analisi di fluorescenza x a dispersione di energia tradizionale ed … · 2010. 2. 5. · x-ray...
TRANSCRIPT
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Analisi di Fluorescenza X a dispersione di energia
Tradizionale ed in Riflessione Totale(EDXRF e TXRF)
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40 eV
400 keV
1 keV
40 keV
The EM spectrum – X-RaysThe EM spectrum – X-Rays
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Interactions of X-Rays with matterInteractions of X-Rays with matter
X-ray Source Sample
Photoelectricabsorption
Elastic (Rayleigh)Scattering
Inelastic (Compton)Scattering
-
Incident photon
X-ray fluorescenceX-ray fluorescence
Photoelectron
Fluorescencephoton
-
Incident photon
Competition: Auger effectCompetition: Auger effect
Photoelectron
Augerelectron
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Fluorescence yieldFluorescence yield
0 20 40 60 800.0
0.2
0.4
0.6
0.8
1.0
ωK 1-ωK ωL 1-ωL
Fluorescent Yield
Auger Electron Yield
Atomic Number Z
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Transition probabilitiesTransition probabilities
Germanium
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X-Ray line families - KX-Ray line families - K
5000 6000 7000 8000 9000 100000.00.20.40.60.81.01.21.41.61.82.02.22.4
counts
/(ch
annel
sec
ond)
photon energy [eV]
Fe K
21000 22000 23000 24000 25000 260000
2
4
6
8
10
12
14
16
18
counts
/(ch
annel
sec
ond)
photon energy [eV]
Ag K
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8000 10000 12000 14000 160000
1
2
3
4
5
counts
/ (
chan
nel
sec
ond)
photon energy [eV]
X-Ray line families - LX-Ray line families - L
Pb L
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Typical energy dispersive set-upTypical energy dispersive set-up
ADC
Pulse heightdiscriminator
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X-raytube
Primarybeam
Fluorescenceradiation
Sample
Energy-dispersivedetector
Conventional EDXRFConventional EDXRF
X-raytube
Sample onOptical flat
Fluorescenceradiation
Energy-dispersivedetector
Totally reflectedbeam
TXRFTXRF
Comparison shows a difference in the geometric grouping ofexcitation and detection units
Comparison shows a difference in the geometric grouping ofexcitation and detection units
TXRF and EDXRF geometriesTXRF and EDXRF geometries
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5 6 7 8 9 10
Ni K edge
Ni Kα
Fe
Cr K edge
Cr Kα
Cr Fe Ni
Energy [keV]
enhancement
absorption
The XRF quantification problemThe XRF quantification problem
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The XRF quantification problemThe XRF quantification problem
Monochromatic
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Thin layer approximationThin layer approximation
No dependence on other elements (matrix)
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TXRFTXRF
EDXdetector
Incident X-ray beam
ReflectedX-raybeam
Reflector
• Thin sample layer deposited on a reflector• The total reflection effect makes the sample support “almost invisible”
n (x-ray range ) = 1- δ - iβ
δ ~ 10-6β ~ 10-8
ϕ critical ≈ √ 2 δ
ϕ critical(Si, 17.5 keV) = 0.1°
= 1.75 mrad
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TXRF basicsTXRF basics
0 1 2 3 4 50.0
0.2
0.4
0.6
0.8
1.0
reflec
tivi
ty,
tran
smittivi
ty
incidence angle [mrad]
reflectivity
transmittivity
Quartz reflectorMo Kα radiation
Incidentbeam
Reflectedbeam
Refractedbeam
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TXRF basicsTXRF basics
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
criticalangle
Background
Fluorescenceline
Arbitrary units
angle [mrad]
Line intensityIL∝ ( 1 + R )
BackgroundIB∝ ( 1 - R ) sinφ
Quartz reflectorMo Kα radiation
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15 200
2000
scatter
Mo
Nb
Rb
Cou
nts
/ cha
nnel
Energy [keV]
massNet
BackgroundDL 3=
timeDL 1∝
Detection limitsDetection limits
16.0 16.2 16.4 16.6 16.8 17.00
500
1000
1500
Nb
Cou
nts
/ cha
nnel
Energy [keV]
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Easy quantification - Taking ratiosEasy quantification - Taking ratios
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Internal standard – relative sensitivitiesInternal standard – relative sensitivities
CALIBRATE
QUANTIFY UNKNOWNS
Compare with theory
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Mo Ka - calibration curveMo Ka - calibration curve
5 10 15 20 25 30 35 50 60 70 80 901E-4
1E-3
0.01
0.1
1
rela
tive
sens
itivi
ty to
Ga
Z
measured fundamental parameters Polynomial Fit of Kα data Exp fit of Lα data
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Principle of TXRFPrinciple of TXRF
EDXdetector
Incident X-ray beam
ReflectedX-raybeam
Reflector
ADVANTAGESADVANTAGES
• Background reduction• Background reduction
• Double excitation of sample by both the primary and reflected beam• Double excitation of sample by both the primary and reflected beam
• Small distance sample-detector(~1mm) large solid angle• Small distance sample-detector(~1mm) large solid angle
• Small sample volumes required• Small sample volumes required
• Detection limits in the pg range with X-ray tube excitation• Detection limits in the pg range with X-ray tube excitation
DISAVANTAGESDISAVANTAGES
• Collimated beam required• Collimated beam required
• Sample preparation necessary for non liquid samples• Sample preparation necessary for non liquid samples
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Comparison between TXRF and EDXRF spectrum
Comparison between TXRF and EDXRF spectrum
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Main Advantages of TXRFMain Advantages of TXRF
• No matrix effects• No matrix effects
• A single internal standard greatly simplifies quantitative analyses
• A single internal standard greatly simplifies quantitative analyses• Calibration and quantification independent from any sample matrix
• Calibration and quantification independent from any sample matrix• Simultaneous multi-element ultra-trace analysis• Simultaneous multi-element ultra-trace analysis• Several different sample types and applications• Several different sample types and applications• Minimal quantity of sample required for the measurement (5 µl)
• Minimal quantity of sample required for the measurement (5 µl)
• Unique micro analytical applications for liquid and solid samples
• Unique micro analytical applications for liquid and solid samples• Excellent detection limits (pptor pg) for all elements from sodium to plutonium
• Excellent detection limits (pptor pg) for all elements from sodium to plutonium• Excellent dynamic range from ppt to percent• Excellent dynamic range from ppt to percent• Possibility to analyse the sample directly without chemical pre-treatment
• Possibility to analyse the sample directly without chemical pre-treatment• No memory effects• No memory effects
• Non destructive analysis• Non destructive analysis
• Low running cost• Low running cost
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The TXRF equipmentThe TXRF equipment
Main components:• Double anode Mo/W X-ray tube• Multilayer monochromator
MoKα, WLα/β, Bremsstr.• TXRF and EDXRF chambers•High resolution Si(Li) detector
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Front viewFront view
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Back viewBack view
Minimum angular step
• monochromator 0.0074°
• tube shield 0.0016°
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Alignment windowAlignment window
Control
• multilayer
• tube shield
Visualise
• X-ray line counts
• Total counts
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• TXRF and EDXRF (traditional45° geometry) spectroscopy inthe same equipment
• TXRF and EDXRF (traditional45° geometry) spectroscopy inthe same equipment
• Automatic switching of primary beam (MoKα W/Lα and Brems-strahlung 33 keV) using double anode Mo/W X-ray tube, based on innovative software. We select the energy required using a high reflectivity 80% (WLα/Lβ/MoKα) multilayer. We can choose also other X-ray tubes and monochromatise the energy that you need
• Automatic switching of primary beam (MoKα W/Lα and Brems-strahlung 33 keV) using double anode Mo/W X-ray tube, based on innovative software. We select the energy required using a high reflectivity 80% (WLα/Lβ/MoKα) multilayer. We can choose also other X-ray tubes and monochromatise the energy that you need• 3.8 liters UHV (Si(Li) 20 mm2detector area) high resolution detector
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Multielement standard - WLβMultielement standard - WLβ
0 1 2 3 4 5 6 7 8 9 100
1000
2000
3000
4000
5000
6000
counts
/channel
photon energy [keV]
Zn
CuNi
Co
FeMn
Cr
KCaBa
Ba
Tl, Pb, Bi
Al SiSr
Kα
Kβ
Lα
Lβ
M
CuNiAgCd
W Lβscatter
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0 2 4 6 8 10 12 14 16 180
1000
2000
3000
4000
5000
6000
7000
8000
counts
/ c
han
nel
photon energy [keV]
Sr
GaZn
CuNi
CoFe
MnCr
KCa
Moscatter
TlPb
Bi
Tl BiPb
Sr
BaBa
Tl, Pb, Bi
ZnAl
SiSr
PbBi
Kα
Kβ
Lα
Lβ
Lγ
M
Multielement standard - MoKαMultielement standard - MoKα
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Multielement standard – 33keVMultielement standard – 33keV
10 20 30 400
2000
4000
6000
8000 lines
LβLα
KβKα Multielement sample10 ng CdW white spectrum monochromatised at about 33 keVload: 45 kV 20 mA; 500s
TlBiTl
PbBi Pb
CrMnFeCo
Ni
Cu
Zn
Ga
Ca
K
Sr
In
Zr
ZrSr Ag
Cd
Cd
In
Ag
W white spectrumscattered radiation
counts
E (keV)
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Excitation radiation
W-L LineW-white Line
Mo-K Line
< 5 pg 5-10 pg 10-30 pg 30-100 pg >100 pg
Detection Limits
Elemental sensitivity periodic tableElemental sensitivity periodic table
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A droplet of 10 µL is pipetted on a carrier with a diameter of 3 cmThe droplet leaves a dry residue after evaporation.
A droplet of 10 µL is pipetted on a carrier with a diameter of 3 cmThe droplet leaves a dry residue after evaporation.
Sample holderSample holder
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Sample preparation schemeSample preparation scheme
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Preparation of a TXRF measuring samplePreparation of a TXRF measuring sample
Aliquotationof some mL
Addition ofsome µLinternalstandard
Homogenizationby shaking
Taking offsome µL
Pipetting onclean carrier
Drying byevaporation
Measurement
Si(Li)-Detector
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ApplicationsApplications
•Environmental Analysis: water, dust, sediment, aerosol•Environmental Analysis: water, dust, sediment, aerosol
• Medicine: toxic elements in biological fluids and tissue samples
• Medicine: toxic elements in biological fluids and tissue samples
• Forensic Science: analysis of extremely small sample quantities
• Forensic Science: analysis of extremely small sample quantities
• Pure chemicals: acids, bases, salts, solvents, water, ultra pure reagents
• Pure chemicals: acids, bases, salts, solvents, water, ultra pure reagents
• Oils and greases: crude oil, essential oil, fuel oil• Oils and greases: crude oil, essential oil, fuel oil
• Pigments: ink, oil pants, powder• Pigments: ink, oil pants, powder
• Semiconductor Industry(direct or after VPD-VPT)• Semiconductor Industry(direct or after VPD-VPT)
• Nuclear Industry: measurements of radioactive elements
• Nuclear Industry: measurements of radioactive elements
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Spectrum of detection limits Chromium in distilled water
Spectrum of detection limits Chromium in distilled water
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Example of detection limits Chromium in distilled water
Example of detection limits Chromium in distilled water
6.2512530050 (5 x 10)1.97
4.008050050 (5 x 10)1.97
4.4044030010 (5 x 2)1.97
4.0040050010 (5 x 2)1.97
3.50355000100 (5 x 20)24.5
5.50551000100 (5 x 20)24.5
7.0070500100 (5 x 20)24.5* (spectr.)
8.5017030050 (5 x 10)24.5
6.0012050050 (5 x 10)24.5
3.7037050010 (5 x 2)24.5
Detection Limit (pg) = ppt x
µl/1000
Detection Limit (ppt)
Live Time(seconds)
Volume µl(5 x N)
Concentration (ppb)
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Choice of the anodeChoice of the anode
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Forensic: gunshot powderForensic: gunshot powder
coun
ts /
chan
nel
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0 5 10 15 200
200
400
600
800
Fi 5
counts
Pb
Pb
SrRb
Br
Ni CuZn
Zn
CuNi
CoFe
Fe
Cr
CrTi
Ti
Ca
Ca
K
ArCl
S
P
Si
Moscattered radiation
black wool, acrylic and polyammide fiber white cotton fiber fiber from gray thermic gloves
E(keV)
Forensic: fiber analysisForensic: fiber analysis
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Food industry: wineFood industry: wine
0 2 4 6 8 10 12 14 16 18 200
100
200
300
400
500
600
1000
10000
counts
/channel
photon energy [keV]
white wine red wine must
Mo Kα40kV 30mA 500s
Ga int standard
white red mustAl 9.397P 41.987S 8.718 162.824 6.144Cl 1.355 31.139 20.424K 1.956 691.89 709.589
Ca 20.674 53.741 29.24Mn 0.875 0.299Fe 0.063 4.39 0.392Ni 0.02Cu 0.081 9.049Zn 0.057 0.507 0.606Br 0.006 0.172Rb 1.547 0.544Sr 0.142 0.577Pb 0.011 0.025
RbGa
Zn
CuFe
MnCr
K
Ca
Moscatter
Pb
Pb
ZnAl
Kα
Kβ
Lα
Lβ
SrSi
Ca
P
S
Cl
Rb
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Industrial application case study:Petrochemical transformation
Industrial application case study:Petrochemical transformation
Monitor corrosion phenomena and possibly give indications on the origin (Fe, Ni, Cr, Mn)
Process assistance and quality control
Individuate transport processes of elements deriving for catalyst (Co, Ni, Pt, Rh, Cr, Cu, …)
Logistics
• Search the probable causes of deterioration (contamination) of the products during Transport and Stocking – Reflects on product price and on logistic costs (e.g. ship stop)
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Raw materials for intermediate products
Intermediate compounds for the synthesis of final products destined to high consumption markets
Cosmetics
Detergents
Lubrication
Paper Industry
Plastics
Food industry
Leather industry
The limits for the metals content are regulated by different norms, mostly dictated by Acceptance Specifications of the client.
ApplicationsApplications
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Olefin C10-13Olefin C10-13
Conc. (ppm) ICP TXRF
Ca 0.36 0.45Cd
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Linear paraffin C10-13Linear paraffin C10-13
Conc. (ppm) ICP TXRF
Ca 0.18 0.13Cd 0.009
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Detection limits: ICP-OES vs. TXRFDetection limits: ICP-OES vs. TXRF
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
Ca V Cr Mn Fe Ni Co Cu Zn Sr Mo Rh Cd Sn Pb
ppm
ICP
TXRF
ICP-OES (ASTM: D 5708-B)Campione : 10g @ 25 ml
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Correlation ICP-OES vs. TXRFCorrelation ICP-OES vs. TXRF
0.0 0.2 0.4 0.6 0.8
0.0
0.2
0.4
0.6
0.8
TXR
F (p
pm)
ICP OES (ppm)
ICP-OES vs. TXRFPaired t-test : results do not differ significantlyLinearly correlated
Y = A + B * X N = 32 R = 0.998 --------------------------------------Param Value IC (t*s)--------------------------------------A -0.0039 0.0046B 1.0137 0.0252-------------------------------------
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ICP-OES TXRF
Sensitivity Comparable, except for Rh and PbDecreases with atomic
number
Sample preparation
Time consuming treatment (days) with risk of
contaminationSimple and fast
Time 3-4 days A few hours (about 3)
CalibrationMultielement: depending
on the element to be determined
ONE ONLY internal standard
Field of application
"non volatile” metals (no Hg, Se, As..)
Simultaneous and accurate determination of the elements with Z > 15
ConclusionsConclusions
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Environmental: soilEnvironmental: soil
0 2 4 6 8 10 12 14 16 18
20
40
60
80
100
120
1000
10000
counts
/chan
nel
photon energy [keV]
Sr
Ga
ZnCu
Ni
Fe
Mn
K
Ca
Moscatter
Pb
Pb
Rb
Al
Kα
Kβ
Lα
Lβ
Rb
Fe
Ca
Si S
Fe e
scap
e GaAs
Microwave mineralisation in10 ml HNO3. Final volume 50 ml
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0 5 10 15 200
200
400
600
800
1000
1200
1400
Sorgente di Mo 35 kV, 30 mA10 μL di campioneTempo di conteggio 200 s.
Benzina Standard ICIP Pb 0.324 g/l
PbPbPb
Pb
Pb
Moradiazione scatterata
Ga Kβ
Ga Kα 15 ppmstandard interno
VS
Si
Conteggi
E (keV)
Counts
Standard Petrol ICP Pb 0.324 g/l
Internal standard
Scattered radiation
Mo X-ray tube 35kV, 30mASample: 10 µLLive time: 200 s
Environmental: gasolineEnvironmental: gasoline
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Environmental: compostEnvironmental: compost
microwave
microwaveTXRF no treatment
ARPAVRING_3-02: esercizio di interconfronto
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Particulate matter monitoringParticulate matter monitoring
Multi-stage Cascade impactors can be usedin order to collect the the particulate matter onto standard quartz carriers that can be analysed directly with the TXRF without anysample preparation.
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SeldomSeldomFrequentlyMaintenance
HighLowHighRunning costs
Very highMediumMediumCapital costs
Nuclear reactor + γ-spectrometer
Special EDSAr-plasma + quadrupoleMS
Equipment
Expenditure
20 min – 30 days< 20 min< 3 minTime consumption
NoNoYesMemory effects
NoneNoneSevereMatrix effects
Some pure element foilsOne internal standardSeveral external and internal standards
Calibration
Quantification
NoNoYesIsotope detection
FewFewSeveralSpectral interferences
Z < 9; Tl, Pb, BiZ < 13H, C, N, O, F, P, SElement limitations
Very goodVery goodExcellentDetection limits
Detection
NoNoYesConsumption
NoneNone1:100Diluition of acids
Any< 1%< 0.4%Dissolvation portion
NoneDigestion or suspensionDigestion or suspensionPreparation of solid
10-200 mg5-50 µL2-5 mLVolume or mass
Samples
INAATXRFICP-MSAnalytical Features
Comparison of Important Analytical Features of the Three Competitive Methods
Comparison of Important Analytical Features of the Three Competitive Methods
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Benefits and Drawbacks of TXRF Applied to Element Analyses
Benefits and Drawbacks of TXRF Applied to Element Analyses
• Unique micro analytical capability• Unique micro analytical capability
• Great variety of samples and applications• Great variety of samples and applications
• Simultaneous multielementdetermination• Simultaneous multielementdetermination
• Low detection limits• Low detection limits
• Impossibility of totally non-destructive analysis• Impossibility of totally non-destructive analysis
• Limitation for non-volatile liquids• Limitation for non-volatile liquids
• Exception of low-Z elements• Exception of low-Z elements
• Limitation by high matrix contents• Limitation by high matrix contents
Benefits:Benefits: Drawbacks or limitations:Drawbacks or limitations:
• Simple quantification by internal standardization• Simple quantification by internal standardization
• No matrix or memory effects• No matrix or memory effects
• Wide dynamic range• Wide dynamic range
• Non-destructive surface and thin-layer analysis• Non-destructive surface and thin-layer analysis
• Simple automated operations• Simple automated operations
• Low running costs and maintenance• Low running costs and maintenance
• Restriction to flat or polished samples• Restriction to flat or polished samples
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ReferencesReferences
R. Klockenkämper, Total-Reflection X-Ray Fluorescence Analysis, John Wiley and Sons Inc., New York, 1997, ISBN 0-471-30524-3
Spectrochimica Acta Part B: Atomic SpectroscopyTXRF Special Issues – TXRF conference proceedings
Vol. 44, Issue 5 (1989) Vol. 46, Issue 10 (1991) Vol. 48, Issue 2 (1993)Vol. 52, Issue 7 (1997)Vol. 54, Issue 10 (1999)Vol. 56, Issue 11 (2001)Vol. 58, Issue 12 (2003)
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ReferencesReferences
Total Reflection XRF (TXRF), P.Kregsamer, C.Streli, P.Wobrauschek,Book chapter "Handbook of X-ray Spectrometry",Ed: R.Van Grieken, A.Markowicz, Marcel Dekker, 2002
Handbook of X-Ray SpectrometryRene E. Van GriekenAndrzej A. Markowicz
ISBN: 0824706005Publisher: Marcel Dekker
Total Reflection X-ray Fluorescence Analysis,P.Wobrauschek, C.Streli, Chapter in :Encyclopedia of Analytical Chemistry,Ed.:R.A.Meyers,Wiley & Sons, 2000, 13384-13414