sample in parallel
AutomationHeating is instant on, instant off,under preprogrammed controlwith feedback