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In Cooperation with our University Partners
Radiochemistry Webinars
Nuclear Materials Analysis− Mass
Spectrometry
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Meet the Presenter… Dr. R. Kenneth Marcus
Contact Information: [email protected]
Dr. Marcus has been a Professor of Analytical Chemistry at Clemson University since1986. His undergraduate education included BS degrees in Chemistry and Physics from Longwood College (now University) in Farmville, VA, in 1982. He received his Ph.D. in Analytical Chemistry in 1986 from the University of Virginia, where he worked for Prof. W. W. Harrison. His current research program covers two distinct lines of study: use of capillary-channeled polymer (C-CP) fibers and films as platforms for protein separations, and development of liquid sampling-atmospheric pressure glow discharge (LS-APGD) microplasmas for spectrochemical analysis. The latter research earned Dr. Marcus the 2015 Lester Strock Award from the Society for Applied Spectroscopy. His research
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program is funded by the National Science Foundation, DTRA, and the Pacific Northwest and Savannah River National Laboratories. His research group has published over 180 refereed journal articles, made over 550 conference presentations (>130 invited), and yielded over a dozen U.S. patents. He serves on the editorial advisory boards of Spectrochimica Acta B, the Journal of Analytical Atomic Spectrometry, and Analytical and Bioanalytical Chemistry. Dr. Marcus takes great pride in the fact that over half of his 34 Ph.D. graduates are employed in federal laboratories including NIST, the CDC, and the Savannah River, Oak Ridge, Sandia, Los Alamos,and Pacific Northwest National Laboratories. Dr. Marcus has been honored as a Fellow of the Royal Society of Chemistry and the American Association for the Advancement of Science.
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Nuclear Material Analysis
Mass Spectrometry Dr. R. Kenneth Marcus Clemson University
National Analytical Management Program (NAMP)
U.S. Department of Energy Carlsbad Field Office
TRAINING AND EDUCATION SUBCOMMITTEE
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Introduction part I – Why mass spectrometry ?
• Complete elemental coverage (H – to - …)
• High sensitivity (low LODs)
• Quantitative analysis
• Relatively uniform figures of merit
• Isotope ratios: all the isotopes, all the time . . . .
• No need for multiple methods (a, g, n. . .)
• No requirement that analyte be “activated”
• Only a few “peaks” per element
• On-line coupling with chemical processing
• Wide diversity of approaches, as dictated by specific
challenges
– Solids, liquids, or gases
– Elemental analysis or isotopic determinations
– Identification of chemical species
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Introduction part II – Why not mass spectrometry
(real and perceived)?
• Too many choices
• Too many experimental variables
• Very high levels of user expertise
• Too much sample prep
• It is destructive
• Vacuum systems, high voltages, weight
• . . . . . .
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Just like anything else, at the end of
the day a cost/benefit analysis must
be done . . . .
Mass spectrometry provides more
bang for your buck than any other
analytical technique ! !
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Isotopes of selected elements
D. C. Harris, Quantitative Chemical Analysis, 6th Ed., WH Freeman
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J. S. Becker, “Inorganic Mass Spectrometry: Principles and Applications”, Wiley
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J. S. Becker, “Inorganic Mass Spectrometry: Principles and Applications”, Wiley
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Mass Spectrometry: Gen-1
J. S. Becker, “Inorganic Mass Spectrometry: Principles and Applications”, Wiley
Parabola mass spectrograph constructed by J. J. Thomson (1910) with a discharge
tube as ion source, a superimposed electrical field and a magnetic field oriented
parallel to it for ion separation and a photoplate for ion detection
Ion source
Collimator
Magnetic and Electric field
Screen or photoplate
N
S
-
+
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J. S. Becker, “Inorganic Mass Spectrometry: Principles and Applications”, Wiley
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Basic anatomy of a mass spectrometer
Vacuum
Pumps
Mass
Analyzer
Ionization
Source Detector
Sample
Introduction
10-3 - 10-10 Torr
Solids
Liquids
Gases
90% of the time, some sort of state
conversion must take place; that
takes energy . . .
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Sidney Harris
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A simple example . . . .
D. C. Harris, Quantitative Chemical Analysis, 6th Ed., WH Freeman
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So, where are we going . . ?
• Simple physics
• Mass analyzer types and figures of merit
• Spectrometer systems
• Ionization sources
• Methods of quantification
• Isotope ratio mass spectrometry
All in an hour ! ! !
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Simple Newtonian Physics
Opposite charges attract; like charges repel
Kinetic energy KE = 1/2 mv2 = zeV
Force F = ma
Centrifugal force FC = (mv2)/r
Centripetal force FM = Bzev
Time-of-flight t = (m/(2zeV))1/2 L
Cyclotron frequency c = 1.537 x 107 (zB/m)
Rule of Practicality: Vacuum pumps and power supplies cost money,
add weight and complexity
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Mass Spectrometer Figures of Merit
• Mass range
• Mass resolution (m/Dm)
• Scan speed
• Native sensitivity
• Ion source acceptability
• Operational overhead
–Operating pressure
–Power/space requirements
–User sophistication
–Transportability
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Time of flight (ToF) MS: the ion dash
t=0 t=x t=y t=z
Start
pulse
Pulsed
laser
field-free region
Acceleration
grids
L
Trigger
Transient
digitizer
Detector
time
KE = zeV = ½ mv2
t = [m/(2zeV)]1/2L
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Most ToFs employ reflectron technology . . .
D. C. Harris, Quantitative Chemical Analysis, 6th Ed., WH Freeman
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ICP-ToF-MS
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Electromagnets
IonSource
Detector
Exitslit
Entranceslit
r
FC = (mv2)/ r
FM = Bzev(mv2)/ r = Bzev
m/ z = (B2r2e)/ 2V
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Electrostatic analyzer
Fc = mv2/ r = ezE
2zeV/ r = ezE
r = 2V/ E
Detector
Exitslit
IonSource
Entranceslit
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Double-Focusing Mass Spectrometer
Detector
Exit
slit
Ion
Source
Entrance
slit
Electrostatic sector Electromagnet Intermediate
slit
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Multicollector ICP-MS
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Faraday Plate Array
J. S. Becker, “Inorganic Mass Spectrometry:
Principles and Applications”, Wiley
Focal plane @ 90° to ion beam
Faraday cups
Separated ion beams
Focal plane
Conversion dynode/multipliers
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Quadrupole Mass Filter
D. C. Harris, Quantitative Chemical Analysis, 6th Ed., WH Freeman
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QMF Scan Functions
0 20 40 60 80 100
+ d.c.- d.c.
+ rf- rf
Time (msec)
0 200 400 600 800 1000
m/z
800
600
400
200
0
-200
-400
-600
-800
3600
2700
1800
900
0
-900
-1800
-2700
-3600
vo
lts (
d.c
.) vo
lts (rf)
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Quadrupole Ion Trap
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Quadrupole Ion Trap
D. C. Harris, Quantitative Chemical Analysis, 6th Ed., WH Freeman
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Quadrupole Ion Trap
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Orbitrap Mass Analyzer
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In Summary . . . .
Analyzer Acronym Pressure
(Torr)
Mass
range
(Da)
Mass
resolution
(m/Dm)
Scan rate
(Da/sec)
Magnetic
sector B <10-8 10,000 5,000 500
Electrostatic
sector ESA, E <10-8 NA NA NA
Double
focusing E/B, B/E <10-8 10,000 40,000 500
Time of
flight ToF <10-7 >100,000 >5,000 10,000 Hz
Quadrupole QMS, Q <10-6 2,000 unit 2,000
Quadrupole
ion trap ITMS <10-3 600 unit-10,000 2,000
Orbitrap <10-9 2,000 60-100,000 Up to 1
kHz
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Ion sources . . . . • What is the physical form of the sample?
– Solid
– Liquid
– Gas
• What type of information do you want?
– Qualitative
– Quantitative
– Isotopic
– Molecular
• What analytical figures of merit?
– Precision
– Accuracy
– Limits of detection
• How much sample prep are you willing to do?
• Time, cost, portability . . . ?
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The cumulative process . . . .
J. S. Becker, “Inorganic Mass Spectrometry: Principles and Applications”, Wiley
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Elemental/Isotopic Ionization Sources
• Thermal ionization (TIMS)
• Secondary ion mass spectrometry (SIMS)
• Inductively-coupled plasma (ICP-MS)
• Glow discharge (GDMS)
• Resonance ionization (RIMS)
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Thermal Ionization Mass Spectrometry • Thermal release of solid analyte (residues,
solids, analytes in polymer matrices) from metal
filament
• Ionization via electron extraction/attachment at
filament surface or in the gas phase with
secondary filament
• Ions emitted with low KE spread
• Very element-specific (poor multi-element)
• Stable operation (great for IR measurements
• Limited concentration sensitivity
• Sample prep comparable radiochem (or worse)
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TIMS
J. S. Becker, “Inorganic Mass Spectrometry: Principles and Applications”, Wiley
Ionization efficiency = E+ = N+/No = A exp(F - IE/kT) where F is the work function of the filament and I is the IE of the analyte
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TIMS
J. S. Becker, “Inorganic Mass Spectrometry: Principles and Applications”, Wiley
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• Direct analysis of solids of various form
• High energy ion beams “sputter” neutrals, ions,
electrons, and clusters from surface
• High degree (<1 mm) of lateral and depth
resolution
• Operation in both positive and negative ion
modes
• Exceedingly high mass sensitivity
• Very low sample throughput and exceedingly
wide of elemental response factors
Secondary Ion Mass Spectrometry
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J. S. Becker, “Inorganic Mass Spectrometry: Principles and Applications”, Wiley
SIMS
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SIMS
J. S. Becker, “Inorganic Mass Spectrometry: Principles and Applications”, Wiley
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Inductively-Coupled Plasma Mass Spectrometry
• Most widely applied elemental analysis ionization
source
• High (kinetic) temperature plasma affects efficient
desolvation/vaporization/ionization
• Very uniform elemental responses, with very low
LODs
• Very high operational overhead (1-2 kW, 16 L min-1
support gas, extreme vacuum challenges)
• Multitude of different sample introduction
approaches; thus a diversity of sample forms
• Diversity of mass analyzers based on analytical
challenges
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ICP-MS
D. C. Harris, Quantitative Chemical Analysis, 6th Ed., WH Freeman
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ICP-MS
J. S. Becker, “Inorganic Mass Spectrometry: Principles and Applications”, Wiley
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ICP-MS
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ICP-MS
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ICP-MS
J. S. Becker, “Inorganic Mass Spectrometry: Principles and Applications”, Wiley
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Glow Discharge Mass Spectrometry
• Direct solids elemental analysis
• Conductive samples via d.c. powering,
insulators via rf
• Extremely stable operation
• Very uniform elemental responses
• Extremely high elemental sensitivity
(sub-ppm in solids)
• Depth profiling with ~10 nm resolution
• Low sample throughput
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GDMS
J. S. Becker, “Inorganic Mass Spectrometry: Principles and Applications”, Wiley
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GDMS
J. S. Becker, “Inorganic Mass Spectrometry: Principles and Applications”, Wiley
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Resonance Ionization Mass Spectrometry
• Elemental specificity based on electronic, optical
transitions
• Elemental selectivity can be fine-tuned to the
isotopic level
• Means of isolating elements that have isobaric
interferences
• Imparting mass resolution not provided by mass
analyzer
• Extremely complex and expensive
instrumentation
• Requires means of converting solid samples into
gaseous atoms
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RIMS
J. S. Becker, “Inorganic Mass Spectrometry: Principles and Applications”, Wiley
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K. B. Knight, M. R. Savina, S. G. Prussin, and I. D. Hutcheon, LLNL CONF 486708
Laser-ablated ions tuned for U off-resonance
tuned for U on-resonance
tuned for Pu on-resonance
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In Summary . . . .
Ion Source Acronym Sample
forms
Sample
introduction Sensitivity
Spatial
resolution
Thermal
ionization TIMS
liquid
(gas)
filament
vaporization pg-ng NA
Secondary
ion SIMS solid sputtering
0.1 ppb-
ppm
<0.2 mm (lat),
1-5 nm
(depth)
Inductively-
coupled
plasma
ICP-MS
solid,
liquid
(gas)
nebulization,
laser ablation,
. .
pg-ng 1-5 mm using
LA
Glow
discharge GDMS
solid
(gas) sputtering
0.1 ppb-
ppm
1-5 nm
(depth)
Resonance
ionization RIMS
solid
(gas)
sputtering,
laser ablation
1-5 mm w/LA
SIMS-like
with ions
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Methods of quantification
• Calibration/response curves
• Relative sensitivity factors (RSFs)
• Isotope dilution mass spectrometry (IDMS)
• Speed and ease
• Susceptibility towards matrix effects
• Extent of prior knowledge about the sample
• Required accuracy
• Required precision
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Calibration curves
• Assumption of some well-behaved relationship between analyte response and concentration
• Some a priori knowledge of analyte concentration
• Matrix matching between sample and standards required
• Most efficient approach if performed in a multi-component mode
• Can be extended to the standard additions method as a means of correcting matrix effects
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Relative sensitivity factors (RSFs)
• de facto use of an internal standard
• Automatically corrects for matrix effects
• Quantification based on the generation of a
response factor relating the counts per unit
concentration of the analyte/standard pair
• Relies on similar chemistries, ionization
efficiencies, and MS detection efficiencies
• Conceptually can use one internal standard for
a diversity of analytes
• Fastest way of performing quantitative analysis
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Isotope Dilution Mass Spectrometry
• An absolute method - A method of chemical
analysis that bases characterization completely
on standards defined in terms of physical
properties
• A definitive method - A method of exceptional
scientific status which is sufficiently accurate to
stand alone in the determination of a given
property for the certification of a reference
material
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IDMS
J. S. Becker, “Inorganic Mass Spectrometry: Principles and Applications”, Wiley
R = NxAx + NsAs
NxBx + NsBs
R=measured ratio, N=#
atoms of x=sample,
s=spike, A & B=isotopic
abundance of x & s
Cx = CsWs As - RBs
Wx RBx - Ax
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Isotope Ratio Mass Spectrometry (IRMS)
J. S. Becker, “Inorganic Mass Spectrometry: Principles and Applications”, Wiley
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The future . . . .
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References
64
• J. S. Becker, “Inorganic Mass Spectrometry:
Principles and Applications”, Wiley, 2007
• D. C. Harris, “Quantitative Chemical Analysis”,
6th Ed., WH Freeman, 2003
• C. Dass, “Fundamentals of Contemporary Mass
Spectrometry”, Wiley, 2007
• F. Adams, R. Gijbels, and R. Van Grieken,
“Inorganic Mass Spectrometry”, Wiley, 1988
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Upcoming Webinars
• Chronometry
• Nuclear Materials Analysis — Radioanalytical Methods (Destructive)
• Development of Signatures
NAMP website: www.wipp.energy.gov/namp