environmental laboratory accreditation course for radiochemistry: day two presented by minnesota...
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Environmental Laboratory Accreditation Course for Radiochemistry: DAY TWO
Presented byMinnesota Department of HealthPennsylvania Department of Environmental ProtectionU.S. Environmental Protection AgencyWisconsin State Laboratory of Hygiene
Instrumentation & Methods: Alpha Scintillation CounterRa226, Ra228
Lynn West
Wisconsin State Lab of Hygiene
Method Review
Radium 226 (EPA 903.1) Radium 228 (EPA 904.0) Alpha-Emitting Radium Isotopes
(EPA 903.0)
Radium Chemistry
Chemically similar to Ca & Ba +2 oxidation state in solution Insoluble salts include: CO3, SO4, &
CrO4
Forms a complex with EDTA Property used extensively in analytical
procedures
Radiochemical Characteristics
Isotope T1/2 Decay Mode
Series
223Ra 11.1 D Alpha Actinium (235U)
224Ra 3.6 D Alpha Thorium (232Th)
226Ra 1622 A Alpha Uranium (238U)
228Ra 5.8 A Beta Thorium (232Th)
Radium 226 (EPA 903.1)
Prescribed Procedures for Measurement of Radioactivity in Drinking Water
EPA 600 4- 80-032 August 1980
Interferences
No radioactive interferences The original method does not use a
yield correction
238U decay series
903.1 Method Summary
1 L acidified sample Ra co-precipitated with stable Ba as
SO4
Precipitate is separated from sample matrix & supernate is discarded
Method summary cont.
(Ba-Ra)SO4 is dissolved in EDTA Solution Transferred to a “bubbler” After a period of ingrowth, 222Rn is
purged for sample & collected in scintillation cell
.
A typical radon de-emanation system
Helium gas in
Vacuum applied
Stopcock 1
Stopcock 2
Stopcock 4
Stopcock 3
Sintered disc
Vacuum gaugeScintillation cell
Stopcock 5
Solutionlevel
Bubbler
Stopcock
O-ring joint
Support
Components
Bubbler Scintillation Cell Vacuum System
& gauge Avoid using Hg
manometer if possible
Scintillation Cell
222Rn from sample is collected in the cell
Progeny establish secular equilibrium in about 4 hrs
The alpha counts from 222Rn & its progeny are collected
Zn(Tl)S
Quartz Window
Alpha Scintillation Cell Counter
Sample counted 4 hrs after de-emanantion
Alpha particles interact with Zn(Ag)S coating & emit light
Light flashes are counted on a scaler
Radon Cell Counters
Instrument Calibration
Each instrument system & scintillation cell needs to be calibrated
Calibration samples should be prepared in the same manner as the samples.
The entire de-emanation system effects the calibration measurement
Use NIST traceable standards
Perform yearly or after repairs
Calculations
)exp(1)exp(
1
)exp(1
1
22.23
3
21t
t
ttYVE
BGD
)exp(1)exp(
1
)exp(1
1
22.2
/)(96.1
3
3
21
3
t
t
ttYVE
tBGUNC
)exp(1)exp(
1
)exp(1
1
22.2
/66.4
3
3
21
3
t
t
ttYVE
tBDL
Calculations cont.
Computer programs should be hand verified
Decay constants and time intervals must be in the same units of time
Minimum background count time should be equal to the minimum sample count time
Method Quality Control
Per each batch of 20 samples, analyze the following: Method blank Laboratory control sample Precision sample Matrix spike sample
Established action limits for each
Method Quality Control, cont.
Instrument operating procedure should describe Daily control charts and acceptance
limits Required action Preventative maintenance
Method SOP main sections
SCOPE AND APPLICATION SUMMARY OF METHOD REGULATORY DEVIATIONS METHOD PERFORMANCE SAFETY SAMPLE HANDLING &
PRESERVATION INTERFERENCES DEFINITIONS EQUIPMENT REAGENTS
METHOD: DETERMINATION OF 226RA
CALIBRATION OF SCINTILLATION CELLS
CALCULATIONS QUALITY CONTROL WASTE DISPOSAL POLLUTION PREVENTION REFERENCES FIGURES
Radium 228 (EPA 904.0)
Prescribed Procedures for Measurement of Radioactivity in Drinking Water
EPA 600 4- 80-032 August 1980
Interferences
The presence of 90Sr in the water samples gives a positive bias to the measured 228Ra activity.
Due to the short half-life of 228Ac, a emitter of similar energy is substituted during instrument calibration. A high or low bias may result depending on which isotope is selected.
Natural Ba may result in falsely high chemical yield.
232Th- decay series
904.0 Method Summary
228Ra in a drinking water sample is co-precipitated with Ba & Pb as SO4
The (Ba-Ra)SO4 precipitate is dissolved in basic EDTA. The progeny, 228Ac, is chemically separated from its parent by repeatedly forming the (Ba-Ra)SO4
Allow at least 36 hrs for the ingrowth of 228Ac & secular equilibrium
904.0 Method Summary, cont.
228Ac is then separated from 228Ra by precipitation as a OH-. (Save supernate)
This is the end of ingrowth & the beginning of 228Ac decay
228Ac is co-precipitated with Y as (Ac-Y2(C2O4)3)
904.0 Method Summary, cont.
Transferred to a planchet & counted on a low-background / proportional counter
The Ba carrier yield is found by precipitating the Ba from the supernatant as BaSO4
Instrumentation
Low background gas flow proportional counter P-10 counting gas (10% CH4 & 90% Ar)
Due to short half-life of 228Ac, a multi-detector system is desirable 6.13 hr Processing time from start of decay to
count is about 250 m
Gas flow proportional counterwindow assembly
Instrument Calibration
Each instrument system needs to be calibrated
Calibration samples should be prepared in the same manner as the samples.
Use isotope with beta energy approximately equal to 0.404 keV
Use NIST traceable standards
Perform yearly or after repairs
Calculations
)exp(
1
)exp(1
1
)exp(122.2132
2
ttt
t
RVE
BGD
)exp(1
)exp(11
)exp(122.2
/)(96.1
132
22
tttt
RVE
tBGUNC
)exp(1
)exp(11
)exp(122.2
/66.4
132
22
tttt
RVE
tBDL
Method Quality Control
Per each batch of 20 samples, analyze the following: Method blank Laboratory control sample Precision sample Matrix spike sample
Established action limits for each
Method Quality Control, cont.
Instrument operating procedure should describe Daily control charts and acceptance
limits Required action Preventative maintenance
Method SOP main sectionsMethod SOP main sections
SCOPE AND APPLICATION SUMMARY OF METHOD REGULATORY DEVIATIONS METHOD PERFORMANCE SAFETY SAMPLE HANDLING &
PRESERVATION INTERFERENCES DEFINITIONS EQUIPMENT REAGENTS
METHOD: DETERMINATION OF 228RA
CALIBRATION OF INSTRUMENT
CALCULATIONS QUALITY CONTROL WASTE DISPOSAL POLLUTION PREVENTION REFERENCES FIGURES
Alpha-Emitting Radium Isotopes (EPA 903.0)
Prescribed Procedures for Measurement of Radioactivity in Drinking Water
EPA 600 4- 80-032 August 1980
Interferences (EPA 903.0)
Natural Ba may result in falsely high chemical yield
Ingrowth of progeny must be corrected for Method only corrects for 226Ra progeny
Does not accurately measure 226Ra if other alpha emitting isotopes are present
Calibration based only on 226Ra
Ac-2286.13 hours
Th-2321.4×1010 y
Ra-2285.75 y
Th-2281.90 y
Ra-2243.64 days
Rn-22054.5 s
Tl-2083.1 m
Po-212300 ns
Po-216158 ms
Pb-208stable
Pb-21210.6 hours
Bi-21260.6 m
Massnumber(N)
Atomicnumber(Z)
67%
33%
beta decay
alpha decay
232Th- decay series
Pa-2341.18 m
238U decay series
beta decay
Atomicnumber(Z)
Massnumber(N)
alpha decay
Po-210138.4 d
U-2384.4×109 y
Th-23424.1 d
U-2342.48×105 y
Th-2308.0×104 y
Ra-2261622 y
Rn-2223.825 d
Pb-206stable
Po-2141.6×10-4 s
Po-2183.05 m
Bi-2105.0 d
Pb-21022 a
Pb-21426.8 m
Bi-21419.7 m
Pa-2313.48×104 y
235U decay series
beta decay
Atomicnumber(Z)
Massnumber(N)
alpha decay
U-2357.3×108 y
Th-23125.6 h
Th-22718.17 d
Ra-22311.7 d
Rn-2193.92 s
Po-2110.52 s
Po-2151.83×10-3 s
Bi-2105.0 d
Pb-207stable
Pb-21136.1 m
Bi-2112.15 m
Ac-22722.0 y
Fr-22322 m
At-2190.9 m
Bi-2158 m
At-21510-4 s
Tl-2074.79 m
903.0 Method Summary
1 L acidified sample Ra co-precipitated with stable Ba &
Pb as SO4 223Ra 224Ra 226Ra
Precipitate is separated from sample matrix & supernate is discarded
903.0 Method Summary, Cont.
Progeny ingrowth starts with the final (Ba-Ra)SO4 precipitation. Since a correction factor is applied to
correct for ingrowth, care needs to be taken to avoid disturbing the radon progeny ingrowth after this step
Transfer to tared planchet & dry under infra-red heat lamp
Instrumentation (EPA 903.0)
Low background gas flow proportional counter P-10 counting gas (10% CH4 & 90% Ar)
Alpha scintillation counter
Instrument Calibration (EPA 903.0)
Each instrument system needs to be calibrated
Calibration samples should be prepared using 226Ra
Use NIST traceable standards
Perform yearly or after repairs
Calculations (EPA 903.0)
RIVEBG
D
22.2
RIVE
tBGUNC
22.2
/)(96.1
RIVEtB
DL
22.2
/66.4
Method Quality Control (EPA 903.0)
Per each batch of 20 samples, analyze the following: Method blank Laboratory control sample Precision sample Matrix spike sample
Established action limits for each Demonstration of capability
Method Quality Control, Cont. (903.0)
Instrument operating procedure should describe Daily control charts and acceptance
limits Required action Preventative maintenance
Method SOP main sectionsMethod SOP main sections (903.0)
SCOPE AND APPLICATION SUMMARY OF METHOD REGULATORY DEVIATIONS METHOD PERFORMANCE SAFETY SAMPLE HANDLING &
PRESERVATION INTERFERENCES DEFINITIONS EQUIPMENT REAGENTS
METHOD: DETERMINATION OF 228RA
CALIBRATION OF INSTRUMENT
CALCULATIONS QUALITY CONTROL WASTE DISPOSAL POLLUTION PREVENTION REFERENCES FIGURES
Instrumentation & Methods: Gamma Spectroscopy
Lynn West
Wisconsin State Lab of Hygiene
Instrumentation – Gamma Spectroscopy/Alpha Spectroscopy
Quick review of Radioactive Decay (as it relates to σ & spectroscopy)
Interaction of Gamma Rays with matter Basic electronics Configurations Semi-conductors Resolution Spectroscopy Calibration/Efficiency Coincidence summing Sample Preparation Daily instrument checks
Review of Radioactive Modes of Decay
Properties of Alpha Decay Progeny loses of 4 AMU. Progeny loses 2 nuclear charges Often followed by emission of gamma
226
88Ra 22286
Rn + 42He + energy
Review of Radioactive Modes of Decay, Cont.
Properties of Alpha Decay Alpha particle and
progeny (recoil nucleus) have well-defined energies
spectroscopy based on alpha-particle energies is possible
Energy (MeV)
Cou
nts
4.5 5.5
Alpha spectrum at the theoretical limit of energy resolution
Review of Radioactive Modes of Decay, Cont.
Properties of beta (negatron) decay No change in mass number of progeny. Progeny gains 1 nuclear charge Beta particle, antineutrino, and recoil
nucleus have a continuous range of energies
no spectroscopy of elements is possible Often followed by emission of gamma
Review of Radioactive Modes of Decay, cont.
Cou
nts
Ar-36
Cl-36
Energy (MeV)
Beta Emission from Cl-36.
From G. F. Knoll,Radiation Detection and Measurement, 3rd Ed., (2000).
Review of Radioactive Modes of Decay, Cont.
Properties of Positron decay No change in mass number of progeny Progeny loses 1 nuclear charge Positron, neutrino, and recoil nucleus
have a continuous range of energies no spectroscopy of elements is possible
Positron is an anti-particle of an electron
Review of Radioactive Modes of Decay, Cont.
Properties of Positron decay When the positron comes in contact
with an electron, the particles are annihilated
Two photons are created each with an energy of 511 keV (the rest mass of an electron)
The annihilation peak is a typical feature of a spectrum
Review of Radioactive Modes of Decay, Cont.
Other modes of decay Electron Capture
Neutron deficient isotopes Electron is captured by the nucleus from
an outer electron shell Vacancy left from captured electron is
filled in by electrons from higher energy shells
X-rays are released in the process
Review of Radioactive Modes of Decay, Cont.
Other modes of decay Auger electrons
Excitation of the atom resulting in the ejection of an outer electron
Internal conversion electrons Excitation of the nucleus resulting in the
ejection of an outer electron Bremsstrahlung
“Braking” radiation Photon emitted by a charged particle as it
slows down Adds to the continuum
Review of Radioactive Modes of Decay, Cont.
Gamma Emission No change in mass, protons, or
neutrons Excess excitation energy is given off as
electromagnetic radiation, usually following alpha or beta decay
Gamma emissions are high-energy, short-wave-length
Source:
http://lasp.colorado.edu
Review of Radioactive Modes of Decay, Cont.
Gamma Emission Decay Schemes
Pb S
hie
ldin
g
Pb S
hie
ldin
g
e-
e
511 γ
511 γ
γ
γ
Pb X Ray
e-
PE
e-
e-
CS
γ γ
Source
γ
γ
γe 511 γ
511 γ
e-
e-
e-PP
CS
CS
KEYPE Photoelectric absorptionCS Compton scatteringPP Pair productionγ gamma-raye- ElectronePositron
Gamma Spectrum Features
Source: Practical Gamma-Ray Spectrometry, Gilmore & Hemingway
Resolution
Basic Electronic Schematic – Gamma Spectroscopy
Detector Bias Supply
Detector PreamplifierMultichannel Analyzer (MCA)Amplifier
Low Voltage Supply
Configurations of Ge Detectors
Electrical contact
True coaxial Closed-end coaxial
Holes
Electrons
+
Holes
Electrons
p-type coaxial, ∏-type
n-type coaxial, v-type
p+ contact
n+ contact
Nature of Semi-conductors
Good conductors are atoms with less than four valence electrons
atoms with only 1 valance electron are the best conductors
examples copper silver gold
Nature of Semi-conductors, Cont.
Good insulators are atoms with more than four valence electrons
atoms with 8 valance electron are the best insulators
examples noble gases
Nature of Semi-conductors, Cont.
Semiconductors are made of atoms with four valence electrons
they are neither good conductors nor good insulators
examples germanium silicon
Nature of Semi-conductors, Cont.
Energy Band Diagram
VALENCE BANDVALENCE BAND
FORBIDDEN BAND
VALENCE BAND
FORBIDDEN BAND
CONDUCTION BAND CONDUCTION
BANDCONDUCTION
BAND
Insulator Semiconductor Conductor
Nature of Semi-conductors, Cont.
Covalent bonds are formed in semiconductors the atoms are arranged in definite
crystalline structure the arrangement is repeated
throughout the material each atom is covalently bonded to 4
other atoms
Nature of Semi-conductors, cont. Pure Semi-conductor
Each atom has 8 shared electrons there are no free electrons
or no electrons in the conduction band however, thermal energy can cause
some valence electrons to gain enough energy to move in to the conduction band this leads to the formation of a “hole”
Nature of Semi-conductors, cont. Pure Semi-conductor
Both holes (+) & free electrons (-) are current carriers
a pure semi conductor has few carriers of either type
more carriers lead to more current doping is the process used to
increase the number of carriers in a semiconductor
Nature of Semi-conductors, cont. Pure Semi-conductor
Impurities can be added during the production of the semiconductor, this is called doping
The impurities are either trivalent or pentavalent
trivalent examples indium, gallium, boron
pentavalent examples arsenic, phosphorus, antimony
n-type Semiconductor
An impurity with 5 valence electrons (group V) will form 4 covalent bonds with the atoms of the semiconductor
One electron is left over & loosely held by the atom
This type of impurity is known as donor impurities.
There are more negative carriers
n-type Semiconductor
VALENCE BAND
CONDUCTION BAND
Valence electron forbidden band
Donor electron forbidden band
Donor electron Energy level
p-type semiconductors
An impurity with 3 valence electrons (group III) will form 3 covalent bonds with the atoms of the semiconductor
The absence of the fourth electron leaves a hole
This type of impurity is known as acceptor impurities.
There are more positive carriers
p-type Semiconductor, cont.
VALENCE BAND
CONDUCTION BAND
Valence electron forbidden band
Acceptor hole forbidden band
Acceptor hole Energy level
Depletion Zone
In the depletion zone the charge carriers have canceled each other out
voltage is developed across the depletion zone due to the charge separation
+-
p-type n-type
Vc
Depletion zone
V
+
++
+ ++
+
+
++
+ ---
-
- --- -
++++
+++
++
++
+
------
---
-
Calibration/Efficiency
Ideally, calibration sources would be prepared such that a point calibration is performed for each nuclide reported this is totally impractical for analyzing
routine unknown samples Sources should be prepared to have
identical shape and density as the sample
Calibration/Efficiency
Differences in density are less important than differences in geometry Newer software packages allow the
user to create different efficiencies mathematically
Source strength should not be so great as to cause pile-up
Calibration/Efficiency
The calibration energies should cover the entire range of interest
For close to the detector geometries, choose a multi-lined source made from a combination of nuclides which do not suffer from True Coincidence Summing (TCS). See Table 7.2 pg 153 Gilmore, G. and Hemingway, J. 1995. Practical Gamma-Ray Spectrometry. John Wiley & Sons, New York
Coincidence Summing
True Coincidence Summing (TCS) The summing of gamma rays emitted
almost simultaneously from the nucleus resulting in a negative bias from the true value
Larger detectors suffer more from TCS than do smaller detectors
TCS can be expected whenever samples contain nuclides with complicated decay schemes
Coincidence Summing
True Coincidence Summing (TCS) TCS can be expected whenever
samples contain nuclides with complicated decay schemes
The degree of TCS is not dependent on count rate
TCS is geometry dependent and is worse for close to the detector geometries
Coincidence Summing
True Coincidence Summing (TCS) TCS is geometry dependent and is
worse for close to the detector geometries
Summed pulses will not be rejected by the pile-up rejection circuitry because the pulses will not be misshapen
For detectors with thin windows X-rays that would normally be absorbed in the end cap may contribute to TCS
Well detectors suffer the worst from TCS
Coincidence Summing
True Coincidence Summing (TCS) Newer software packages have systems
for reduces this problem
Coincidence Summing
Random Coincidence Summing Also known as pile-up Two or more gamma rays being
detected at nearly the same time Counts are lost from the full-energy
peaks in the spectrum Affected by count rate Pile-up rejection circuitry reduces
problem
Sample Preparation
Acidify water samples Note: Iodine is volatile in acidic solutions
Active material should be distributed evenly throughout the geometry Samples should be homogenous
Calibration materials should simulate samples (actual or mathematical)
Daily Instrument Checks
Short background count Linearity check Resolution check Additionally, a long background
count is needed for background subtraction
Instrumentation & Methods: Gamma Emitting Radionuclides USEPA 901.1
Jeff Brenner
Minnesota Department of Health
EPA Method 901.1Gamma Emitting Radionuclides
Gamma Emitting Radionuclides
EPA Method 901.1What we’ll cover Scope of the method Summary of the method Calibration
Determining energy calibration Determining efficiency calibration Determining system background
Quality control Interferences Application Calculations
Activity
EPA Method 901.1Scope
The method is applicable for analyzing water samples
Measurement of gamma photons emitted from radionuclides without separating them from the sample matrix.
Radionuclides emitting gamma photons with the following energy range of 60 to 2000 keV.
EPA Method 901.1 Gamma Emitting Radionuclides Summary
Water sample is preserved in the field or lab with nitric acid
Homogeneous aliquot of the preserved sample is measured in a calibrated geometry.
EPA Method 901.1 Gamma Emitting Radionuclides Summary
Sample aliquots are counted long enough to meet the required sensitivity.
EPA Method 901.1 Gamma Emitting Radionuclides Summary
EPA Method 901.1 Gamma Emitting Radionuclides Summary
EPA Method 901.1 Calibrations Gamma Emitting Radionuclides
Library of radionuclide gamma energy spectra is prepared
Use known radionuclide concentrations in standard sample geometries to establish energy calibration.
Single solution containing a mixture of fission products emitting Low energy Medium energy High energy Example (Sb-125, Eu154, and Eu-155)
EPA Method 901.1 Gamma Emitting Radionuclides Summary
86.54 Eu-155 105.31 Eu-155 123.07 Eu-154 176.33 Sb-125 247.93 Eu-154 427.89 Sb-125 463.38 Sb-125 591.76 Eu-154 600.56 Sb-125 635.90 Sb-125 692.42 Eu-154 723.30 Eu-154 756.86 Eu-154 873.20 Eu-154 996.30 Eu-1541004.76 Eu-1541274.51 Eu-1541596.45 Eu-154
EPA Method 901.1 Gamma Emitting Radionuclides
Counting efficiencies for the various gamma energies are determined from the activity counts of those known standard values.
A counting efficiency vs. gamma energy curve is determined for each container geometry and for each detector.
EPA Method 901.1 Gamma Emitting Radionuclides Summary
86.54 Eu-155
105.31 Eu-155
176.33 Sb-125
427.89 Sb-125
463.38 Sb-125
600.56 Sb-125
996.30 Eu-154
1004.76 Eu-154
1274.51 Eu-154
EPA Method 901.1 Calibrations Gamma Emitting Radionuclides
FWHM used to monitor peak shape Smaller tolerance for low energy Greater tolerance for high energy
Document a few FWHM to determine instrument drift
EPA Method 901.1 Gamma Emitting Radionuclides Summary
86.54 Eu-155 105.31 Eu-155 123.07 Eu-154 176.33 Sb-125 247.93 Eu-154 427.89 Sb-125 463.38 Sb-125 591.76 Eu-154 600.56 Sb-125 635.90 Sb-125 692.42 Eu-154 723.30 Eu-154 756.86 Eu-154 873.20 Eu-154 996.30 Eu-1541004.76 Eu-1541274.51 Eu-1541596.45 Eu-154
EPA Method 901.1 Gamma Emitting Radionuclides Summary
EPA Method 901.1 (Determine System Background)
Contribution of the background must be measured
Measure under the same conditions, counting mode, as the samples
Background determination is performed every time the liquid nitrogen is filled
EPA Method 901.1 (Batch Quality Control)
Instrument efficiency check Analyzed daily Control chart Establish action limits
Low background check Analyzed weekly Control chart Establish action limits
Analytical Batch Sample Duplicates at a 10% frequency Sample Spikes at a 5% frequency Control chart Establish action limits
EPA Method 901.1Interferences Significant interference occurs when
counting a sample with a NaI(Tl) detector. Sample radionuclides emit gamma
photons of nearly identical energies. Sample homogeneity is important to
gamma count reproducibility and counting efficiency. Add HNO3 to water sample container to
lessen the problem of radionuclides adsorbing to the container
EPA Method 901.1Application
The limits set forth in PL 93-523, 40 CFR 34324 recommend that in the case of man-made radionuclides, the limiting concentration is that which will produce an annual dose equivalent to 4 mrem/year.
If several radionuclides are present, the sum of their annual dose equivalent must not exceed 4 mrem/year.