QXAS Manual

QXAS
Quantitative X-ray Analysis System
IAEA
Documentation Version 2.0 (2005)

2
FOREWORD
The QXAS is a comprehensive quantitative analysis package that has been developed by the
IAEA through using research and technical contracts, as well as inviting short-term experts.
Additional development has also been carried out in the IAEA Laboratories in Seibersdorf as
well as extensively tested. The present manual covers the version 3.6 of this software
package, and is the most recent update. It is a trimmed-down and re-arranged version that
includes the frequently used packages in the software. The new additions in this version are
the Voigt peak fitting profile, and the Backscatter Fundamental Parameters’ (BFP) method.
Also included is a description of the Emission-Transmission method (ET-10).
QXAS as well as the other IAEA software packages for nuclear analysis are distributed free
of charge. The IAEA is not responsible or liable for the accuracy of analytical results
produced using QXAS. Such accuracy depends, among other factors, on sample preparation
issues, calibration procedures, experimental aspects, experience, etc, many of which are in
the hands of the user. Many good and accurate results using the QXAS have been published
in peer review journals.
Any queries, comments, or suggestions for improvement may be directed to:
XRF Group
IAEA Laboratories Seibersdorf
A-2444 Seibersdorf, Austria
E-mail: Official.Mail@iaea.org
Fax: +43 1 2600 28222
3
4
TABLE OF CONTENTS
INTRODUCTION ................................................................................................................................................ 9
1. INTRODUCTION TO THE SPECTRUM FITTING (AXIL)............................................................................................ 9
1.1 Conventions ................................................................................................................................................. 9
2. INTRODUCTION TO THE QUANTITATIVE METHODS.......................................................................................... 10
3. DESCRIPTION OF THE MAIN MENU.................................................................................................................... 11
4. BRIEF HISTORY OF QXAS.................................................................................................................................. 12
QXAS INSTALLATION PROCEDURE ......................................................................................................... 14
1. SYSTEM HARDWARE SETUP ................................................................................................................................ 15
1.1 SELECTION OF GRAPHICS ADAPTER AND OTHER HARDWARE ............................................................................ 15
1.2 SELECTION OF COMMUNICATION PARAMETERS................................................................................................ 16
2. STARTING AXIL................................................................................................................................................ 16
SPECTRUM FORMAT CONVERSION ......................................................................................................... 18
1. PROGRAM FLOW ................................................................................................................................................ 18
2. DETAILED DISCUSSION....................................................................................................................................... 18
SPECTRUM FITTING...................................................................................................................................... 26
1. MENU AXIL (& VOIGT PEAK PROFILES OPTION FOR HIGH ENERGY K-LINES) .................................................. 26
1.1 MENU Load............................................................................................................................................... 28
1.2 Calibration (MENU Calib)........................................................................................................................ 28
1.3 Select (groups of) Lines (MENU X-lines) .................................................................................................. 30
1.3.1 X-LINES ADD el-group ...................................................................................................................................... 31
1.3.2 Voigt Peak Profiles............................................................................................................................................... 31
1.3.3 X-LINES ADD el-group,inc / el-group,coh ......................................................................................................... 33
1.3.4 X-LINES ADD ener, rin ...................................................................................................................................... 34
1.3.5 X-LINES ADD SUM ........................................................................................................................................... 35
1.3.6 X-LINES REMOVE el-group .............................................................................................................................. 35
1.3.7 X-LINES REMOVE ALL.................................................................................................................................... 35
1.3.8 X-LINES SHOW.................................................................................................................................................. 35
1.4 Select ROI (MENU ROI)............................................................................................................................ 35
1.5 Select Background (MENU Backgrnd)...................................................................................................... 36
1.6 Fit Spectrum (MENU FIT)......................................................................................................................... 36
1.7 Inspect Reports (MENU Reports) .............................................................................................................. 37
1.8 Make Result File (Sav_Res)....................................................................................................................... 38
1.9 Analyze Spectrum in Batch Mode (&BATCH)........................................................................................... 38
1.10 MENU Stop.............................................................................................................................................. 39
1.11 MENU Display......................................................................................................................................... 39
1.12 MENU KLM-mark ................................................................................................................................... 40
1.13 MENU SCAT_ROI ................................................................................................................................... 40
1.14 MENU PLOT ........................................................................................................................................... 40
2. MENU SPECIFY PARAMETERS FOR SPECTRUM ANALYSIS .................................................................................. 41
3. MENU MANAGE X-RAY LIBRARY ..................................................................................................................... 48
QUANTITATIVE ANALYSIS.......................................................................................................................... 54
DIRECT COMPARISON OF COUNT RATES.............................................................................................. 56

1. INTRODUCTION .................................................................................................................................................. 56
2. CALIBRATION .................................................................................................................................................... 56
2.1 MENU Define calibration and standards.................................................................................................. 56
2.1.1 Create a new calibration file................................................................................................................................. 57
2.1.2 Edit existing *.CAL file ....................................................................................................................................... 58
2.2 MENU Perform calibration ....................................................................................................................... 59
3. MENU QUANTITATIVE ANALYSIS OF UNKNOWN SAMPLES ................................................................................ 61
4. DEMONSTRATION .............................................................................................................................................. 62
ELEMENTAL SENSITIVITIES ...................................................................................................................... 66
1. INTRODUCTION .................................................................................................................................................. 66
5
2. CALIBRATION .................................................................................................................................................... 66
4. DEMONSTRATION .............................................................................................................................................. 73
TXRF AND THIN SAMPLES .......................................................................................................................... 78
1. INTRODUCTION .................................................................................................................................................. 78
1.1 Principles of TXRF .................................................................................................................................... 78
2. CALIBRATION .................................................................................................................................................... 79
2.2.1 Regression analysis for the standard elements ..................................................................................................... 83
2.3 MENU Extend calibration for not measured elements .............................................................................. 83
4. DEMONSTRATION .............................................................................................................................................. 86
EMISSION TRANSMISSION METHOD FOR INTERMEDIATE THICK SAMPLES ........................... 92
1. INTRODUCTION .................................................................................................................................................. 92
1.1 Some limitations of this METHOD ............................................................................................................ 92
2. CALIBRATION .................................................................................................................................................... 93
3. CALCULATION OF THE ABSORPTION CORRECTION ............................................................................................. 94
4. RESULTS FOR UNKNOWN SAMPLES .................................................................................................................... 95
5. DEMONSTRATION .............................................................................................................................................. 95
FUNDAMENTAL PARAMETERS – MONOCHROMATIC EXCITATION / SCATTER PEAKS ........ 98
1. INTRODUCTION .................................................................................................................................................. 98
2. CALIBRATION .................................................................................................................................................... 99
2.1 Pre-requisites for calibration .................................................................................................................... 99
2.2 FORM Enter calibration data.................................................................................................................... 99
3. ANALYSIS OF UNKNOWN SAMPLES................................................................................................................... 102
4. DEMONSTRATION ............................................................................................................................................ 102
FUNDAMENTAL PARAMETERS – MONOCHROMATIC EXCITATION - NBS ALPHA
COEFFICIENTS .............................................................................................................................................. 106
1. INTRODUCTION ................................................................................................................................................ 106
2. CREATING THE STANDARD FILE ....................................................................................................................... 106
3. CREATING THE α-COEFFICIENTS FILE ............................................................................................................... 108
4. QUANTITATIVE ANALYSIS OF UNKNOWN SAMPLES .......................................................................................... 111
5. DEMONSTRATION. ........................................................................................................................................... 115
FULL FUNDAMENTAL PARAMETERS .................................................................................................... 118
1. INTRODUCTION ................................................................................................................................................ 118
2. CALIBRATION .................................................................................................................................................. 118
2.1 FORM Excitation conditions ................................................................................................................... 120
2.1.1 Radioisotope excitation ...................................................................................................................................... 120
2.1.2 X-ray tube excitation.......................................................................................................................................... 120
2.1.3 FORM User defined excitation .......................................................................................................................... 121
2.1.4 FORM Parameters for Synchrotron.................................................................................................................... 122
2.2 FORM Detector characteristics............................................................................................................... 122
2.3 FORM Excitation - detection geometry ................................................................................................... 122
2.4 FORM Filter between source and sample ............................................................................................... 122
2.5 FORM Average instrumental constant .................................................................................................... 123
2.6 Libraries .................................................................................................................................................. 124
3. SPECIFICATION OF STANDARDS FOR CALIBRATION + SPECIFICATION OF UNKNOWN SAMPLES ........................ 124
3.1 FORM Select calculation mode ............................................................................................................... 125
3.1.1 Type of instrument constants for standards........................................................................................................ 125
3.1.2 Type of instrument constants for unknown samples .......................................................................................... 125
3.2 FORM Information on sample................................................................................................................. 126
6
3.2 FORM MENU FOR SETTING UP OPTIONS ........................................................................................................ 127
3.3 FORM Analyzed elements........................................................................................................................ 129
3.4.1 Known elements................................................................................................................................................. 129
3.4.2 Known matrix..................................................................................................................................................... 130
3.4.3 Scatter peaks ...................................................................................................................................................... 130
4. CALCULATE INSTRUMENTAL CONSTANTS + ANALYSIS OF UNKNOWN SAMPLES ............................................. 131
4.1 Average instrumental constants............................................................................................................... 131
4.2 Analysis of unknown samples .................................................................................................................. 132
5. PROBLEMS RELATED TO MEMORY SPACE ......................................................................................................... 132
6. DEMONSTRATION ............................................................................................................................................ 133
UTILITIES........................................................................................................................................................ 136
FUNDAMENTAL PARAMETERS’ TABLES.............................................................................................. 138
CALCULATION OF AVERAGE ATOMIC NUMBER .............................................................................. 140
SPECTRAL DISTRIBUTION OF X-RAY TUBES...................................................................................... 142
ABSORPTION COEFFICIENTS, ABSORPTION CORRECTIONS........................................................ 144
INCIDENT – AND TAKE-OFF ANGLES, GEOMETRY CONSTANTS, *.SEN FILE........................... 146

1. INTRODUCTION ................................................................................................................................................ 146
2. CALIBRATION .................................................................................................................................................. 146
2.1 Excitation with an annular source........................................................................................................... 146
2.2 Secondary target excitation ..................................................................................................................... 148
2.3 Source files............................................................................................................................................... 149
2.4 Addition of Standards .............................................................................................................................. 150
2.5 Sensitivity................................................................................................................................................. 151
APPENDIX 1 .................................................................................................................................................... 154
THEORY OF NON-LINEAR FUNCTION FITTING ................................................................................. 156

1. LEAST SQUARES FITTING METHOD ................................................................................................................... 156
2. LINEAR FUNCTION ........................................................................................................................................... 157
2.1 Uncertainty in the calculated coefficients................................................................................................ 158
3. DESCRIPTION OF FLUORESCENCE LINES AND APPERTAINING PEAKS ................................................................. 158
3.1 Single Gaussian ....................................................................................................................................... 158
3.2 Response function for an element group.................................................................................................. 159
3.3 Peak shape correction, escape peaks and sum peaks .............................................................................. 160
4. BACKGROUND MODELS FOR LEAST SQUARES FITTING ...................................................................................... 160
4.1 Linear polynomial.................................................................................................................................... 160
4.2 Exponential polynomial ........................................................................................................................... 161
4.3 Bremsstrahlung background.................................................................................................................... 161
4.4 Background estimation methods.............................................................................................................. 162
5. NON-LINEAR LEAST SQUARES FITTING ............................................................................................................. 162
5.1 Gradient method ...................................................................................................................................... 163
5.2 First order expansion method.................................................................................................................. 163
5.3 Marquardt algorithm ............................................................................................................................... 164
6. CRITERIA FOR THE QUALITY OF THE FIT ........................................................................................................... 165
APPENDIX 2 .................................................................................................................................................... 166
THEORY OF THE EMISSION TRANSMISSION METHOD ................................................................... 168
APPENDIX 3 .................................................................................................................................................... 170
THEORY OF THE ALPHA COEFFICIENTS METHOD .......................................................................... 172
APPENDIX 4 .................................................................................................................................................... 174
THEORY OF THE FULL FUNDAMENTAL PARAMETERS METHOD............................................... 176
7
1. ABSORPTION CORRECTION ............................................................................................................................... 176
2. PRODUCTION CROSS SECTION .......................................................................................................................... 177
3. ENHANCEMENT CORRECTION FACTOR ............................................................................................................. 177
4. INSTRUMENT CONSTANT .................................................................................................................................. 178
5. DETECTOR EFFICIENCY .................................................................................................................................... 178
6. SCATTER RADIATION ....................................................................................................................................... 178
APPENDIX 5 .................................................................................................................................................... 182
USER INTERFACE......................................................................................................................................... 184

1. MENU ............................................................................................................................................................ 184
1.1 Input Rules ............................................................................................................................................... 184
1.1.1 Keyboard............................................................................................................................................................ 184
1.1.2 Mouse................................................................................................................................................................. 184
2. FORM............................................................................................................................................................. 184
2.1 Input Rules ............................................................................................................................................... 185
2.1.1 Numerical & Alphanumerical Input Fields ........................................................................................................ 185
2.1.2 Toggle Input Fields ............................................................................................................................................ 185
2.2 Mouse....................................................................................................................................................... 185
3. SCROLL BOX................................................................................................................................................ 186
3.1 Input Rules ............................................................................................................................................... 186
3.2 Mouse....................................................................................................................................................... 186
4. SELECTOR BOX........................................................................................................................................... 186
4.1 Input Rules ............................................................................................................................................... 187
4.2 Mouse....................................................................................................................................................... 187
5. COMMAND LANGUAGE ............................................................................................................................ 187
5.1 Input Rules ............................................................................................................................................... 187
5.2 Mouse....................................................................................................................................................... 188
APPENDIX 6 .................................................................................................................................................... 190
STRUCTURE OF FILES ................................................................................................................................ 192

STRUCTURE OF SETUP.AX ................................................................................................................................ 192
STRUCTURE OF A *.SPE FILE (C0001.SPE) ....................................................................................................... 194
STRUCTURE OF AN *.OUT FILE - FULL REPORT (SD0023.OUT )......................................................................... 195
STRUCTURE OF A *.DMP FILE (C0001.DMP)...................................................................................................... 196
STRUCTURE OF AN *.ASR FILE (C0001.ASR) ..................................................................................................... 197
STRUCTURE OF A *.FPC FILE (TEST6.FPC)........................................................................................................ 198
STRUCTURE OF A *.SOU FILE (MOTAR45.SOU) ............................................................................................... 199
SCROLL BOX: LIST OF DATA AND RESULTS ...................................................................................................... 200
STRUCTURE OF A *.SEN FILE (TEST4K.SEN) .................................................................................................... 201
STRUCTURE OF A *.STD FILE.............................................................................................................................. 201
STRUCTURE OF A *.STD FILE .............................................................................................................................. 202
STRUCTURE OF A *.CAL FILE (TEST2.CAL) ...................................................................................................... 202
STRUCTURE OF A *.CAL FILE (TEST2.CAL) ...................................................................................................... 203
APPENDIX 7 .................................................................................................................................................... 206
SPECTRUM FORMAT CONVERSION UTILITIES.................................................................................. 208
TABLE: STANDARDS.................................................................................................................................... 210
REFERENCE SHEET FOR SOIL 7 .............................................................................................................. 212
REFERENCES ................................................................................................................................................. 213
8
Introduction
The QXAS (Quantitative X-ray Analysis System) software package is an integrated system
for the quantitative evaluation of spectra measured with energy dispersive X-ray
spectrometers. It runs on IBM-PCs and compatible computers.
For the determination of the net peak areas of characteristic lines of interest the AXIL
software package (Analysis of X-ray spectra by Iterative Least-squares fitting) is utilized.
For the quantification procedure several METHODs, according to the needs of the user, are
available.
QXAS „communicates“ with the user by means of various kinds of pop-up windows, such as
MENU, FORM, SCROLL BOX and SELECTOR BOX. A special command language is used
by AXIL.
User Interface (see Appendix) provides a detailed description of the way the user can interact
with the various user interface components. The user is encouraged to read this appendix
thoroughly, since in this document the appearance of the interactive windows is indicated by the
words MENU, FORM, SCROLL BOX and SELECTOR BOX.
1. Introduction to the Spectrum Fitting (AXIL)
The AXIL package offers an environment in which rather complex tasks regarding the
evaluation and processing of X-ray spectra can be performed. In order to obtain qualitative and
quantitative information from experimentally collected X-ray spectra, specific chains of
successive actions should be followed. These actions are described in this guide.
1.1 Conventions
An overview of the various file types, which are used by the package, is shown in the table
below. Each file type is characterized by a specific extension, e.g. "ORCHARD.SPE" is a
spectrum file, because the name has the extension SPE. In this document the file type is indicated
by naming the corresponding extension, e.g. an *.XRL file is an X-ray library file.
Table of File types
File Name File type File contents

Extension
SPE Spectrum Spectral data in AXIL standard format

INP Input, Model or Parameter Parameters of the fitting model
ASR Axil Saved Results Results of the spectrum analysis
XRL X-ray Library X-ray energy and relative line intensities, line ratios
PSL Peak shape correction library Numerical peak shape corrections
9
Functional Description of AXIL (Appendix) contains the functional descriptions of the input
windows of the AXIL package.
2. Introduction to the Quantitative METHODs
All quantitative METHODs consist of 3 sections that must be passed in the correct order.
• The measuring conditions, like kind of excitation source, detector, geometry, etc., must
be specified.
• Standards of known composition measured with the users XRF spectrometer must be
entered and described. The measured net intensities usually should be entered as result
files of AXIL. It is advised to cover an elemental range that is corresponding to the
elements of the unknown sample.
With the aid of the two first steps Sensitivities or an Instrument constant are
determined and so called sensitivity-, calibration-, or instrument parameter files are to
be stored for the further use.
• Unknown samples can be analyzed for the concentrations of detectable elements. Again
an AXIL result files must be loaded, containing, among others, the net peak areas.
Elements not covered by standards can be accessed by interpolation or extrapolation, or
theoretical calculations based on fundamental parameters.
Only characteristic Kα and / or Lα lines can be treated, with the exception of Full
Fundamental Parameters that basically can handle any line of an element in an unknown
sample.
Any reported uncertainty for a concentration value is related to the standard deviation of the
fitted peak area due to counting statistics only. As a consequence the standard deviations
represent only the statistical and, if applicable, peak overlap contributions.
The desired total uncertainty is composed from addition of the uncertainties of standards used
for calibration, sample preparation, instrumental fluctuations, etc. The quantification of all
effects together is usually quoted as the precision. Practically only the repeated preparation
and evaluation of identical standards and samples in a statistically significant number can
lead to correct values for the precision. For a theoretical approach the interested reader is
referred to reference /WEG03A/.
By accuracy usually the deviation of a concentration value from the “true” value is
understood. Only repeated analysis of standard reference materials can lead to an idea of the
accuracy for a particular kind of sample.
If the concentration of any element in a sample is falling below the detection limit, this will
be indicated by a “ < “ (smaller than) sign in front of a concentration value or „LD“. The
detection limit will be reached, if the calculated net peak area is equal or smaller than three
times the appertaining standard deviation (“3σ criterion”). The standard deviation is
determined by the background under a peak and by other overlapping peaks (see reference
/ESP02/). The program Fundamental Parameters – monochromatic excitation / scatter
peaks will unfortunately also report concentration values which are smaller than the quoted
standard deviations, so the user will have to reject such values.
10
Warning: For source excitation none of the quantitative programs had been test after
the year 1999 for their behavior concerning the so-called Millennium bug. Therefore
the response of each program to the input of dates (after 12/31/1999) must be
inspected with care. The dates are needed for the correction of the source decay
between calibration and measurement of samples. It is proposed to use dates before
the turn of the millennium, but with correct time interval between calibration and
sample measurements. E.g. calibration on 1st January 2000, sample measurement on
1st December 2002, use the years 1990 and 1992 respectively instead.
Hint: Many samples will be prepared as pressed pellets where a binder has to be
added. I.e.: the sample will be diluted. All reported concentration values would have
to be corrected with the dilution factor.
3. Description of the main MENU
All files either generated with AXIL, or with any of the quantitative METHODs, will be
stored in the default directory C:\AXIL\SPECT. In order not to end in a mess, one either can
straighten up this directory from time to time by transferring files to other directories or
diskettes. Or one can select an appropriate path for each session with QXAS in the very first
FORM (QXAS) to appear. The ITEM Select directory can be edited as required (default
C:\AXIL\SPECT). Consequently all files can be redirected to an (already existing!) directory.
Warning: Also files needed as input data for certain programs will be traced there by
default. The ITEM Search in directory preceding the SELECTOR BOXes must be
edited accordingly. Problems will be indicated with an error message:
No files (*.xxx) found;
The main MENU of QXAS Axil X-ray Analysis Package consists of ITEMs that contain
various conversion routines (Spectrum format conversion) to bring certain binary formatted
spectra to the ASCII format as expected by AXIL (Spectrum fitting), which will calculate
net peak areas from the spectra. Under Quantitative analysis among several programs the
user will have to select a suited METHOD in order to calculate the desired concentration
values or perform a calibration.
Utilities contain several programs, which can be helpful but are not directly needed for the
above listed tasks.
11
4. Brief history of QXAS
1977-87 AXIL is developed by Van Espen and co-workers for Digital PDP-11
computers. It is written in FORTRAN, without any graphical display and
difficult to use. Later AXIL is adapted for Digital Professional computer and
IBM-PC without any major changes. A new version of AXIL is developed for
IBM-PC and Digital Professional, with graphical interface and a more intuitive
command language. Still it is written in FORTRAN, with many assembly
language routines (PC version).
1987 QXAS becomes the combination of AXIL and some of the quantitative
methods. The block structured file format and the MENU system are
established. The programming language C begins to be used for the PC
version.
1990-93 The Full Fundamental Parameters method is added and spectra measured with
Total Reflection XRF spectrometers can be quantified. Introduction of the
Orthogonal Polynomial background.
1995-96 Documentation of QXAS and implementation of the XPARAM library as a

consistent source of fundamental parameters in the software.
Early 1990’s New Emission Transmission method ET-10 implemented by N. Haselberger.
1997 Voigt peak profile option for peak fitting written.
1999 Backscatter Fundamental Parameters method for source excitation developed.
2005 Revision of the documentation and rearrangement of the QXAS package.
12
13
QXAS installation procedure
From the Internet under the IAEA home page with
http://www.iaea.org/OurWork/ST/NA/NAAL/pci/ins/xrf/pciXRFdown.php
all necessary files and programs can be downloaded. The installation procedure assumes that
the installation will be done on the hard disk C: During the installation among others the
directories C:\AXIL and C:\AXIL\BIN will be created. The directory C:\AXIL\BIN contains
the executable files of the package.
Two more sub-directories can be found in C:\AXIL, namely \INSTALL, which is empty and
was used during the installation procedure only (it can be erased), and \SPECT. A
comprehensive set of sample spectra and other files is copied during the installation
automatically to this directory. The file CALSAMP.TXT describes some of the samples and
standards from which these spectra were measured as well as the experimental conditions.
All spectra, calibration-, sensitivity-, and result files, etc., generated in the future, will also be
saved there, if the default path C:\AXIL\SPECT is kept. All of them are in ASCII format, i.e.
they are readable by text editors.
There exists a so-called batch file AXIL.BAT that will contain a few important commands.
The advanced user should be aware of the PATH setting.
PATH=%PATH%;C:\AXIL\BIN
and the SET command that is included (in a new line).
SET AXIL$SETUP=C:\AXIL\SETUP.AX
The important setup file SETUP.AX will be found in C:\AXIL (and a copy in
C:\AXIL\BACKUP). Whenever QXAS is started, the programs will use this file to obtain
information about graphics mode, allocation of various files, etc.
Warning: This file setup.ax can get corrupted. The reason is that many times during
the run of QXAS information will be read from the file or information will be stored
into it. During such events the file can be partly destroyed (the executable files of the
directory BIN are usually not effected). As result MENUs or sub-MENUS will not be
found as usual. Simply replace the corrupted setup.ax by its back-up copy (to be found
in the directory BACKUP).
For the advanced user who wishes to adapt QXAS to his personal needs and edit the setup.ax
file:
The modules of the package are arranged in tree structure, which is defined in the $MENUTREE: section of
the file 'setup.ax'. The user may adapt this structure to his needs by adding or removing nodes or leaves,
which are defined as follows:
Node: @<parent node> <actual node> <menu title/item>
Leaf: @<parent node> <actual node> <menu item> <program>
14
where menu title/item and menu item are enclosed by quotation marks, and program is stored in the directory,
which is specified in, the $AXIL$BIN: section of the setup.ax file. A node (or MENU) typically has leaves
and/or is connected with other node(s); these relationships are expressed by specifying the name of the node
(actual node in the definition of the node itself) as the name of the parent node of the leaves and/or connected
node(s). Selection of a menu item, representing a node, from the MENU, which is defined by parent node of
the concerning node, causes a MENU to appear with the specified menu title and menu items of its leaves
and/or connected node(s), while the selection of a menu item, representing a leaf, causes the execution of the
correspondingly specified program.
Note that when capital letters are found at certain positions small letters will not be an alternative.
1. System hardware setup
Selections concerning the graphics adapter, the mouse driver, and the RS232 COM ports can
be made. The hardware setup can be activated, if required, by AXSETUP.exe. Usually this is
only done, if under the operating system DOS any problems with, e.g., graphics, printer, and
other hardware configuration are encountered.
For each ITEM (highlighted line) one option can be selected from at least two possible ones.
Switch between these options by the use of the arrow left/right keys, +/- keys, or <SPACE
BAR>. After such a selection continue with either arrow up/down keys, <ENTER>, or click
onto a line with the mouse. From one FORM to the next use the <ESCape>.
1.1 Selection of graphics adapter and other hardware
The FORM Axil setup enables the selection of the graphics adapter. Two adapters are
currently supported: CGA 640x200 - this is the color graphics adapter with a resolution of
640 pixels horizontally and 200 vertically and EGA 640x350 - this is the enhanced graphics
adapter with a resolution of 640x350 pixels. The EGA is the default adapter.
15
Further one can enable/disable colors. When one is working with a color monitor, selecting
enable colors (default) for an EGA adapter, displays both text and graphics in color; for a
CGA adapter only the text will be in colors, but the graphics will be black and white.
Another option is concerning the line-drawing characters (with the default enable). Line-
drawing characters are part of the IBM character set to draw lines around a text. Some CGA
cards do not support the extended character set. Most printers can be set to print these
characters, or some other (national) character sets. Disable the line drawing characters, if
either strange characters are seen on the screen, or if the printouts contain strange characters.
Sometimes the second kind of problem can be overcome by a different setting of the
dipswitches of the printer (see printer manual).
1.2 Selection of communication parameters.
The RS232 serial communication ports of the PC can be used to connect an external Multi
Channel Analyzer, such as the Canberra S35+ MCA.
One can select the baud rate, the parity, the number of data bits, and the number of stop bits
for each available COM port in the FORM Parameters for COM. Usually the default values
are appropriate. The higher the baud rate the faster the spectra will be transmitted. If
problems are encountered with the transmission of data, consider reducing the baud rate.
One of the ports can be selected in the FORM MCA communication port.
The hardware setup MENU will terminate with setting all parameters to the selected values
and writing them to the setup file. One does not have to run this MENU each time one wants
to communicate with an external MCA.
2. Starting AXIL
The QXAS software package usually will be started with the shortcut
from the desktop.
At the level of DOS it should have been configured in such a way that it is possible to start the
QXAS package by typing "AXIL" and pressing <ENTER> at the system prompt "C:\>":
C:\>AXIL
A FORM appears on the screen and the user is asked to enter or accept a directory name. The
Current directory is the directory where the executable programs are kept. By default it is BIN
and cannot be changed.
The Set directory name can be changed using the input rules for FORMs. The Set directory is
the place where all (readable) files will be loaded from and saved to during the use of the QXAS
package, if no additional directory information is given in a file specification. The starting value
is always SPECT.
16
It should be noted that, according to these rules, the name is not changed unless <Enter> is
pressed after the directory name. After pressing <ESCape>, the main MENU of AXIL appears.
The programs of the package are arranged in a tree structure, which is defined in the file
"setup.ax". The user may adapt this structure by adding or removing sub-MENUs and menu
items in the tree definition.
Prior to the actual spectrum analysis some preliminary actions should be performed: the
spectrum format conversion to change from several possible MCA spectrum formats to the
format acceptable by QXAS, with extension *.SPE, create an *.INP (input, model or parameter)
file.
The results of the spectrum analysis must be saved for further processing in an *.ASR (AXIL
Saved Results) file, which can be used as input for the quantitative METHODs.
17
Spectrum Format Conversion
The AXIL package requires all spectral data to be in one particular format (block structured
ASCII files). The extension of these files is always SPE. Since most of the X-ray spectrometers
store spectral data in their own format, conversion to the standard AXIL spectrum format has to
be performed as the first step of any kind of analysis.
The service of spectrum format conversion in QXAS is provided by a tailored version of the
Spedac Pro format conversion program. Each format is handled by a different *.EXE file and
a reasonably well-documented procedure exists to write conversion applets as new
spectrometers and spectrum formats appear on the market. In order to get the full version of
Spedac Pro and documentation, please consult the IAEA Physics Section.
1. Program flow
The program converts spectral data from a source format to a target format. The following
logical sequences are executed:
1. Select format of spectrum to be converted from (source).

2 Select format of spectrum to convert to (target).
3 Select directory and filenames of all source spectra.
4 Select directory for target spectra.
For each selected source file:
4.1 Read the spectrum in the source format.
4.2 Display the spectrum (for visual inspection).
4.3 Save the spectrum in the target format.
2. Detailed discussion
After starting the program, a full screen will be displayed.
Below the scroll box (at the bottom of the screen) two lines are visible. The first indicates the
current directory. This is the directory that was current when you started the program. The
18
second line indicates which table SPEDAC is using for the conversions (see later). This
should normally read:
Using table: C:\AXIL\BIN\SPEDAC.TAB
The scroll box itself, labeled "Select format of source data” contains all the possible sources
you can select to convert from, in alphabetic order. Use the up arrow <↑> or down arrow <↓
> to highlight the desired source, e.g. "APTEC Version 4.3". Once the right choice is made,
press the Enter key <↵>. (If you press the <Esc> key, no selection is made and the program
terminates). The selected source format is indicated below the line “SOURCE format:”.
Next a scroll box to select the target is displayed on the right side of the previous scroll box.
The label of this scroll box is "Select format of target data". The version of Spedac Pro
included in the QXAS package supports only IAEA QXAS, which will create a *.SPE file,
and ASCII as target formats. (The IAEA GANAAS format is identical to IAEA QXAS.)
The bottom line of the screen (in reverse colors) always indicates what you can do at a
certain moment while input is active.
A frame labeled "Select SOURCE files" is displayed.
19
In this example C:\WINDOWS\APTEC is displayed because this is the default directory
where the APTEC Version 4.3 spectrum files (*.S0) are located.
The scroll box allows changing to other directories as well as to select the spectrum files in a
directory. E.g., the entry "MCARD\" highlighted and <Enter> pressed, will move to that
directory. Highlight the entry "..\" moves to the parent directory of the current directory (one
up in the hierarchy). Moving the highlighted bar of the scroll box down will bring entries for
other drives like [-A-]. Only the files with the correct extension, in this case *.S0, will be
displayed.
Highlighting the desired file names and pressing <Enter> will select the files, and an " * " is
put in front of the spectrum name (maximum 10 spectra per run). Pressing <Enter> again
while a selected file is highlighted will un-select this file. In the example "QCY48.S0" and
"QCY48CAL.S0" had been selected.
Only files in one directory can be selected per run. Pressing <ESCape> without selecting any
files will terminate the program.
The next form sets the target directory.
This is the directory into which all converted spectra will be stored. The directory displayed
is the default directory. Another directory or drive can be chosen by moving the highlight bar
and <Enter>.
For a short while the message "Reading Source..." and "Displaying Spectrum..." will
appear after which the source spectrum is displayed on the screen.
20
The top line shows the spectrum file name, the next line the spectrum identification (ID) if
any, e.g.
Spectrum: C:\WINDOWS\APTEC\QCY48.S0
ID: Un-calibrated Spectrum
The MAIN MENU on the right side lists all possible actions. The usually sole action on this
screen will be <ESCape>, which terminates the display of the spectrum, and SPEDAC
continues as explained below. All other actions will not have any effect onto the conversion,
but can help to identify spectra.
The left and right arrow keys <←>,<→> move the spectrum cursor one channel; the channel,
its content and its energy are displayed on the bottom line. The energy is only correct if the
spectral data contains energy calibration parameters. With the up arrow and down arrow keys
<↑>,<↓> the cursor moves in larger steps (10 channels). Also use of the mouse to move the
cursor and to point to the MENU is enabled.
Pressing <F1> (RoiBeg) marks the current cursor position as the beginning of the region of
interest (ROI). Pressing <F2> (RoiEnd) sets the end of the region of interest to the current
cursor position. If a region of interest has been defined in this way, pressing the <F3> key
will display the region of interest only. With <F4> the entire spectrum is displayed. Finally,
<F5> (Scale) changes the vertical scale and a sub-MENU appears.
21
F1 sets the vertical scale to linear; F2, to logarithmic; and F3, to square root.
The next form is displayed as shown below
The label of the form shows the number of the spectrum, which is currently processed out of
the list of selected files. The first 3 lines in the form identify the source spectrum by its full
file name, the first and last channel number, and the (optional) ID information. The line
below identifies the target directory chosen.
Certain fields of this form can be altered. The name of the target spectrum to be saved
22
(TARGET Name:)
By default the target has the same name as the source and the extension is *.SPE, e.g. if the
source spectrum is the APTEC spectrum QCY48.S0 and the target is IAEA QXAS, the
proposed file name will be QCY48.SPE. Alterations of the name and extension (which only
gives sense when no further processing with QXAS is desired) are possible. If a file with the
same name and extension already exists on the target directory, a warning will be given
The next line of the FORM holds three fields:
Copying from channel 0 to 1023 Squeezing factor 1
Changing these values allows saving only parts of the source spectrum into the target file, by
altering the beginning channel (default 0) and/or the ending channel (the default is the last
channel in the source spectrum).
The squeezing factor can be used to reduce the number of channels in a spectrum. With a
squeezing factor of 1 (the default) each channel in the source corresponds to one channel in
the target. If the squeezing factor is two, the sum of two channels in the source spectrum will
be stored into one channel of the target spectrum, and so on. With this option a too large
spectrum size can be reduced. E.g. an 8K spectrum can be stored as a 2K spectrum.
If more than one spectrum has been selected for conversion, three more fields appear in this
FORM:
Cont in batch mode OFF
Graphics display: ON
Overwrite protection: OFF
You can move to these fields using the up and down arrow keys, use <Enter>, or the mouse.
Since these are toggle fields, you can switch between ON and OFF with “+” or “-“ or the
Space bar.
When Continue in batch mode is ON, the current and the remaining selected files will be
converted without further intervention of the user. When Graphics display is OFF, the
remaining spectra will not be shown on the screen during conversion in batch mode. And
finally, when Overwrite protection is ON, any file with the same name will not be
overwritten during batch mode operation.
The final dialog determines the action to be taken.
23
Use the arrow keys or mouse to highlight one of the three options and confirm with <Enter>.
Write spectrum writes the spectrum in the selected format. Skip this spectrum will not
write the current spectrum to disk. In both cases the program will continue to process the next
spectrum of the list selected, if any. Skip all spectra will skip the current and all other
selected spectra, and the program will be terminated.
Hint: Some conversion routines might not contain the measuring time after
conversion. In such a case the peak fitting will be no problem, but any quantification
will fail. The time has to be added manually to the respective *.spe files, matching the
format as given in the appendix (Structure of a *.SPE file).
24
25
Spectrum fitting
The evaluation of energy-dispersive X-ray spectra by means of AXIL (Analysis of X-ray spectra
by Iterative Least-squares fitting) is achieved by fitting the measured spectra with suited
mathematical functions, using a non-linear least squares strategy. Certain parameters have to be
defined by the user and an appropriate *.INP (model) files should be selected or created prior to
the actual spectrum analysis.
Menu item Task
1. X-ray library management Edit or select *.XRL file

2. Specify parameters for spectrum analysis Edit or select *.INP file
3. Perform spectrum fitting Analyze spectrum, select *.INP file
1. MENU AXIL (& Voigt peak profiles option for high energy K-lines)
The actual spectrum analysis is done by fitting the X-ray spectrum with a mathematical function
that is defined by the user. To build this function, an appropriate library file should have been
selected in MENU X-ray library management (Section 3) and a suitable model or parameter
file should have been created, prior to the actual spectrum analysis.
26
This MENU enables the user to select a model file. Every time spectrum analysis is started by
selecting Analyze Spectra, the values of the parameters of the current model file are used as
default values for the model. While analyzing spectra the user can alter some of the parameters.
(If such changes should be saved, the menu item Save model must be activated, before returning
to the upper MENU AXIL (& Voigt peak profiles option for high energy K-lines).
Starting the spectrum analysis (Analyze Spectra), the screen consists of several parts. Top right
there is the command MENU, the two top lines are used to display information. On the bottom
there is the command line. The line above and the lines below the command line are also used to
display information. The free area enclosed by the command MENU and the top and bottom
information lines are used to display spectra and text.
Depending on the state of the program, only meaningful commands appear in the command
MENU.
In the beginning the user can only load a spectrum, stop the analysis, and execute commands in
batch mode. One has to use the COMMAND LANGUAGE (see User Interface, Appendix). A
command typically consists of a verb followed by a number of qualifiers.
The command menu displayed in the right hand part of the screen gives the commands and
qualifiers, which can be entered together with its format. Note that any non-ambiguous
abbreviations of the command are accepted, e.g. L, LO or LOA instead of LOAD. Qualifiers are
separated with spaces, and commands are entered after the command line prompt ">>" where the
cursor "_" appears. E.g. typing "L S=C0001" the spectral data of the SPE file "C0001.SPE",
which can be found in the current directory, is loaded and displayed together with the commands
applicable in the current state.
An overview of the commands is shown below. A detailed description can be found in

Functional description of AXIL (Appendix).
Overview of commands for Analyze Spectra

27
Paragraph Command Task Description
1.1. LOAD (*) Select *.SPE file,

1.2. CALIB (*) Calibration
1.3. X-LINES (*) Select (groups of) lines
1.4. ROI (*) Select Region-of-Interest (ROI)
1.5. BACKGRND (*) Select background model
1.6. FIT (*) Fit Spectrum
1.7. REPORT Create report *.OUT file
1.8. SAVE_RES (*) Save result *.ASR file
1.9. &BATCH Execute instructions of Batch File
1.10. STOP (*) Return to upper MENU Analyze Spectra
1.11. DISPLAY Change the display of the spectrum
1.12. KLM-MARK Identify lines in spectrum
1.13. SCAT_ROI
1.14. PLOT
The functions indicated by "(*)" are used to perform main tasks of the spectrum analysis. The
other functions are auxiliary functions.
After the selection of a model, the spectrum is loaded (see paragraph 1.1.) prior to the actual
spectrum analysis. The model can be changed by calibration (see paragraph 1.2.), selection of
lines (see paragraph 1.3.), definition of a region-of-interest (ROI) (see paragraph 1.4.) and
selection of a background model (see paragraph 1.5.) to improve the fit of the spectrum (see
paragraph 1.6.) of which the results can be inspected by means of reports (see paragraph 1.7.)
and the so-called plot of residuals (see paragraph 1.11.). For further quantitative analysis of a
spectrum an *.ASR file (see paragraph 1.8.) will have to be created. The spectrum analysis can
be automated by means of a batch file (see paragraph 1.9.).
1.1 MENU Load
A spectrum must be selected as the first step of the spectrum analysis. Note that the spectral data
file must be in a particular format.
Typing the command "LOAD SPEC=filename" loads the named spectrum. It is not necessary to
add the extension SPE to the name, since this extension is added automatically. The program
searches in the current directory only. It is sufficient to type L S=c0001 to load the spectrum
C0001.spe .
A spectrum can also be loaded by entering the command "LOAD DIR_SEL". By this a
SELECTOR BOX is displayed, which gives a list of *.SPE files in the current directory, but also
other directories are accessible (<enter> into the line ..\ ) and a spectrum can be selected.
Warning: Only 100 files (of the kind *.spe) in a directory can be handled by AXIL,
therefore only this number of files will be selectable in a SCROLL BOX. In such a
case a new directory has to be created (alternatively files will have to be removed or
deleted).
1.2 Calibration (MENU Calib)
During the least squares fitting the energy and resolution calibration parameters will be
optimized to get the best agreement between the measured and the calculated spectrum. An
28
initial estimate of these parameters should be made using the CALIB command prior to the
actual spectrum fitting. The calibration equations can be found in paragraph 2.
A vertical cursor appears in the spectrum, and information about values of the calibration
parameters and the position of the vertical cursor is given. The commands of this MENU and an
example are given below.
Overview of CALIB commands

COMMAND Description
CALIB ZERO=number Set energy of channel 0 (eV)

CALIB GAIN=number Set slope (eV/ch)
CALIB NOISE=number Set the electronic noise contribution to the peak broadening
CALIB FANO_F=number Set the FANO factor
Example: CALIB ZERO=0 GAIN=20 NOISE=120 FANO_F=0.114
For the calibration special keyboard functions can be used (can also be activated by mouse click)
as described below.
CALIB keyboard functions

KEYBOARD FUNCTIONS DESCRIPTION
arrow left (right) moves the vertical cursor to previous (next) channel;
arrow up (down) moves the vertical cursor to the top of the next (previous) peak if any;
<INS> moves the vertical cursor to the top of the nearest peak;
<F1> starts or continues the energy calibration;
<F2> includes the peak at vertical cursor position in the resolution calibration;
<SPACE BAR> continues the energy calibration; this can move the vertical cursor again;
<F3> gives the line of which K-α is nearest to the position of the cursor;
<F4> gives the line of which K-ß is nearest to the position of the cursor;
<F5> gives the line of which L-α is nearest to the position of the cursor;
It should be noted that the results of the identification functions <F3>, <F4> and <F5> depend on
the current energy calibration.
The energy calibration is performed in the following way. Once the cursor is positioned on the
top of a peak to be used for calibration, press <F1> to start the energy calibration. Then, the
name of the X-ray line or the energy of that line should be entered, e.g. if the cursor is positioned
on top of a Fe - Kα peak , then FE-KA, FE or 6.400 should be entered. Do not use <ENTER>
between different points of the energy calibration, because <ENTER> terminates the calibration.
The calibration is continued by pressing <SPACE BAR>, moving the cursor to the next peak,
pressing <F1> and entering the name of that line or its energy, etc. Only at the end of the energy
calibration use <ENTER>.
Performing the calibration certain rules should be taken into account:
a) energy calibration should be performed prior to the resolution calibration, since the latter
depends on the former;
b) the more lines are selected, the more accurate the energy calibration will be (2 lines are
sufficient);
c) the best estimate of the energy calibration will be obtained by the selection of lines in the
beginning, in the middle and the end of the spectrum;
d) if the energy calibration is performed with only one line, only the ZERO will be calculated;
e) resolution calibration is performed by the selection of well defined peaks (not overlapped
with other peaks);
29
f) if peaks are much wider than 160 to 200 eV, the NOISE parameter should be adjusted by the
selection of one peak in the middle of the spectrum.
1.3 Select (groups of) Lines (MENU X-lines)
Prior to the least squares fitting, (groups of) lines must be added to the model. The command
KLM-Mark (see paragraph 1.12.) and the command CALIB must give the user some idea of
which lines should be included in the model. It should be noted that the position of the lines
depend on the energy calibration and that the lines only appear when they are included in the
current library file.
Overview of X-LINES commands
COMMAND Description
a. X-LINES ADD el-group adds X-ray line(s) as one group;

b. X-LINES ADD ener,rin adds X-ray line(s) as one group;
c. X-LINES ADD SUM adds an extra line group, considering possible sum peaks;
d. X-LINES REMOVE el-group removes line group;
e. X-LINES REMOVE ALL removes all lines;
f. X-LINES SHOW shows list of lines in the model.
Using the commands of this MENU, (groups of) lines may be added to or removed from the
model and a list of the lines in the model can be inspected. Also, when estimating net peak areas
of small peaks, corrections should be made for tails of intense lines by means of the so-called
peak shape correction.
It is important to understand the concept of "X-ray line groups". A group of X-ray lines is treated
by the fitting procedure as one entity. A net peak area is determined for each group during the
spectrum fitting. Lines within a group have fixed intensity ratios during the fit. The X-ray
energies and the relative intensities are read from the current XRL (library) file. The relative
intensities are modified by any absorption that is specified in the model (e.g. absorption of the
detector windows and/or sample absorption).
Although the line ratios within the groups K and L are fundamental constants, the actual ratios
between these groups depend on the experimental conditions. E.g. if strong absorption takes
place in the sample, and no adequate correction is made for this absorption by specifying the
sample absorption characteristics, the observed Fe Kß/Kα ratio will be (typically) higher than
expected, resulting in a bad fit. In case of the L-lines, additionally the ratios depend on the
excitation energy and therefore it is necessary for accurate work to measure the subgroup ratios
for the excitation conditions used.
It is recommended to specify all lines of one element as one group, because entering lines
separately would increase the number of parameters in the fitting model and may cause problems
estimating peak areas of small, strongly overlapping peaks. However, if the fit indicates that
intense peaks are fitted badly, one should specify the lines of the concerning element as
independent groups (e.g. instead with FE, iron with a high content in a sample/standard could be
included as FE-KA FE-KB).
30
1.3.1 X-LINES ADD el-group
The general format of "el-group" is: EL-GRX.

EL is the chemical symbol of an element. If only EL is entered, the Kα and Kß lines of the
corresponding element are added as one group.
GR is the group identifier and X is a special qualifier. The following entries are allowed:
Values for the Group Identifier GR
GR group
K Kα and Kß
KA Kα
KB Kß
L L1, L2 and L3
L1 or LG L1
L2 or LB L2
L3 or LA L3
KL Kα, Kß, L1, L2 and L3
M M
KLM Kα, Kß, L1, L2, L3 and M
The following qualifiers are allowed:
Values for the special qualifier X
X effect
+ the escape energies and intensities for the specified X-ray lines are calculated in this group;
* the escape lines are included and a peak shape correction will applied to this line group; this is
only relevant when the specified group contains a K-α line of elements between Mg and Br;
@ the line in question is treated as an analytical line (by default, only Kα and Lα lines are treated
as units); by this the peak area of the Kß, Lß or Lτ line contained in that group will be outputted to the
ASR file for further use in quantitative analysis; note that the @ character is allowed to come before or
after the + or * character.
Peak shape corrections describe the deviation from the Gaussian peak shape. This is done by
means of numerical values, which are stored in the AXIL.PSL library file and calculated from
spectra, which were acquired with very good counting statistics. Unfortunately the peak shape
correction will improve results in respect of the Chi-square, but the correction will not be added
to net peak area, but treated rather as background for the other lines. In many cases the net peak
area will be slightly less for the use of peak shape corrections, as compared to the Gaussian only
peak shape.
The name of the added group is EL-GR, which should be used when removing this group
from the model. E.g., when Fe-Ka was used one also will have to remove it as Fe-KA, Fe
only will not be accepted for the removal of that previous entry.
1.3.2 Voigt Peak Profiles
A few changes were made to AXIL input and output screens as compared to previous
version. The user is now allowed to choose Voigt peak shape when adding a group of X-ray
lines in the MENU X-LINES by specifying the character ‘&’ after the symbolic name of that
31
group. When this symbol is omitted the K-series peaks in this particular group will be given
Gaussian profiles. When the symbol ‘&’ is added the K-series peaks will be approximated
with Voigt functions. The Voigt profiles are only allowed for groups containing K-series X-
ray lines. In addition, it is also assumed that one would have already selected a library file
containing K-series of heavy elements or that the current library file has been modified as
needed. However, with the availability of newly published experimental and theoretical data,
the program can be easily adapted to assign the Voigt shape also to other groups of peaks. An
example of the operator input specifying the lead K-α and K-β groups to be included in the
model as Voigt profiles is shown in the picture below (demonstration spectrum PBSIM.spe).
The operator can assure his choice by examining the screen listing of all the groups
already included in the fitting model by issuing a command SHOW under the menu X-
LINES. If a given line was appointed to have Voigt profile, an appropriate comment is
placed next to this line:
32
After the fitting procedure is finished the operator can examine the results by selecting the
main MENU option REPORT then FULL. The results reported under this MENU show also
which of the groups of peaks were fitted using the Voigt peak profiles. This is indicated by
the symbol ‘&’ next to the group name in the listing:
Also altered has been the structure of the model files (files with extension *.INP). The
changes were introduced in such a way that the model file remains backward compatible with
the previous versions of AXIL. When the operator introduces some groups of lines, using
Voigt profiles, this information is stored in the model file. However, the part of it concerning
the peak profile shapes is transparent to the older versions of AXIL. Also, the model files
saved in previous versions of AXIL can be retrieved in the new AXIL version. Then, they
can be altered accordingly to the operator needs. All other changes were made to the fitting
procedures and are invisible to the operator of the program. The only noticeable difference in
program operation is longer fitting time when Voigt profiles are included in the model. This
is due to the more complicated algorithm, which involves a numerical differentiation
procedure.
1.3.3 X-LINES ADD el-group,inc / el-group,coh
The elastic and inelastic scatter peak regions can be included, so that the fit results are
included into the *.ASR result file for further use for some of the quantitative methods.
E.g. for Mo-Kα the 2 scatter peaks will be included with
Mo,inc
Mo-Ka,coh
For the incoherent peak only one line will be included, so by default it will be, e.g., the Ka
line, whereas for the coherent peak Kα has to be specified. Otherwise both Kα and Kß will
be fitted (which for the scatter region is not recommended). The command SCAT_ROI
33
should not be used, because it will generate entries in the respective *.ASR files which are
not compatible with the quantitative methods.
Hint: Usually it will be necessary to fit the lines of interest in a different run than the
scatter peaks. The reason is that the background under the characteristic lines will
need high background parameter numbers. After a successful fit of this region the
results will be saved. Whereas under the scatter peaks the simplest models will more
adequately describe the situation (the background might be strongly overestimated
otherwise). Consequently with a different ROI and a different background model the
fitted scatter peaks will be saved too. When a warning appears that such a file already
exists (ASR exists), add the results with A=add.
1.3.4 X-LINES ADD ener, rin
The X-ray lines can be added to the model by explicitly entering the energies and relative
intensities of the lines contained in the group. The general input format of "ener, rin" is:
E1,R1,E2,R2,E3,R3 ...
The energies E1, E2, E3, ... are expressed in keV. R1, R2, R3, ... are the relative intensities
of the lines with energies E1, E2, E3, ... The lines entered in this way are considered as one
group, which gets automatically the name GRnn where nn is the number of the group. This
name should be used when removing this group from the model.
34
1.3.5 X-LINES ADD SUM
Entering the qualifier SUM, the program will create an extra line group with energies and
relative intensities based on the possible combinations of other lines present and the Pulse
pile-up resolution time (FORM Set detector characteristics), in order to identify sum
peaks (pile-up effect).
1.3.6 X-LINES REMOVE el-group
Removes the group from the model. A group that has not been entered yet cannot be
removed.
1.3.7 X-LINES REMOVE ALL
Removes all lines from the model.
1.3.8 X-LINES SHOW
The list of lines (group, energy, relative intensity) of the model is displayed in a SCROLL
BOX. The list can be scrolled using the arrow up, arrow down, <PgUp>, <PgDn>, <Home>,
and <End> keys or by using the left mouse button and the command menu.
1.4 Select ROI (MENU ROI)
Prior to the least squares fitting, an appropriate region of interest must be defined. The region of
interest (ROI) is the part of the spectrum that is actually fitted.
By default there will be set an automatic region of interest (including all lines, as to be added
under the MENU X-Lines, and begin and end defined by the lowest and highest lines). Like with
the command AUTO the program defines the ROI based on the X-ray lines entered starting at
the channel corresponding to the lowest X-ray energy entered minus 6 times the width of that
peak, and end at the channel corresponding to the highest X-ray energy entered plus 6 times the
width of that peak.
The other commands of this menu are needed to define the ROI manually. Typing the
command "ROI BEG=channel" sets the first channel of the ROI and entering the command
"ROI END=channel" sets the last channel of the ROI. Additional to the commands, the
selection of the ROI can be done by using special keyboard functions and mouse functions,
which are described below. When typing a qualifier of this MENU, these functions are
inactive and removing the qualifier (using <BACKSPACE>) these functions are reactivated.
ROI Keyboard and Mouse Functions
35
KEYBOARD FUNCTIONS DESCRIPTION
arrow left (right) moves the vertical cursor to previous (next) channel;
arrow up (down) moves the vertical cursor to the top of the next (previous) peak if any;
<INS> moves the vertical cursor to the top of the nearest peak;
<F1> sets the first channel of the ROI to the position of the vertical cursor;
<F2> sets the last channel of the ROI to the position of the vertical cursor.
MOUSE FUNCTIONS
Selecting command menu items representing arrow items and function keys <F1> or <F2> by putting the mouse pointer on
the menu item and pressing the left mouse button, is equivalent to pressing the corresponding key; putting the mouse cursor
at a particular position on the spectrum and pressing the left mouse button, moves the vertical cursor to the pointed position.
1.5 Select Background (MENU Backgrnd)
The commands of this menu are needed to select a background type and to set its parameters,
if they are not already defined (MENU Specify parameters of LS Fit).
The following background models are available in the package:
Overview of Background Models
BACKGROUND DESCRIPTION PARAMETERS
LINEAR linear (orthogonal) background order

EXPONEN exponential background order
BREMS Bremsstrahlung background order
FILTER smooth filter background number of iterations
ORTPOL orthogonal polynomial background order and r
E.g. entering "BA O P=12 R=1.5" selects the orthogonal background with a polynomial of
order 12 and the adjustable parameter r of 1.5.
The order or the number of the background iterations (in case of FILTER) should be entered
by the user. In case of ORTPOL background models, the decision whether a data point is to
be included as background depends on the adjustable parameter r. A too high value for this
parameter will include the tails of the peaks into the fit. Values between 1 and 2 are
acceptable in most cases. The order of the linear terms of the exponential background is
determined by the selection of the order of the linear background.
The explanation of the various background models can be found in appendix 1.
1.6 Fit Spectrum (MENU FIT)
The least squares fitting is based on minimizing Chi-square as defined in the chapter Theory
of non-linear function fitting. The optimization is done by means of a modified Marquardt
algorithm /MAR63/. This method changes model parameters in an iterative way and stops the
iterations, if the percentage difference between two consecutive Chi-square values becomes
smaller than a preset value (e.g. 0.1%), a maximum number of iterations is reached (e.g. 20),
or a preset value for the Chi-square has been achieved. The actual Chi-square value is an
indicator of how well the fitted model and the measured spectrum agrees (the ideal value is
1). The percentage difference is calculated from the previous and the actual Chi-square. In
36
any case at least 2 iterations for each spectrum should be performed, since uncertainties in the
parameters (peak areas) cannot be calculated in the initialization phase.
Entering the command without qualifier, one iteration is performed. Repeatedly executing a
FIT command has the same effect as requesting more than one iteration. To perform a
number of n iterations the user has to enter "FIT N_ITER=n". For fitting spectra without
supervision, the parameters, the maximum number of iterations, the minimum Chi-square and
the maximum difference are relevant. These parameters can be altered in the MENU Fitting
control parameters (sub-MENU under Specify parameters for spectrum analysis, Specify
spectrum analysis).
Hint: An error message
Illegal Fano factor
can appear, which usually can be ignored, because for such cases there will be an
internal self-correction for consecutive fits.
Hint: When the fit crashes because of problems with the background model, with a
message
Error during fit !
a change of the kind of background, or easier, a different order of the polynomial

might be useful. For severe cases the program will have to be relaunched with a more
adequate model (from the MENU Spectrum fitting start AXIL again).
1.7 Inspect Reports (MENU Reports)
The decision whether a line must be excluded from the model also should depend on the
corresponding net peak area and its uncertainty, which are calculated when fitting the
spectrum. A line should be removed from the model when the corresponding area is smaller
than 3 times its standard deviation. The user can apply this rule when consulting the report,
which reflects the results of the last least squares fitting. A partial list of the commands of
this MENU is given below:
Overview of the REPORT Commands
COMMAND short description
REPORT SHOW displays default (brief) report in a SCROLL BOX;

REPORT BRIEF displays short report in a SCROLL BOX;
REPORT FULL displays extended report in a SCROLL BOX;
REPORT SAVE saves the default report in a file
REPORT SAVE BRIEF saves the short report in a file.
REPORT SAVE FULL saves the extended report in a file
REPORT DUMP saves the results of the fit as spectral data in a *.DMP file;
The various Save commands will not create the *.ASR files as needed by the quantitative
programs. Reports are displayed in a mutated SCROLL BOX. The list can be scrolled using
the arrow up, arrow down, <PgUp>, <PgDn>, <Home>, and <End> keys or by using the left
mouse button and the command menu. The report file is created in the current directory and
37
its name is the name of the spectrum file with extension OUT or DMP (in case of REPORT
DUMP). The resulting report files are ordinary ASCII files. If the *.OUT or *.DMP file
already exists and if the program is in interactive mode, the user can add the report to the
existing file or overwrite the old one; in batch mode the report is added to the already
existing file.
Hint: The dump command is an elegant way to load raw spectral data into programs
that allow to generate publication-ready spectra: A *.dmp file (see appendix) contains
in the first column the channel number, in the next column the energy, column three
the measured spectrum, column four the fitted spectrum, and the last column the fitted
background (the number 0.1 is found instead of a channel content zero). Many times it
will be sufficient to copy columns two and three from this file and paste them into a
data sheet of EXCEL, etc.
1.8 Make Result File (Sav_Res)
Performing this command saves the results of the spectrum analysis in a file, which has the
name of the spectrum file with extension ASR, in the current directory. The *.ASR file
contains basically the same information as the *.OUT file, however, in contrast to the *.OUT
files, no information about the model is saved. All quantitative METHODs will need *.ASR
files as input.
If the *.ASR file already exists and if the program is in interactive mode, the user has the
possibility to U=update (old values will be kept, if there is no new one), to R=replace the
old results by new ones (old entries are deleted, irrespective of the values), to A=add (new
entries are include, old entries will not be touched) or to C=cancel this operation (the old
result file is kept without any alteration). In batch mode (see there) the old results are
replaced.
Warning: Sometimes it will be advisable to inspect the actual effect of the commands
(U=update, R=replace, A=add) onto the desired *.asr file.
1.9 Analyze Spectrum in Batch Mode (&BATCH)
The spectrum analysis can more or less be automated by the use of the command @BATCH.
The batch file is a text file and consists of lines of commands of the COMMAND
LANGUAGE (User Interface, Appendix).
E.g.:
LOAD SPEC=TEST1
ROI BEG=636 END=825
X-LINES REMOVE ALL
X-LINES ADD SR RB
CALIB ZERO=2. GAIN=19.9
BA FILTER P=12
FIT N=5
REPORT SAV FULL
SAVE_RES
38
In this example TEST1.SPE is loaded from the current directory and fitted with the FILTER
background to obtain the net peak areas of Sr and Rb. The full report TEST1.OUT is created
for diagnostic reasons. This instruction file should be created and edited by means of an
editor or word processor (not provided by this package).
Warning: The batch files must only contain full commands. No abbreviations are
allowed. E.g.: Load Spec=test1. Not: L S=test1 , which will result in error message(s).
A batch file can call another batch file with the @BATCH command, with a nesting level of
10. The various commands accepted by AXIL are listed in Functional description of AXIL
(Appendix).
After entering this command, e.g. by typing "@BATCH TEST.BAT" where TEST.BAT is
the name of the batch file, the commands in the batch file are executed in batch mode.
Warning: Unfortunately the extension BAT has to be typed in too after the filename,
otherwise the file will not be found. Not conform to the use of filenames without
extension throughout the QXAS package!
Hint: It will be sometimes advisable to keep the parameters of energy calibration and
resolution fixed (alternatively only small deviations should be allowed), because the
calibration can drift after a series of similar spectra, when there is one spectrum with
low statistics, an extra peak or one peak less as compared to the others.
1.10 MENU Stop
This command causes the program to return to the upper MENU Perform spectrum fitting.
(It is not possible to use the <ESCape> to get to the upper MENU.)
1.11 MENU Display
The commands of this MENU change the display of the spectrum on the screen.
Overview of the DISPLAY Commands
COMMAND Description
DISPLAY BEG=channel sets the first channel to be displayed;

DISPLAY END=channel sets the last channel to be displayed;
DISPLAY MIN=count sets the minimum value of the Y-axis;
DISPLAY MAX=count sets the maximum value of the Y-axis;
DISPLAY ROI plots the ROI of the spectrum;
DISPLAY SPECTR plots the whole spectrum, automatically setting MIN and MAX
values;
DISPLAY RESIDUAL plots the spectrum and the residuals
DISPLAY LIN changes to linear display mode;
DISPLAY LOG changes to logarithmic display mode.
Although the Chi-square values gives an indication of the goodness of a fit, visual inspection
of the fit is highly recommended. Because of the large dynamic range of the data, a plot of
39
the spectrum and the fit on a linear scale nearly always give the impression of a perfect fit. A
plot of the logarithm of the data is more appropriate.
The best method is to plot the residuals of the fit. Residuals in excess of +3 or -3 indicate
regions of bad fit. It should be noted that the sum of the squares of these residuals is equal to
the Chi-square value.
The displayed part of a spectrum (BEG, END) is not related to the ROI for the fit and has to
be changed there.
1.12 MENU KLM-mark
Using the commands of this MENU it is possible to display the position of all lines of an
element (staring from the element Fe) and is meant to facilitate the identification of elements.
The name of the element considered and its atomic number are given. The position of the
lines depends on the correct energy calibration. Lines appear, if they are included in the
current library file.
KLM-MARK Keyboard and Mouse Functions
Keyboard Functions
Pressing the arrow right (left) key selects the next (previous) element.
Pressing the arrow up (down) key increments (decrements) the atomic number of the currently displayed element
by 10.
Mouse Functions
Selecting command menu items representing arrow keys by putting the mouse pointer on the menu item and
pressing the left mouse button is equivalent to press the corresponding key.
1.13 MENU SCAT_ROI
It is not recommended to use this command, although it will integrate the defined ROIs and
provide good results, but these results will not be read by the quantitative methods.
1.14 MENU PLOT
This command will very likely not generate the desired plot of a spectrum.
It is recommended to use the command DUMP under REPORT (only is accessible after a
successful fit of a spectrum) and create a file (ASCII format) with the extension DMP (see
appendix). Such a file will contain in the form of 5 columns:
channel number energy measured data fitted spectr. fitted backbr.
of a spectrum. The five entries of one line belong to each other. Usually one will load the
columns containing the energy and the measured spectrum into a program like EXCEL, etc.
and create spectra of an outfit that also can be used in publications.
40
2. MENU Specify parameters for spectrum analysis
All the parameters required for spectrum analysis, i.e. the fitting model and some additional
control parameters are held in the model (*.INP) file. The values of the most important
parameters can be set directly in the least squares fitting program.
Remark: Any values used to specify the absorption and/or attenuation, etc., are not very critical,
because only the line ratios of the element groups (e.g., the Kα/Kß ratio) and the background
modeling are affected.
Warning: There is no linking of the data concerning absorption and/or attenuation

between the MENU Specify parameters for spectrum analysis and any of the
Quantitative METHODs (Quantitative analysis). The explanation is that the *.asr files
carry all information that is handed over and their format does not contain absorption and
related data. Therefore it is possible to use parameters for the model of a fit, which will
lead to good results for the fit, but not necessarily describe the real experiment. For the
quantitative METHODS the experimental parameters will have to be described closer to
reality.
By means of the MENU Specify parameters for spectrum analysis less frequently changed
parameters are manipulated. The name of the current model file is displayed in the header of the
MENU and the last two menu items are only applicable to the current parameter file. The current
parameter file contains the default values of the model parameters.
Select parameter file will cause a FORM to appear, in which the user is asked to enter the name
of the directory which contains the model file, followed by a SELECTOR BOX with which a
parameter file can be selected. The selected parameter file then becomes the current parameter
file.
By selecting Create new parameter file a FORM will appear and the user is asked to enter the
name of the new model file. The file name will automatically get the extension INP. All
parameters in the newly created parameter file are set to default values. Two MENUs then
appear one after the other. By means of the first MENU the experimental parameters can be
altered (Specify experimental parameters) and by means of the second MENU the spectrum
analysis parameters can be changed (Specify spectrum analysis parameters). The created
parameter file becomes the current parameter file.
When Specify spectrum analysis parameters is selected, a number of parameters for evaluating
spectral data can be specified: the background parameters, the calibration parameters, the fitting
41
control parameters and the sample absorption. Selecting the menu item Background
parameters causes two FORMs to appear, one after the other. In the first FORM the user has to
select a background type and in the second FORM values of the parameters of the chosen
background can be changed. The other menu items display only one FORM with which values
of the various parameters may be altered.
Overview of spectrum analysis parameters
BACKGROUND TYPE:
Smooth Filter Background number of background iterations

Orthogonal Polynomial or Linear Background order of polynomial
Exponential or Bremsstrahlung Background order of the linear polynomial
order of the exponential polynomial
number of constant terms
values of parameters
flag indicating whether the parameters are initialized automatically
energy near background maximum
CALIBRATION
zero (eV) with its standard deviation

gain (eV/ch) with its standard deviation
noise (eV) with its standard deviation
FANO-factor with its standard deviation
FITTING CONTROL
minimum Chi-square
maximum number of iterations
minimum difference in Chi-square
flag indicating whether the results of the fit will be used as starting values of the next fit
SAMPLE ABSORPTION
sample thickness (g/cm2)

sample composition (element and w%)
By the selection of a background type, the user influences the strategy followed to obtain net
peak areas. Two main classes of approaches can be distinguished: background estimation
methods and least squares fitting methods.
Background Estimation and Least Squares Fitting Methods
Abbreviation
Background Estimation Methods
Smooth Filter Background FILTER
Orthogonal Polynomial Background ORTPOL
Least Squares Fitting Methods

Linear Background LINEAR
Exponential Background EXPON
Bremsstrahlung Background BREMS
The abbreviations of the various methods in the table are the qualifiers used to select the
corresponding method during the spectrum analysis.
Applying background estimation methods, the background is estimated and then subtracted
from the original spectrum prior to the least squares fitting of the resulting spectrum.
42
The (Smooth) FILTER background method is based on the removal of rapidly varying
structures in a spectrum by comparing the channel content yi with the channel content of its
neighbors:
1
mi = (y i−w + y i+ w ) (1)
2
If mi is smaller than yi , the content yi is replaced by mi, which is the mean of the contents of two
channels, a distance w from channel i. The value of the parameter PARAM= (number of
background) # iterations determines how many times this procedure is applied to the spectrum.
Repeating this procedure gradually causes peaks to be "stripped" away. A typical value of this
parameter is 15.
Applying the Orthogonal polynomial background method (ORTPOL), the background is

estimated by a linear combination of orthogonal polynomials and to fit the background channels
as good as possible. For this, the background function is used to minimize the Chi-square, which
is the weighted sum of squares, over the background, of the differences between the background
polynomial and the measured spectrum The crucial step in this method is the decision whether a
channel is a background channel or not. A channel i does not belong to the background if its
counts yi is statistically higher than its approximation ybackgr(i):
IF yi > ybackgr (i)+ rٛ ybackgr (i)

(2)
THEN i is NOT a background channel
r is an adjustable parameter, which must be set (R=) when selecting the background during
spectrum analysis. The order of the orthogonal polynomial should depend on the shape of the
background. High numbers of fluctuations or oscillations, and higher curvatures request higher
orders.
In contrast with the background estimation methods, the least squares fitting methods use fitting
models containing also a part, which describes the background:
ymod (i) = ybackgr (i) + ∑y

peaks
peak (i) (3)
where ymod(i) is the calculated content of channel i, and the first part describes the background
contribution and the second part the contributions from all characteristic lines.
These lines are added to the model while analyzing spectra (see item 1.3.). The general concept
of least squares fitting is to minimize the Chi-square, which is the weighted sum of squares, over
a region of the spectrum, of the differences between the model and the measured spectrum yi:
1 n (yi − ymod (i))2

χ =
2
∑ σ2
n − m i=1
with σ i2 ≈ yi (4)
i
where n is the number of channels and m the number of parameters used in the fit. By selecting a
fitting method, the user determines the analytical function used to describe the background.
In case of LINEAR background the background is estimated as sum of polynomials as a

function of the energy. The parameters of the resulting background function are then optimized
in the least squares fitting. The user may set the default order of the polynomials (PARAM=).
43
High numbers of fluctuations or oscillations (= higher curvatures) and wider ROI request higher
orders of polynomials.
When EXPONential background is selected, the background is modeled by functions of type:
m
n 
ybackgr (i) = ∑ ak ∆E k +b0 exp ∑ bl ∆E l 
k =0  l =1  (5)
with ∆E = Ei − E0
where Ei is the energy in keV of channel i and E0 is a suitable reference energy, often the middle
of the fitting region (energy near background maximum). E0, the default order m of the linear
polynomial (specified in Linear background) and the default order n of the exponential
polynomial may be set by the user.
In order to describe the radiative background of electron and particle induced X-ray spectra, the
user should select BREMSstrahlung background, which describes the background by an
exponential polynomial, as described above, multiplied with the absorption characteristics of the
spectrometer T(Ei):
m
n 
ybackgr (i) = ∑ ak ∆E k +b0 ⋅ T(Ei ) ⋅ exp ∑ bl ∆E l  (6)
k =0  l =1 
The user may set essentially the same parameters as for EXPONential background. The total
absorption correction factor T(Ei) is composed of a number of contributions:
T(Ei ) = TDetector (Ei ) + TPath (Ei ) + TSample (Ei ) (7)
To build up the different correction terms, additional parameters are needed.
Contributions to the absorption correction factor
Correction term Parameters
TDetector(Ei) see "Detector characteristics"

("Specify experimental parameters")
TPath(Ei) see "Path length",

"Filter absorption",
"Funny filter absorption"
44
("Specify experimental parameters")
TSample(Ei) see "Sample absorption"

("Specify spectrum analysis parameters)
In order to express channel i into a meaningful energy Ei, the spectrum should be calibrated.
Hint: It is possible, but not necessary to energy calibrate the system in the below
described manner. Inside the fitting procedure with 2 (or more) well known lines the
calibration can be achieved.
For this, default values of additional parameters can be specified in a FORM, which appears after
the selection of Calibration parameters. These values are the initial values of the parameters,
which are optimized in the least squares fitting (see paragraph 1.2). The calibration equations
are:
Ei = ZERO+ GAIN ⋅ i (8)
where Ei is the energy in eV corresponding to channel i; ZERO is the zero offset in eV (the
energy of channel 0) and GAIN is given in eV/channel;
FWHM2 = NOISE2 + 2.352 ⋅ ε ⋅ FANO⋅ E (9)
FWHM is the Full Width at Half Maximum of the detector response function in eV of a
characteristic line having energy E , NOISE is the electronic noise contribution (in eV) to the
peak broadening, ε is the average energy required to create an electron-hole pair and FANO is the
Fano factor. For the definition of the term Fano factor see the appendix.
Default values for these parameters are: ZERO=0 eV, GAIN=20 eV/channel, NOISE=120 eV,
FANO=0.114.
When performing the least squares fitting, the optimal values of the model parameters are to be
found in an iterative way. These iterations should be stopped when certain conditions are
fulfilled. These conditions can be specified in a FORM, which appears after selecting Fitting
control parameters. The user may set the maximum number of iterations, the minimum Chi-
square and the maximum difference in Chi-square, and a flag, which indicates whether the
results of the fit will be used as starting values for the next fit.
45
Sample absorption: In case of X-ray fluorescence the absorption correction term T(Ei) contains
the sample absorption correction term TSample(Ei):
1 − e − χ s fs
T Sample (E i ) =
χs fs (10)
with f s = ( ρ d) s
and the sample attenuation coefficient is given by:
µ s ( E0 ) µ s ( Ei )
χs = + (11)
sin θ1 sin θ 2
where µs is the mass attenuation coefficient, fs the product of the density and the thickness of the
sample, E0 the excitation energy, θ1 and θ2 are the angle of incidence and the detector take-off
angle.
E0, θ1 and θ2 are set as experimental parameters (see Excitation conditions of the MENU
Specify experimental parameters).
The sample attenuation coefficient can only be calculated accurately, if the weight fractions of all
elements constituting the sample are known. Although in many cases the sample composition is
not known, since the aim of the spectrum analysis is to obtain the net peak areas from which the
concentrations are to be calculated, a rough estimate of the sample composition is often
sufficient.
The sample composition, together with the value of fs, is asked in a FORM, which appears after
selecting Sample absorption in the MENU Specify spectrum analysis parameters.
In many cases where there are problems with fitting, the specification of the sample/standard
self-absorption will correct “bad” Kα/Kß ratios and improve results.
Selecting Specify experimental parameters, the experimental conditions related to the

excitation mode, excitation conditions, detector characteristics, filter and funny filter placed
46
between sample and detector, and the atmosphere in the excitation chamber can be specified.
The menu items display FORMs with which values of the various parameters may be altered.
Overview experimental parameters
Menu item Parameters

EXCITATION MODE mode: XRF, PIXE or EPMA
EXCITATION CONDITIONS primary excitation energy (keV)
angle of incidence (degrees)
detector take-off angle (degrees)
DETECTOR CHARACTERISTICS thickness of the beryllium window (µm)
thickness of the gold layer (µm)
detector type ( Si(Li) or Ge(Li) )
detector dead layer (µm)
detector active depth (mm)
pulse pileup resolution time (micro seconds)
FILTER ABSORPTION thickness of the absorbers (g/cm2)
composition of the absorbers (element and w%)
FUNNY FILTER ABSORPTION thickness (g/cm2)
hole fraction
composition of the filter (element and w%)
PATH LENGTH path between sample and detector (Air, Helium or

Vacuum)
path length (cm)
By selecting Excitation mode a FORM appears, with which the excitation mode (XRF, PIXE or
EPMA) is selected.
When Excitation conditions is selected, a FORM appears and the user is asked to enter the
primary excitation energy (keV), the angle of incidence (degrees) and the take-off angle of the
detector (degrees). These values are used to correct for sample absorption (see Sample
absorption of the MENU Specify spectrum analysis parameters).
After selecting the Detector characteristics the values of various parameters, with which the X-
ray attenuation by the detector can be taken into account, can be entered in a FORM.
47
The detector efficiency model contributes to the absorption correction term T(Ei) (see
explanation of Bremsstrahlung Background above) is in the case of a Si(Li) detector:
TDetector =e
− ( µ s ρd )Be
⋅e
− ( µ s ρd ) Au
⋅e
− ( µ s ρd )Si
[
⋅ 1− e
− ( µ s ρD )Si
] (12)
where the exponents are the products of the mass attenuation coefficient, the density and the
thickness of the Be-window, the gold contact layer and the silicon dead layer. In the last term D
is the thickness of the detector crystal. The user may select the Si(Li) or the Ge(Li) detector.
Other detector types like HgI are not supported.
Any absorption of X-rays along the path between the sample and the detector is to be described
in an absorption correction term. It is calculated from the composition and the thickness of the
absorber entered in a FORM, which appears after selecting Filter absorption.
If there is a funny filter (absorber with a hole) between the sample and the detector, the
absorption behavior of this structure is modeled by:
TFunny filter (E) =(1 − H )⋅ e − (µρd ) (13)
This correction term is calculated from the composition and the thickness of the filter, and the
hole fraction H (the fraction of the detector solid angle subtended by the hole) of the funny filter
(Funny filter absorption).
Absorption of X-rays along the path between the sample and the detector is taken into
account by another absorption correction term. The user may select Air, Helium or Vacuum
as medium, and set the path length. The mass attenuation coefficient of air is calculated
assuming a composition of 79.8% N2, 19.9% O2 and 0.3% Ar and a density of 1.2 kg/m3.
3. MENU Manage X-ray library
48
The X-ray library contains the X-ray energies and relative intensity ratios of all chemical
elements and is primarily used by the least squares spectrum analysis program to obtain these
data when an element is included in the fitting model.
The ITEMs Select X-ray library and Inspect/Modify X-ray library are most often used. The
last three menu items are only applicable to the current library of which the name is displayed in
the header of the MENU. The current library, which is the library used by the spectrum analysis
program, can be selected by means of the ITEM Select X-ray library.
When Create new, empty library is selected, a FORM appears and the user is asked to enter the
name of the new *.XRL file. The file name will automatically get the extension XRL and the
data in the created library are set to zero, i.e. none of the chemical elements will have any
characteristic lines associated with it. It should be stressed that newly created libraries do not
automatically become the current library and that the user should select the appropriate library,
which will be used in the spectrum analysis, before leaving the MENU.
After selecting Select X-ray library, a FORM appears in which the user has to enter the name of
the directory which contains the *.XRL file, followed by a SELECTOR BOX with which a
library can be selected. The selected library then becomes the current library.
If Inspect/Modify X-ray library is selected, and one of the menu items is selected, two FORMs
appear one after the other. The first FORM is used to enter the symbol of an element and in the
second FORM the user can alter energies (keV) together with the corresponding relative
intensities of the lines belonging to the element given in the previous form, or its ratios between
groups of lines. When the user leaves this FORM, the current *.XRL file is immediately updated
with the new information (if any).
The selection of Write content of library to text file will cause a FORM to appear in which the
name of the text file must be entered together with the range of elements, defined by entering
symbols of the first and the last element, to be exported. The data of the elements within the
specified range is then copied from the current library to the text file in a particular format (see
below).
After selecting Update library with data in text file a FORM appears in which the name of the
text file must be entered. The current library is then updated with the information in the text file.
The text file must be in a particular format (see below).
49
After creating (Create new, empty library) or selecting an *.XRL file (Select X-ray library),
the data can be altered one by one (Inspect/Modify X-ray library), or updated (batch-wise)
with data in a text file (Update library with data in text file), which was created from another
*.XRL file (Write content of library to text file) and changed by means of a word processor or
an editor.
For each of the elements H to Lw, the *.XRL file contains data related to 5 groups of X-ray lines:
the K, LI (L1), LII (L2), LIII (L3) and M groups. For each group a number of X-ray transitions
are defined as indicated in the table below.
50
Different X-ray transitions defined in the XRL file
Group Transition
K Kα1 (KA1)
Kα2 (KA2)
Kß1 (KB1)
Kß2 (KB2)
Kß3 (KB3)
LI L1-M3
L1-M2
L1-N3
L1-N2
L1-O3
L1-O2
L1-M5
L1-M4
L1-N5
L1-N4
LII L2-M4 (LB1)

L2-N4
L2-M1
L2-N1
L2-O4
L2-O1
L2-M3
LIII L3-M5 (LA1)

L3-M4 (LA2)
L3-N5
L3-N4
L3-M1 (Ll)
L3-N1
L3-O1
L3-O5
L3-O4
M M1
M2
These transitions represent the major X-ray lines in each group. Not all the lines are present for
all elements. E.g. for the Fe K lines the following data is present:
Fe K lines
Line Energy (keV) Rel.Int.
Kα1 (KA1) 6.399 0.8298

Kα2 (KA2) 0. 0.
Kß1 (KB1) 7.059 0.1702
Kß3 (KB3) 0. 0.
Kß2 (KB2) 0. 0.
The relative intensity (Rel.Int.) is the fraction of X-ray photons emitted with the corresponding
energy to the total number of X-ray photons emitted in that group, in this case the K-group.
Although the 5 transitions exist, the separation between Kα1 and Kα2 is so small (about 10 eV)
that both can be represented in the spectrum analysis by one line with an energy equal to the
weighted average:
51
E(Kα1,2) = w1 E(Kα1) + w2 E(Kα2) (14)
with weights w1 and w2 for the lines Kα1 and Kα2 defined as
w1 = R1 / (R1 + R2)
w2 = R2 / (R1 + R2) (15)
R1 and R2 are the relative intensities for the lines Kα1 and Kα2. Thus the first entry represents the
Fe Kα1,2 energy and relative intensity, because the second entry has zero energy. The same is
true for the Fe Kß1 and Fe Kß3 lines; the third entry represents the Fe Kß1,3 energy and relative
energy. The Fe Kß2, which corresponds to a forbidden transition, is negligible for Fe; therefore
its energy and relative intensity is zero.
For Al only the Kα1 entry is non-zero, it represents the average K-energy of Al(Kα1, Kα2 and
Kß). For Ba all entries are non-zero.
The relative intensities within each group K, LI, LII, LIII are physical constants and independent
of the excitation mode (monochromatic or polychromatic photons, electrons or protons). These
relative line intensities within one group as observed in a spectrum may be altered by absorption
in the sample or the detector, but these effects are corrected for in the spectrum analysis.
However, the relative intensities between the groups depend on whether X-ray, electron or
charged particles are used for the excitation and on the energy of the exciting projectiles. In the
library the following ratios between the various groups can be entered for a given experimental
condition:
Relative intensities between groups
Ratio
L1/L
L2/L
L/K
M/L
Once the first two ratios for a certain element are known the L-lines of that element can be used
as one group in the spectrum analysis. The default library AXIL.XRL contains L1/L and L2/L
ratios for most common elements assuming a monochromatic excitation with X-ray photons of
approximately 20 keV.
The X-ray library management functions should be used to create an XRL file for the particular
experimental set-up. The line group ratios are calculated using the results of the spectrum
analysis (1. MENU Perform spectrum fitting) in which the concerning line groups are added
separately to the model.
Adding an L group, whose ratios are zero (L1/L=L2/L2=0) will automatically set these ratios to
the default value of 0.1 and 0.3. In the absence of the knowledge of group ratios, however, it is
still possible to analyze a spectrum for this element by considering the group lines individually.
It is possible to write the contents of an XRL file to a text file. E.g. for Fe the following data
should be found in the text file:
52
Format of a text file, created from an *.XRL file
Fe 4
KA1 6.399 0.8298
KB1 7.059 0.1702
L1M3 0.941 1.0000
L2M4 0.869 0.9524
0.0000 0.0000 0.0000 0.0000
where the first line indicates the element and the total number of characteristic lines listed. The
first column of the next 4 lines contains the label of the transition as indicated in the table above,
the second column contains the X-ray energies in keV, the third one the relative intensities. The
last line contains the ratios of the groups. The text file can be edited by a text editor and used to
update the current XRL file, replacing the old values of the current library by the corresponding
values encountered in the text file.
53
Quantitative
analysis
54
55
Direct comparison of count rates
1. Introduction
The simplest METHOD for the Quantitative analysis is Direct comparison of count rates.
By use of the sensitivities determined from standards, concentrations of elements in unknown
samples can be determined.
No absorption (or inter element effect) corrections are calculated. Therefore it is advised to
work with this METHOD only as long as these corrections are equal for standards and
unknown samples, i.e., specimens with similar composition. For thin and intermediate thick
samples (standards) the area density must be constant.
If more than 3 standard elements are found, concentration values for elements of an unknown
sample (not represented by standards) can be interpolated or extrapolated. Kα-lines and Lα-
lines are treated independently.
2. Calibration
2.1 MENU Define calibration and standards
The first ITEM of the MENU Direct comparison of count rates will be Define Calibration
and Standards.
Choosing this option, the next MENU Current calibration allows to either select an old
calibration file or create a new one, the last calibration file used is mentioned there; when no
files with extension .cal are present in the current directory if you try to Select a calibration
file the message No files (*CAL) found appears.
Warning: If there exist calibration files generated by other quantitative METHODs

(e.g. Elemental sensitivities, ... ), those cannot be loaded, due to incompatibility.
Error message: Calibration file not set up for direct comp.
56
2.1.1 Create a new calibration file
Continuing correctly, a FORM is displayed that asks for many inputs.

As Excitation source basically only 2 options are available: Tube excited XRF and Radio
source. <ESCape> is needed to continue.
The excitation source has to be specified as Fe-, Zr-, Mo- secondary target or Fe-55, Cd-
109, Am-241 source. For a choice User defined one can define his own Source name (max.
19 characters).
For source excitation the Source half live is used to correct for the decay of the radioactive
source.
In the ITEM Filename, if the default directory C:\AXIL\SPECT is kept, only a name for this
calibration file has to be entered. The extension CAL is automatically used for these files. If
one chooses
E.g. the name TEST1, an ASCII file TEST1.CAL can be found afterwards in the sub-
directory C:\AXIL\SPECT.
There are 4 ways to achieve this: With the mouse click behind the last slash and type TEST1,
or using the right arrow key repeatedly, and counting the passed characters of
C:\AXIL\SPECT, will bring to the same position, alternatively one can use the <END> key,
and finally by retyping the string C:\AXIL\SPECT\TEST1 (overwriting).
Warning: If a file with the same name already exists, the old file will be overwritten
without any message!
57
2.1.2 Edit existing *.CAL file
If the MENU displays Current calibration and the newly created file (or an already existing
one) and the directory where it can be found, the user can Add standards.
Under Select standard files one will find a SELECTOR BOX with several files, all with the
extension ASR (result files of AXIL). The user should select the applicable standards from
the SELECTOR BOX by highlighting the respective lines and selecting them by pressing
<ENTER>. An asterisk at the beginning of the line indicates selected items.
Only such files will be useful for the calibration procedure, that were obtained from samples
with well specified concentration values for the elements represented by characteristic X-ray
lines.
The following FORM (Data for standard) allows editing the measuring Live time (usually
not to be changed) and the Date (used to correct for the decay of the source for excitation
with a radioactive source). The Tube current has to be entered (for tube excitation only).
In the next FORM (also named Data for standard) one has to navigate from one entry to the
next. Within such an ITEM it is possible to move from one character to its neighboring one
and overwrite it (if necessary). Again clicking at the desired position with the mouse
substitutes any arrow key movements. Changes have to be confirmed with <ENTER>.
Entries are needed for a Compound of each listed element. If one enters the element name
only (usually already the default), this means that the compound is not known, or the element
is not bound at all. For any compounds the concentration values to be entered are the ones for
the whole compound.
Concentration units can be selected as ppm or % (use arrow left/right). Leaving any values
at the default 0.0 suppresses this line for the sensitivity calculations (e.g. contamination lines
that had to be included in the fitting procedure).
58
The relative standard deviation (%stddev) from these concentration values will be used for
weighting the measured sensitivities (section 2.2 of this chapter MENU Perform
Calibration). It should contain any deviations from the concentrations of the used chemicals
from the certificate (hopefully given by the manufacturer), as well as uncertainties in the
preparation of the standards. Practically only the repeated preparation and evaluation of
identical standards in a statistically significant number can lead to correct values. As
compromise a default value of 5% has been adopted.
As mentioned above it is recommended to establish sensitivities with more than one standard.
On the one hand to cover a range of elements (if one wants to quantify most of the
measurable elements) on the other hand it is possible to determine the sensitivity of one
element by different standards. (An average value will be used for further treatment of
unknown specimens, the individual values are given in the later mentioned report.)
Consequently the same procedure of this MENU has to be repeated as many times as ASR
files were marked under Select standard files.
Finally one arrives again in the MENU Current calibration. More standards can be added
(if e.g. for testing purposes one only loads a single *.ASR file), or it is possible to Remove
standards (e.g. one erroneously added an unknown to the standards list), or the option Edit
standards might be convenient to correct any typing errors. With the <ESCape> character
one gets back to the upper MENU.
2.2 MENU Perform calibration
All previous attempts to start the MENU Perform Calibration of X-ray system would have
ended with the message no files (*.CAL) found. With the newly created *.CAL file, that also
can be loaded under Select Calibration file one can continue. From now on usually a default
one will already be present: it is the last calibration file having been used in the previous
sessions.
If a suited *.CAL file was created or loaded one can Perform the Calibration and a
SCROLL BOX Calibration report is displayed. The actual calibration is performed by the
calculation of the sensitivities (K-ratios) of all elements for which concentration and peak
area are supplied in the current *.CAL file.
59
counts
K= ⋅ 100
time ⋅ current ⋅ conc
K sensitivity (K-ratio)
counts net peak area of a characteristic line
time live time of the spectrum
current Tube current of the X-ray tube.

For source excitation the tube current has to be substituted by the decay
correction.
conc Concentration of the element producing the above characteristic line in the
standard.
Kα and Lα lines are treated separately; this continues for the rest of this program. If more
than one sensitivity can be calculated for a certain element, the average sensitivity will be
calculated. The report contains all individual results for each standard ( *.ASR file) and a
summary of the calculated sensitivities. This report can be saved as a text file (extension
ARP) and/or printed, but is not needed for further calculations. The calculated sensitivities
are stored in the current calibration file, which is used for the analysis of unknown samples.
By the use of the <ESCape> the final step of the calibration, namely Optimize calibration
with least square fit, can be performed. Through all previously determined sensitivities a
polynomial function of the atomic number Z of the form
Sensitivity(Z) = a0 + a1 ⋅ Z + a2 ⋅ Z 2 +...
or
log(Sensitivity(Z)) = b0 + b1 ⋅ Z + b2 ⋅ Z 2 +...
can be fitted. This procedure thus calculates the sensitivities as smooth function of the atomic
number. Small uncertainties of individual results are eliminated (this does not necessarily
improve results!), and more important, calculates (by interpolation and extrapolation)
sensitivities for elements for which no standards were available. At least 3 elements for K, as
well as for the L-lines are needed, otherwise only the respective elements will be analyzed.
E.g. If one is interested in a sample that contains lead as sole emitter of detectable L-
lines, one could cover Pb only with a suited standard. The Optimize calibration with
least square fit procedure will fail (only one standard for the L lines). Still it is
possible to analyze the lead content of unknown specimens, whereas Hg, Au, ...
cannot be analyzed.
60
In the FORM polynomial fit of Ka sensitivities several parameters for the actual fitting
procedure have to be fixed (but can be altered again by repeating this procedure). The
selection of the order of the polynomial (max. equal to number of data points), whether a
linear or logarithmic function (according to the above formulas) is assumed, and the Yes/No
option for weighting of the data points with the already mentioned standard deviation
(concentration of standards), are quite arbitrary. With the selection of the First element and
the Last element one can force the program to extrapolate to elements not represented by
standards, or one can exclude troublemakers.
E.g. elements with low Z, because for some specimens the absorption correction for
their characteristic lines cannot be done adequately.
Even sensitivities one element below the first and one above the last element are calculated.
If one attempted to fit a sensitivity curve through less than 3 points, one will receive an error
message: Less than 3 values for sens. Can not fit. Still one can continue with the calibration
and will obtain concentrations for all elements of the unknown that are represented by
standards.
The result of a successful fit is displayed graphically. The option to toggle between Lin and
Log plot does not affect the fitting results, but the video display only.
If applicable the procedure continues with Polynomial fit of La sensitivities.

The updated Calibration report is displayed again. If no further changes are desired for the
Current calibration, <ESCape> will lead to the upper MENU.
3. MENU Quantitative analysis of unknown samples
If well established *.CAL files already exist, all the previous steps can be omitted, and only
such a file, appropriate for a certain unknown sample, has to be loaded.
The ITEM Quantitative analysis of unknown samples leads to similar MENUs as for the
standards. For the excitation mode with X-ray tube the Tube current can be different to the
measurements of the standards. For source excitation the Date (of the actual measurements)
will be needed to correct for the decay of the excitation source.
61
The possibility to enter compounds rather than elements exists again in the FORM Data for
sample, what will result in a final report that contains concentration values for the whole
compound. If one enters the element only (usually already the default), this means that the
compound is not known, or the element is not bound at all.
The result sheet Sample (SCROLL BOX) contains the desired concentrations of elements
(compounds) in the unknown sample. Under Define file to save analysis results it can be
stored as ASCII file with the extension ARP .
4. Demonstration
For demonstration purpose one brass standard (NBS 1107, spectrum file BRA1107.spe)
serves to calibrate the system (Zr-secondary target geometry, described in table 2), which
was used for the measurements. As the METHOD does not correct for absorption or inter
element effect, the “unknown” sample must be close in composition, like e.g., the reference
standard NBS 1108 (BRA1108.ASR).
Table 1: Brass standards
NBS 1103, NBS 1107 NBS 1108

file BRA1103.ASR file BRA1107.ASR file BRA1108.ASR
Element concentration
in %
Fe 0.26 0.037 0.050
Ni 0.15 0.098 0.033
Cu 59.27 61.2 64.9
Zn 35.72 37.3 34.4
Pb 3.73 0.18 0.063
62
Table 2: Experimental conditions
Mo X-ray tube: 30 kV high Voltage, 20 mA current.

Zr secondary target.
Si(Li)-detector.
A new *.CAL file has to be created by the user as described above.

If the standard is treated in an adequate way, the sub MENU Perform calibration will result
in a SCROLL BOX Calibration report, containing all information available to the
METHOD and the calculated K and/or L sensitivities.
In the sub MENU Optimize calibration with least square fit (FORMs Polynomial fit of
Ka/La sensitivities) for the Type of fit the option Linear and an Order of 3 should be
selected. As example the linear display of the fitted curve for the K sensitivities is given.
63
For the L-lines the METHOD will given an error message Less than 3 values for sens. Can
not fit, automatically, because lead is the only element for the determination of the L
sensitivities.
After the fit an updated Calibration report is displayed.
64
It will contain the coefficients calculated during the fitting procedure and the individual
sensitivities for the measured standard elements and for elements that can be interpolated. K
and L lines are separated.
The user should then select the MENU Analyze unknown samples and select the file:
BRA1108.ASR
The SCROLL BOX Sample will provide the user with the desired concentrations.
65
Elemental sensitivities
1. Introduction
The quantitative METHOD Elemental sensitivities determines the sensitivity of

characteristic lines from standards, taking into account the self-absorption in the standards.
The calculated sensitivities are then used to determine the concentrations of elements in
unknown samples, again correcting for the sample self-absorption. The composition of the
dark matrix must be known. Also intermediate thick and thin specimens can be evaluated, if
their aerial density is known.
If more than 3 standard elements are found, concentration values for elements of the
unknown sample (not represented by standards) can be interpolated and extrapolated. Kα-
lines and Lα-lines are treated independently.
It is assumed that the excitation radiation for standards and samples can be represented by a
single X-ray line with specified energy. For the calculations of the absorption coefficients the
values of reference /THI79/ are used.
An on-line HELP can be activated throughout the whole METHOD with the <F1> key.
2. Calibration
The first ITEM of the MENU Elemental sensitivities will be Define Calibration and
Standards.
calibration file or create a new one. The last calibration file used is mentioned there. If no
files with extension .cal are present in the current directory, when one tries to Select a
calibration file, the message No files (*CAL) found appears.
66
(e.g. DIRECT COMPARISON OF COUNT RATES, ... ), those cannot be loaded,
due to incompatibility. Error message: Calibration file not set up for elem. sens.
Continuing correctly a FORM is displayed that asks for many inputs:

(active) source. The Angle of incidence and the take-off angle are defined as the angles
between the respective directions of X-rays and sample surface; their values must be greater
than 0o and smaller than 90o. <ESCape> is needed to continue.
109, Am-241 source. For a choice User defined (max. 20 characters) one can define an own
Average excitation energy. If one uses
E.g. a Rh secondary target the weighted average of its Kα and K β line yields
E = 20.6keV . For the excitation with the primary radiation of an X-ray tube
sometimes so called effective energies are defined. Such procedures might lead to
good results, from the theoretical point of view it is not recommended to apply
polychromatic excitation.
All previous steps are needed for the absorption corrections calculations. For source
excitation the Source half live is used to correct for the decay of the radioactive source.
67
In the ITEM Filename, if the default directory C:\AXIL\SPECT is kept, only a name for this
calibration file has to be entered. The extension CAL is automatically used for these files. If
one chooses
E.g. the name TEST2, an ASCII file TEST2.CAL can be found afterwards in the sub-
Many inputs of the above described MENU Create a new calibration file are needed for its
creation only and are not used for the final calculations, but the data of a *.SOU file (source
file), to be loaded later in the MENU System sensitivity, instead.
If the MENU displays Current calibration and the newly created file (or an already existing
one) and the directory where it can be found, one can Add standards.
extension ASR (result files of AXIL). At least one, but preferably several of them have to be
Selected by <ENTER> at the respective lines, which is indicated by an asterisk at the
beginning of the line.
lines. Their whole composition must be known.
The following FORM (Data for standard) allows editing the measuring Live time (usually
not to be changed) and the Date (used to correct for the decay of the radioactive excitation
source). The Tube current has to be entered (for tube excitation only). The Sample mass
(rather aerial density) is needed for the use of thin and intermediate thick standards.
Hint: The input for any previous standard (current, mass) is kept as default value for
the next one.
next. Within such an ITEM it is possible to move from one character to its neighboring one
68
and overwrite it (if necessary). Again clicking at the desired position with the mouse
substitutes any arrow key movements. All changes have to be confirmed with <ENTER>.
Entries are needed for a Compound of each listed element. If one enters the element name
the whole compound. The absorption corrections will be calculated according to the
compound. Alternatively, instead of explicitly entering a compound, or in the presence of
binders, etc., the FORM Concentration of other elements can be used to specify other (non
fluorescing) elements of the standard.
E.g. the standard calcium carbonate can be treated as CaCO3 for Compound with
100% in the FORM Data for standard, or as Ca with 40.04%, and entries in the
FORM Concentration of other elements for C with 12% and O with 47.96%.
Warning: Use upper and lower case characters correctly. If the standard contains e.g.
calcium carbonate, enter as compound CaCO3. Do neither enter CACO3, nor CaCo3,
nor caco3 instead!
Concentration units can be selected as ppm or % (use arrow left/right). Leaving any values
at the default 0.0 suppresses this line for the sensitivity calculations (e.g. contamination lines
that had to be included in the fitting procedure).
weighting the measured sensitivities (see section 2.2: FORM Polynomial fit of sensitivities).
It should contain any deviations from the concentrations of the used chemicals from the
certificate (hopefully given by the manufacturer), as well as uncertainties in the preparation
of the standards. Practically only the repeated preparation and evaluation of identical
standards in a statistically significant number can lead to correct values. As compromise a
default value of 5% has been adopted.
As mentioned above, it is recommended to establish sensitivities with more than one
standard. On the one hand to cover a range of elements (if one wants to quantify most of the
measurable elements) on the other hand it is possible to determine the sensitivity of one
element by different standards. (An average value will be used for further treatment of
unknown specimens, the individual values are given in the later mentioned report.)
Consequently the same procedure of this MENU has to be repeated as many times as ASR
files were marked under Select standard files.
Finally one arrives again in the MENU Current calibration. More standards can be added
(if e.g. for testing purposes only a single *.ASR file was loaded), or it is possible to Remove
69
standards (e.g. one erroneously added an unknown to the standards list), or the option Edit
standards might be convenient to correct any typing errors. With the <ESCape> character
one gets back to the upper MENU.
All previous attempts to start the MENU Perform Calibration of X-ray system would have
can be loaded under Select Calibration file one can continue. From now on usually a default
sessions.
When a suited *.CAL file was created or loaded one can Perform the Calibration and a
SCROLL BOX Calibration report is displayed. The actual calibration is performed by the
calculation of the sensitivities of all elements for which concentration and peak area are
supplied in the current *.CAL file.
counts ⋅ abs.fac
Sens =
time ⋅ current ⋅ conc
Sens sensitivity
counts net peak area of a characteristic line
abs.fac absorption correction factor
time live time of the spectrum
current tube current of the X-ray tube
For source excitation the tube current has to be substituted by the decay
correction.
conc Concentration of the element producing the above characteristic line in the
standard.
Kα and Lα lines are treated separately; this continues for the rest of this program. If more
than one sensitivity can be calculated for a certain element, the average sensitivity will be
calculated. The report contains all individual results for each standard ( *.ASR file) and a
summary of the calculated sensitivities. This report can be saved as a text file (extension
ARP) and/or printed, but is not needed for further calculations. The calculated sensitivities
are stored in the current calibration file, which is used for the analysis of unknown samples.
70
With <ESCape> the final step of the calibration, namely Optimize calibration with least
square fit, can be performed. Through all previously determined sensitivities a polynomial
function of the atomic number Z of the form
Sensitivity(Z)
= a0 + a1 ⋅ Z + a2 ⋅ Z 2 +...
µm (Z)
or
 Sensitivity(Z) 
 = b0 + b1 ⋅ Z + b2 ⋅ Z +...
2
log 
 µ m (Z) 
can be fitted. µm (Z) is the mass attenuation coefficient for an element with the atomic
number Z. This procedure thus calculates the sensitivities as smooth function of the atomic
number. Small uncertainties of individual results are eliminated (this does not necessarily
improve results!), and more important, calculates (by interpolation and extrapolation)
sensitivities for elements for which no standards were available. At least 3 elements for K-,
as well as for the L-lines are needed, otherwise only the respective elements will be analyzed.
Hint: If the user is interested in a sample that contains lead as sole emitter of
detectable L-lines, one could cover Pb only with a suited standard. The Optimize
calibration with least square fit procedure will fail (only one standard for the L
lines). Still it is possible to analyze the lead content of unknown specimens, whereas
Hg, Au, cannot be analyzed in that case.
71
In the FORM Polynomial fit of Ka sensitivities several parameters for the actual fitting
selection of the Order of the polynomial (max. equal to number of data points), whether a
option for weighting of the data points with the already mentioned standard deviation
(concentration of standards), are quite arbitrary. With the selection of the First element and
the Last element one can either force the program to extrapolate to elements not represented
by standards, or one can exclude troublemakers.
E.g. elements with low Z, because for some specimens the absorption correction for
their characteristic lines cannot be done adequately.
Even the sensitivities one element below the first and one above the last element are
calculated.
Attempting to fit a sensitivity curve through less than 3 points, one will receive an error
and will obtain concentrations for all elements of an unknown sample that are represented by
standards.
If applicable the procedure continues with Polynomial fit of La sensitivities.

Finally the updated Calibration report is displayed again by use of the <ESCape>. If no
further changes are desired for the Current calibration, <ESCape> will lead to the upper
MENU.
will be needed to correct for the decay of the isotope source. The Sample type: Thin, thick,
intermediate thick sample does not have to be in accordance with the standards.
E.g. the standards are usually thick pellets of pressed powders or drums of pure
metals, whereas the samples could be thin filter materials.
sample, what will result in a final report that contains concentration values for the whole
compound. If one enters the element name only (usually already the default), this means that
the compound is not known, or the element is not bound at all.
72
For thick and intermediate thick samples again Known constituents can be entered and a
Compound by difference, that represents any unknown, non-detectable light elements (dark
matrix). This compound by difference will be treated in such away, that its concentration
always sums up to 100% with the other elements of that sample, known to the program. This
information is needed again for the absorption correction calculations.
The compound by difference should be selected so that the absorption of the dark matrix is
represented adequately. The important point is the average atomic number of this compound
or element. For
E.g. soil samples the matrix will consist of oxygen from the oxides, quartz, etc. One
can try to match reality with a fictitious SiOx . The integer x will adjust the oxygen
contribution to the absorption. For this compound by difference the average atomic
number of the matrix will be limited to the range Zmean = 8 -14. For quartz is Z mean =
10.8 .
Since the estimations of the sample absorption and of the concentrations are done iteratively,
the number of iterations required and the mean and maximum concentration difference
between the last two iterations are indicated in the result sheet Sample (SCROLL BOX), that
contains the desired concentrations of elements (compounds) in the unknown sample. Under
Define file to save analysis results it can be stored as ASCII file with the extension ARP .
4. Demonstration
The *.spe files, as found in the directory C:\AXIL\SPECT, and listed in the table: Standards
(appendix), have to be fitted first in order to obtain *.asr result files of AXIL. The matching
spectra were measured under the conditions as given in the table: Experimental conditions.
The twenty-five SD00*.spe files represent the standards, covering a wide range of K- as well
as L-lines. Several of them are metallic foils (thick samples), the others are pressed pellets,
usually with binders added.
73
No *.CAL file exists; so it has to be created by the user as described above.
In the FORM Data for standard no compounds were entered, but the FORM Concentration
of other elements was edited instead.
Warning: Several of the pure standards contain contaminations, like Cu, Fe, etc.
Their lines have to be included for the sake of the fitting procedure for some cases;
such concentration values should be set to zero.
If all standards were treated in an adequate way, the sub MENU Perform calibration will
result in a SCROLL BOX Calibration report, containing all information available to the
method and the calculated K and/or L sensitivities. In the sub MENU Optimize calibration
with least square fit, FORMs Polynomial fit of Ka/La sensitivities, for the Type of fit the
option Linear and an Order of 3 should be selected. As example the linear display of the
fitted curve for the K sensitivities is given.
74
Table: Experimental conditions
Ag X-ray tube: 45 kV high Voltage, 5mA current.

Mo secondary target.
Si(Li)-detector.
Angle between secondary target and sample surface =
angle between sample surface and detector = 450.
After the successful fit an updated Calibration report is displayed. It will contain the
coefficients, calculated during the fitting procedure and the individual sensitivities for the
measured standard elements and for elements that can be interpolated. K and L lines are still
separated.
75
The unknown sample - C0001.spe - was prepared from the IAEA reference standard SOIL7.
It was mixed with a binder and pressed to a pellet, representing 87.06% of the total sample
mass (dilution factor of 1.149) with a total aerial density of 0.0354 g/cm2.
With Intermediate thick sample as Sample type in the MENU Data for sample. The dark
matrix of SOIL7 mainly consist of SiO2 , Al2O3 , ... As a compromise an input for the
Compound by difference (FORM Known constituents in the MENU Quantitative
analysis of unknown samples) the fictitious compound SiO4 (mean atomic number 9.8) is
adequate. Finally the SCROLL BOX Sample will provide the user with the desired
concentrations.
76
In order to compare the results with the certified values, all concentration values must be
multiplied with the dilution factor.
77
TXRF and Thin samples
1. Introduction
The METHOD TXRF and Thin samples is designed particularly for measurements with
Total Reflection X-ray Fluorescence (TXRF) spectrometry. I.e. thin film samples (standards),
which are spiked with an element of known concentration (Internal Standard method).
More generally this METHOD is also applicable to thin samples or specimens with
comparable composition (absorption corrections are equal for standards and samples), which
were measured in conventional geometry.
No absorption (or inter element effect) corrections are calculated.
If more than 3 elements with known concentrations are available, values for elements not
represented by standards can be interpolated and extrapolated. Kα -lines and Lα -lines are
treated independently.
1.1 Principles of TXRF
A small droplet of the liquid sample ( 1 − 10µl ) is deposited in the center of the plane-
polished surface of a suited substrate (usually a disk shaped quartz reflector, with a diameter
of 30mm). Due to the geometrical arrangement the primary radiation of an X-ray tube will
impinge on the surface of the substrate under a rather shallow angle (in the range of 1mrad)
and will be totally reflected on this surface.
This physical phenomenon can be explained by the refraction index slightly smaller than 1
for X-rays. It can be shown that only a small amount of the primary photons can penetrate
into the reflector, thus contributing to the spectral background very little. On the other hand is
the small sample excited by the primary radiation (irregularly shaped, no total reflection) and
the interesting fluorescence radiation is collected very efficiently by the detector that is
positioned much closer to the sample (~ 5mm) than in conventional energy dispersive XRF.
As a result superior detection limits can be achieved.
78
Special equipment is needed and practically only samples in liquid form that must be spiked
with an Internal Standard element can be analyzed. For more detailed information see e.g.
references /KRE91/, /KRE02/ and /WOB89/.
Users of a TXRF equipment quantify their samples by the addition of a suited internal
standard. From the intensity ratios (element of interest/internal standard element) the
concentration values are determined.
For TXRF a standard will consist of several elements with properly chosen concentration
values (in order to cover the elements as well as their concentration range as expected in the
sample) and an extra element as Internal Standard (should not interfere with the spectral lines
of the sample). The concentrations of such a set of elements will change from one standard to
another, whereas the concentration of the Internal Standard will be kept fixed for all of them
and is preferably close to the value corresponding to the amount added to the unknown
samples.
2. Calibration
The first ITEM of the MENU Regression of count rate versus concentration will be
Define Calibration and Standards.
calibration file or create a new one, the last calibration file used is mentioned there. If no files
with extension .cal are present in the current directory, when one tries to Select a calibration
file the message No files (*CAL) found appears.

(e.g. Direct comparison of count rates, ... ), those cannot be loaded, due to
incompatibility. Error message: Calibration file not set up for regression
79
Continuing correctly a FORM is displayed that asks for many inputs:

As Procedure the 4 options: Element as internal standard, which should be selected for
TXRF measurements, Incoherent radiation as int. stand., suited for the compensation of
unknown aerial densities of thin samples measured in conventional geometry, Coherent
radiation as int. stand., and No internal standard are available.
The incoherent scatter peak is practically directly proportional to the sample mass and
independent of the atomic number for thin samples. The coherent scattering depends on the
atomic number of the elements that contribute to it. Therefore it is not advised to use the
coherent scatter peak for the assessment of the sample mass. The option No internal
standard can be used for thin samples with known aerial densities.
Recommendation: Do not use the coherent scatter peak for the specification of the
aerial density of thin samples. The same holds true for not well separated elastic and
inelastic scatter peaks (e.g. excitation with a Cu anode).
The potential contributions from the sample support or other components of the
experimental set-up should be checked carefully.
For TXRF measurements no scatter peaks, but the Internal Standard, should be used.
For Element as internal standard the characteristic Line must be in accordance with the
data found in the *.ASR files later to be loaded for the standards as well as the unknown
samples. For Concentration Units the user can choose any 10 characters.
Warning: If the < % > character is needed, it must be typed twice <%%>.
(active) source. <ESCape> is needed to continue.
109, Am-241 source. For a choice User defined one can define his own Source name (max.
19 characters).
80
For source excitation the Source half live is used to correct for the decay of the radioactive
source.
In the ITEM Filename, if the default directory C:\AXIL\SPECT is kept, only a meaningful
name for this calibration file has to be entered. For
E.g. the name TEST3 an ASCII file TEST3.CAL can be found afterwards in the sub-
Under Current calibration into the newly created file (or an already existing one) one can
Add standards.
extension ASR (result files of AXIL). At least one, but preferably several of them have to be
Selected from the SELECTOR BOX by <ENTER> into the respective lines, which is
indicated by an asterisk at the beginning of the line.
lines.
The following FORM Data for standard allows editing the measuring Live time (usually
not to be changed) and the Date (used to correct for the decay of the radioactive excitation
source). The Tube current has to be entered (for tube excitation only).
next. All changes have to be reconfirmed with <ENTER>.
Entries can be made for a Compound of each listed element. If one enters the element name
the whole compound. To exclude lines (e.g. contamination lines that had to be included in the
fitting procedure) the value for Concentration is left 0.0 .
81
weighting the measured sensitivities (2.3., FORM Polynomial fit of sensitivities). It should
contain any deviations from the concentrations of the used chemicals from the certificate
(hopefully given by the manufacturer), as well as uncertainties in the preparation of the
standards. Practically only the repeated preparation and evaluation of identical standards in a
statistically significant number can lead to correct values. As compromise a default value of
5% has been adopted.
For the selection of one of the scatter peaks as internal standard the information is read
directly from the *.ASR file (if no entry was found, 0.0 is displayed) and can be edited -
analogous to the characteristic line intensities.
As mentioned above, it is recommended to establish the sensitivity for each measured
element with more than one standard (with different concentration values). Consequently the
same procedure of this MENU has to be repeated as many times as ASR files were marked
under Select standard files. Finally one arrives again in the MENU Current calibration.
More standards can be added (if e.g. for testing purposes only a single *.ASR file was
loaded), or it is possible to Remove standards (e.g. one erroneously added an unknown to
the standards list), or the option Edit standards might be convenient to correct any typing
errors. The feature Change calibration setup is unique for this METHOD and enables the
user to edit the (already existing) FORM New calibration.
<ESCape> brings back to the upper MENU.
All previous attempts to start this MENU Perform Calibration of X-ray system would have
can be loaded under Select Calibration file, one can continue. From now on usually a default
sessions.
Warning: If previously for an element as internal standard a characteristic Line

was selected (FORM New calibration) not in accordance with the standards *.ASR
files an error message: No experimental data will be displayed.
82
2.2.1 Regression analysis for the standard elements
In TXRF usually the ratio of the intensity of an element of interest and the intensity of the
internal standard element versus the concentration of the element of interest (concentration of
internal standard is kept constant) shows a linear behavior. If there are no blank problems,
even the intercept should be zero. This linearity can be found for a range of several orders
magnitude for the concentrations of many elements - as long as the thin film approximation is
valid. The program extracts the individual sensitivities from those graphs with regression
analysis.
The FORM Regression estimate displays the named intensity ratio of the standard element
and the Internal Standard and the concentration units (as selected previously). Also the
number of concentration-intensity ratio pairs is displayed.
As Type of fit are available: Neighed straight line (parabolic) fit, weighted straight line
(parabolic) fit, and Robust regression. For the weighted option the data points are weighted
with the already mentioned standard deviation (concentration of standards). If the data points
are not normally distributed (outliners) least square fitting methods can fail. In that case the
concept of robust regression is preferable (very deviant outliners are statistically excluded).
For the usual case that no blank problems exist the origin should be included in the regression
analysis (Include point 0.0) with the option Yes.
The last <ESCape > will display the so specified regression line. With <F1> any ITEMs of
the previous FORM can be changed.
For each element of the standards this procedure has to be repeated. The final <ESCape>
activates the SCROLL BOX Calibration report. The Fitted R-values (intensity ratios) will
be used fur the further calculations.
2.3 MENU Extend calibration for not measured elements
The actual calibration is performed by the calculation of the relative sensitivities of all
elements for which concentration and peak area are supplied in the current *.CAL file.
and lines are treated separately. The calculated sensitivity ratios are stored in the current
calibration file, and can be used for the analysis of unknown samples. In order to continue the
calibration procedure the MENU Extend calibration for not measured elements and the
sub-MENU Extend calibration by linear fitting must be entered. The default *.CAL file
can be exchanged to any other, created by this METHOD, with Select calibration file.
For the MENU Extend calibration by fundamental parameters no program exists and
therefore is not accessible.
83
Through all previously determined relative sensitivities (intensity ratios) a polynomial
function of the atomic number Z of the form
relative Sensitivity(Z) = a0 + a1 ⋅ Z + a2 ⋅ Z 2 +...

or
log(relative Sensitivity(Z)) = b0 + b1 ⋅ Z + b2 ⋅ Z 2 +...
can be fitted. This procedure thus calculates the relative sensitivities as smooth function of
the atomic number. Small uncertainties of individual results are eliminated (this does not
necessarily improve results!), and more important, calculates (by interpolation and
extrapolation) sensitivities for elements for which no standards were available. At least 3
elements for K, as well as for the L-lines are needed, otherwise only the respective elements
will be analyzed.
Hint: If the user is interested in a sample that contains lead as sole emitter of
detectable L-lines, one could cover Pb only with a suited standard. The Extend
calibration by linear fitting procedure will fail (only one standard for the L lines).
Still it is possible to analyze the lead content of unknown specimens, whereas Hg, Au,
cannot be analyzed in this case.
In the FORM Polynomial fit of Ka rel. sensitivities several parameters for the actual fitting
selection of the order of the polynomial (max. equal to number of data points), whether a
option for weighting of the data points with the relative standard deviation (concentration of
standards), are quite arbitrarily. With the selection of the First element and the Last element
one can force the program to extrapolate for elements not represented by standards.
Warning: extrapolation of elements outside the range defined by the standards may
not be accurate.
Even the relative sensitivities one element below the first and one above the last element are
calculated.
If one attempts to fit a sensitivity curve through less than 3 points, one will receive an error
and will obtain concentrations for all elements of the unknown that are represented by
standards.
84
If applicable, the procedure continues with Polynomial fit of La sensitivities.
Finally the updated Calibration report is displayed again. If no further changes are desired
for the Current calibration, <ESCape> will lead to the upper MENU.
Notice: The intercept from the regression analysis for the individual standard
elements cannot be transferred to the MENU Extend calibration for non-measured
elements. (Only the slope is used for the interpolation of non-measured elements). It
is also therefore why the concentration ranges of the calibration should span so wide
that all expected concentrations of unknown samples are well included. It is not
advisable to establish a calibration within a range of e.g. 10-100ppm and the unknown
sample concentration of certain elements were found close to the detection limit. It is
highly advisable in such cases to extend the calibration range for these elements
(preparation and measurement of further standards) after finding such results in order
to have also standards measured so that all concentration values are included.
The concept of the extension for non-measured elements is to quantify elements,
which are not available to the user for calibration and are found in the samples with
their concentrations well described by neighboring elements.
85
will be needed to correct for the decay of the isotope source.
sample, what results in a final report that contains concentration values for the whole
compound. If one enters the element only (usually already the default), this means that the
compound is not known, or the element is not bound at all.
In the FORM Conc. of Reference elements the concentration of the Internal standard
element must be entered, as actually added to the unknown sample.
The result sheet Sample (SCROLL BOX) contains the desired concentrations of elements
(compounds) in the unknown sample. Under Define file to save analysis results it can be
stored as ASCII file with the extension ARP .
4. Demonstration
In order to demonstrate this METHOD for TXRF, three standards (described in table 2) were
prepared from 1000ppm standard solutions. Ga serves as Internal standard.

Mo X-ray tube: 50 kV high Voltage, 16 mA current.
TXRF geometry, Cut-off reflector (suppression of high energy photons).
Sample chamber evacuated.
Si(Li)-detector.
86
Table 2: Standards for TXRF
KAL8A100.spe KAL8A10.spe KAL8A1.spe

Element concentration in
ppm (=µg/g)
S 98.8 9.9 0.9
Ca 101.7 9.9 1.0
Ti 107.9 10.9 1.3
Cr 99.0 10.0 1.0
Fe 103.5 10.1 0.9
Cu 97.8 10.0 0.9
Ga (Int. Std.) 99.27 0.94 0.94
Se 97.6 10.7 1.0
Sr 97.2 10.6 1.0
The *.CAL file has to be created by the user as described above.
The Internal standard element Ga is represented by its Kα line. For the Type of fit (FORM
Regression estimate) Weighted straight line fit and Include point 0.0 were chosen for all
standard elements.
If the standards are treated in an adequate way, the sub-MENU Perform calibration will
result in a SCROLL BOX Calibration report, containing all information available to the
METHOD and the Fitted R-values.
87
In the FORM Polynomial fit of Ka rel. sensitivities (MENU Extend calibration for non
measured elements) for the Type of fit the option linear and an order of 3 should be
selected. The linear display of the fitted curve for the relative sensitivities is given.
After the fit the updated Calibration report is displayed.
88
It will contain the coefficients as calculated during the fitting procedure, the individual
sensitivities for the measured standard elements and calculated sensitivities for all the
elements that can be interpolated.
The sample was taken from a bottle of mineral water “Radenska” (file MIN-R54.spe). The
volume, as pipetted onto the reflector before drying, was 10 µl. The Quantitative analysis of
unknown samples MENU must be fed with all necessary input, e.g. the concentration of the
internal standard Ga (= 0.96ppm).
The SCROLL BOX Sample will provide the user with the desired concentrations. In order to
compare the results with the certified values as given on the label of the bottles, one must
multiply them with the dilution factor. The elements Fe and Rb are not specified on the label.
The element Ni can be attributed to impurities of the spectrum of the X-ray tube and had to
be included for the fitting procedure.
89
In order to stabilize the water sample, nitric acid was added, what results in a dilution factor
of 1.01.
Table 3: Certified values for the mineral water “Radenska” (as indicated on the label)
Element concentration in
ppm (=mg/l)
K 75
Ca 219.5
Mn 0.25
Br 0.09
Sr 1.8
90
91
Emission Transmission method for
Intermediate thick samples
1. Introduction
The EMISSION TRANSMISSION (ET-) METHOD is restricted to intermediate thick

samples. This technique corrects adequately the absorption caused by those elements, which
are not recognized by characteristic lines in the spectrum (dark matrix).
A carefully selected, so called, irradiator (its characteristic lines should not interfere with the
ones of the sample) is positioned at the backside of the unknown sample and its front side is
excited by the excitation source as usual. In a second measurement the sample is removed
and the irradiator is kept at the same position. Finally the unknown sample is excited in a
third measurement without the irradiator. As a consequence at least three *.ASR files are
necessary in order to analyze unknown samples with an unspecified matrix.
The energy dependence of the intensity ratios (with and without the sample of interest) of the
characteristic lines of the irradiator are used to calculate the matrix absorption and, by
interpolation, absorption correction factors for each element in the sample.
The irradiators can either be pure element standards (e.g. metal drums), or pressed pellets,
mixed from single element standards (oxides, simple compounds), etc.
For the calibration of the system several suited standards are needed, in order to cover a wide
elemental range. By means of a Fundamental Parameters approach (references /TAN85/,
/TAN86/), an average geometrical factor is determined and the individual sensitivities are
calculated, K-lines and L-lines are treated independently.
One basic assumption of this METHOD is, that the excitation source is monoenergetic. To
fulfill this requirement at least partially, either a secondary target set-up or isotope source
excitation has to be used. It is not straightforward to adapt this METHOD for varying values
of the tube current for a set of standards and unknown samples.
The attenuation caused by fluorescing elements is corrected with theoretical values taken
from /THI79/.
1.1 Some limitations of this METHOD
It is assumed that a calibration had been established before with the METHOD Elemental
sensitivities (valid *.cal file).
The X-ray spectra collected for the target and sample+target should only be fitted for those
elements which are present in the target (X-ray peaks corresponding to possible
contaminations should be omitted, or for the advanced user: the *.asr file should be edited
such that the unnecessary lines are erased manually. This will provide the more accurate
results for the lines originating from the target.)
The ET-method is applicable with good precision for minor and trace elements only. If the
spectrum of a sample contains an element with a concentration exceeding about 20%, the
results for this element and the ones with lower atomic number are questionable.
92
Only intermediate thick samples can be analyzed. If the absorption factor for any target
elements exceeds 20 (corresponds to absorption >95%) its X-ray lines are not considered in
the calculation.
The setup.ax file must contain the following lines:
$axil$fundlibs:
c:\axil\krause.lbr
c:\axil\mcmast.lbr
c:\axil\scatpar.lbr
(c:\axil has to be replaced by the correct path in case the library files are in another
directory.) If the program cannot find the libraries at the specific place or if the entry is
missing in the setup.ax file, the program will give an error message.
Hint: Many samples will be prepared as pressed pellets where a binder has to be
added. I.e.: the sample will be diluted. All reported concentration values would have
to be corrected with the dilution factor.
2. Calibration
In the start screen, if no calibration file had been selected previously, only the first line
(Select calibration file) of the MENU Current calibration will show up, and the user has to
select a valid *.cal calibration file. This is a calibration file that had been created previously
with the METHOD Elemental sensitivities.
The measuring parameters can be edited by activating the second line (Change Measuring
Parameters) of this MENU. The term Path will take into account the distance in air between
sample and detector, HalfL. (of the excitation source) will correct for the decay of the
excitation source in between the calibration and the measurement of unknowns (in days),
Incid.A. and Emerg.A. refer to incident and take-off angle in respect to the sample surface,
S.Diam. is the diameter of the sample (in cm). There is the possibility to measure the
unknown samples with higher current (Cur(S)) than the target plus sample and target only
with lower current (Cur(T)) in the case of tube excitation.
93
The last line (Define File to Save Analysis Results) of the MENU Current calibration
opens a menu, which allows defining a file name for saving the results (*.arp).
Warning: If such a file had not been created/selected, the results will not be saved
after the calculations.
3. Calculation of the Absorption correction
The third MENU line (Select Files for Analysis) opens consecutively 3 SCROLL BOXes to
choose in this order:
Sample file
Target file
Sample + Target,
all three of the format *.asr .

After the appropriate selection (there is no consistency check!) a window to enter the sample
mass (in grams) will activate a further window that summarizes the 3 respective file names
and the mass. In case of any problems the third MENU line for the selection of result files
can be activated again.
Next the user has to <Enter> into line 4 (Perform calculation of Concentrations) of the
MENU. A list of elements together with the net peak areas pops up. The user has to select
appropriate elements for absorption calculation (must correspond to the elements of the
target). Only such elements should be selected which are present in the target at high
concentration levels (trace elements should be omitted) and should not originate from the
sample. At least 3 entries have to be marked. For too high absorption of target element lines
by the sample (more probable for lower atomic numbers) i.e. absorption factor >20, certain
elements will not be used for calculation.
The absorption for the selected element peaks is calculated and a linear regression of the
form ln(A) versus ln (energy) is performed. As compared to the nomenclature of the appendix
capital A should be a (attenuation coefficient).
Fact is the correction factor as found by this METHOD for sample self-absorption. Both:
logE and Lg(E) stand for the natural logarithm. If the regression coefficient is smaller than
0.99 , one or more elements should be removed. In this case the user refuses to accept the
94
regression and types <n>. Again the list for element selection pops up and a new selection of
elements has to be performed.
Warning: The suppression of „disturbing“ elements is easy, but there might be a

reason for bad results.
When the regression coefficient is better than 0.99, the user will accept the result by typing
<y> .
Next the chemical symbol of an element should be entered for which an edge correction
should be considered (Enter Element to start iter.:). The edge correction makes sense only
for elements, which concentration values expected to be greater than about 1% (eventually
such a correction will be applied after a first run, without correction, to know the range
through the preliminary results). Such an edge correction will be applied for the selected
element and for all other elements of lower atomic number found in the sample result file. No
edge correction is applied for L-lines.
4. Results for unknown samples
The result of the calculation is shown on the next screen. It is possible to scroll up and down,
<F10> will print a report, and the results can be saved in a file *.ARP . F is the correction
factor as found by this METHOD for sample self-absorption (named Fact in the previous
window), <ESCape> will bring up the start screen and the calculation can be repeated with
the same files for a different edge correction, or new result (*.asr) file names can be used for
a new run.
5. Demonstration
The already existing calibration file CH_MO.CAL (had been established with Elemental
sensitivities) was used to calibrate the system for this METHOD. The measuring parameters
are found in table 1.
The “unknown” sample - C0001.spe - was prepared from the IAEA reference standard
SOIL7. It was mixed with a binder and pressed to a pellet (diameter 3cm), representing
87.06% of the total sample mass (dilution factor of 1.149) with a total mass of 0.25g. Of
course the sample contains a low Z matrix.
As target a pellet with a mixture of Zn, As, Rb, Sr powder (oxides) was pressed.
Mo secondary target, 45 kV high voltage, 5mA current.

Path length: 0.45 cm in air for (exciting and) fluorescence radiation.
Incident angle = take-off angle = 45o.
95
In order to compare the concentration results with the certified values one must multiply
them with the dilution factor.
96
97
Fundamental Parameters – monochromatic
excitation / scatter peaks
1. Introduction
The Fundamental Parameters program for monochromatic excitation and use of the
scatter peaks (backscatter fundamental parameter method, BFP) is a very versatile
METHOD for quantification and is suited for completely unknown samples. Source and X-
ray tube excitation can be covered. The basis for this METHOD is reference /WEG03B/.
The Fundamental Parameters approach calculates concentrations from measured intensities of
characteristic lines of elements and takes several theoretical values into account: The spectral
distribution of the excitation source, the fundamental parameters, various absorption
corrections, the inter element (enhancement) effect, and the detector efficiency. The sample
self-absorption by the dark matrix is corrected by the use of the scatter peaks. Standards are
used to determine the geometry factor (average instrumental constant).
The range of elements that can be analyzed by this METHOD is not limited or correlated to
any range defined by the elements of the standards. One constraint of the METHOD is the
fact that only monochromatic excitation can be handled, which implies that direct X-ray tube
excitation (bremsstrahlung continuum) can not be treated. Even for more than one line of a
source or secondary target a weighted average must be calculated.
E.g. for a Rh secondary target the weighted average of its Kα and K β line yields
E = 20.6keV . For the excitation with the primary radiation of an X-ray tube
sometimes so called effective energies are defined. Such procedures might lead to
good results, from the theoretical point of view it is not recommended to apply
polychromatic excitation.
A handicap of the program is the missing <ESCape> command throughout the various lines
that have to be entered with appropriate information. Any single mistake in the input will
force the user to terminate the program with the <BREAK> (some computers
<Ctrl>+<BREAK>, <Fn>+<BREAK>) command. In case, certain information is missing
which only can be retrieved from e.g. a directory, one can open a second window of DOS
(Command Prompt usually under the Accessories under Programs), which WINDOWS will
allow.
98
2. Calibration
2.1 Pre-requisites for calibration
As minimum one spectrum with known content of the sample composition, typically pure
metal specimens or homogenously mixed pressed powder pellets, will serve for the
calibration. (Reference Standard materials are not well suited, because of their trace elements
content, which will introduce high statistical uncertainties in the average constants to be
determined.)
Except the tube current, no parameters may change from in between calibration and also not
for unknown sample measurements.
The program expects that at least one of the spectra is fitted also for its elastic as well as
inelastic scatter peaks, i.e., the *.asr files must contain information of the form:
$COH_SCAT:
$INC_SCAT:
Under Spectrum Analysis, Perform spectrum fitting, the MENU X-LINES ADD
the command MO,inc and Mo-KA,coh will include the elastic and inelastic Mo-Ka
scatter peaks. In many cases the fit of the spectra will require that the element lines be
fitted separately from the scatter peaks region. Usually the element lines will need a
careful description of the background, whereas the scatter peaks will need a region of
interest (ROI) around them with a very simple background model, otherwise their
underlying background will be overestimated. Update the previously created *.asr file
(fit of characteristic lines), which will be needed to save two fits of one spectrum into
a single file.
It is possible to fit a spectrum of materials, e.g., cellulose, SiO2, etc., even without
characteristic lines (matrix close to the unknown sample matrix) to serve for the scatter
calibration and other spectra for their characteristic lines only (pure metals, alloys).
No re-runs, to add or remove standards from the calibration procedure, are possible. In such
cases the calibration has to be started from the beginning.
At least one so-called blank sample file must exist. Usually this will be a spectrum without
any standard/sample in the usual position of the sample holder and it should represent the
scatter contribution from the spectrometer and the ambient air. If necessary, blank problems
for certain elements can be treated here, but the basic idea is the determination of the scatter
region.
Hint: The observation was made that better results were achieved when the scatter
peaks of the blank sample *.asr file were set to zero (manual editing).
As result of a calibration run a *.clb file will be created, only then unknowns can be
analyzed.
2.2 FORM Enter calibration data
99
The first screen of this METHOD (Select:) will lead to the calibration (1.Perform
calibration) only by typing “1” . Any other character will not be accepted (and “2” brings to
the later to be passed quantification of unknown samples). The FORM Enter calibration
data (and all other FORMS of this program) will have to be filled in very correctly, e.g.
numbers must be entered that are between certain limits (any < signs will rather mean that the
actual limits are included into the range and are also applicable). If capital/small letters are
expected, as usually specified one line above the expected input, the operator will have to
follow, otherwise the program will respond with an error message and the input will have to
be repeated correctly.
For tube excitation the first line of the FORM will have to be passed with ”0” .
The excitation energy can be different from the coherent scatter peak energy, because the
weighted average for K-excitation
Eav. = pα x Eα + pß x Eß
is usually higher than the coherent scatter peak (Energy of the coherently scattered
radiation) of the Kα line
Eel.scat = EKα
Incident and Exit angle refer to the sample-beam-geometry (lines 4, 5)
A Mylar foil between detector and sample can be used to protect the detector window and/or
represent the exit window of an (evacuable) sample chamber. The unit of the thickness (um)
is µm.
The next line takes into account the absorption of the characteristic radiation by air on the
way from the sample to the detector (Length of the air path).
100
Three different detectors, predefined so that dead layer and gold layer are taken into account,
are for selection. The Si-PIN detector is the same as Si - except that no Au layer is used for
the model. Type exactly Si, Ge, or Si-PIN.
The thickness of the detector crystal is important for the higher energy intrinsic efficiency,
whereas the beryllium window thickness (unit µm) is of influence to the lower energetic
radiation.
After the successful completion of that icon the so-called blank sample file name (an *.asr
file, but the extension .asr must be omitted) has to be entered. It contains the fit results of the
scatter peaks originating from the empty sample holder (no sample in the usual position) and
the ambient air. Enter the x-ray tube current refers to the blank measurement.
The question Save results in the file report will enable to save the individual calibration
results to a report (file name *.rpt, which later also can be used to store final results of sample
analysis) in readable ASCII format, but the further calculations are not affected by this
decision. (The file used for this purpose will have the extension *.clb and is created at the end
of the calibration procedure.)
The next screen refers to the standards and their spectra (No of sample components <1,50>)
and expresses the need of the program for an input of the total number of elements measured
in the first standard. The input must be an integer between 1 and 50.
The aerial density of the first standard must be entered next after the line Enter the sample
mass per unit area (for infinitely thick standards any high number will do).
Of course, the measured elements can be present in the standard as unbound elements or a
compound, nevertheless their concentration (in weight percent) also must be known
(expressed for example, in the respective line of the MENU for calcium carbonate with a
concentration of 25.5% : CaCO3 25.5).
The number of times a line, with the need of an input for an element/compound and its
concentration, will show up, corresponds to the previously entered integer (No of sample
components <1,50>.
The next screen (Enter sample filename) will need the *.asr file name of the matching
standard, i.e., all defined elements/compounds as specified above will have to be found in the
spectrum fit as well as the scatter peaks (no immediate check for consistency!). The
consecutive screen refers to the tube current as used for the measurement of this standard.
After the successful completion of the first standard the question Next sample? (Y/N) will
permit the definition one standard after the other (Y, or y), in the same way as for the first
standard. The successful termination of the calibration after at least one calibration standard
is achieved with N or n .
The last-but-one screen for the calibration procedure summarizes the calculated AVERAGE
CALIBRATION CONSTANTS for the coherent and incoherent scatter peaks and for
fluorescence. The scatter constants will be used for the estimation of the dark matrix and the
thickness of unknown samples.
Finally all relevant data will be stored (FORM Enter the name for the calibration file). A
meaningful name, but no extension (its by default *.clb) is needed. It is advisable to match its
name with the report file name (*.rpt), in case this option to create and save it had been
selected previously.
101
3. Analysis of unknown samples
The first screen of this METHOD (Select:) will lead to the analysis of unknown samples (2.
Analyze unknown sample(s)) by typing “2” only. Any other character will not be accepted
(and “1” opens the calibration procedure). The relevant calibration file (*.clb) and the blank
file (*.asr) names (usually the same blank as already used for this calibration procedure), both
without extension, are to be entered. Independent of the selection for a report file name
previously for the calibration file, the results can be saved in a file with the extension *.rpt .
So it is possible to create a new report file, or use the same report file as for the calibration
measurements, if any was created, or not.
The calculation will be started after the unknown sample *.asr file name was entered.
Hint: Usually the unknown samples *.asr files should contain the fitted scatter ROIs.
However, when no scatter peak information is found, all concentration values will be
normalized to 1 (e.g. for alloys this will be a good option).
Warning: The program will crash for elements included into the *.asr files with
absorption edges above the excitation energy. If it has to be done for fitting purposes,
the *.asr file has to be edited manually to remove such elements.
Although in the simplified model it were impossible to excite, e.g., Zr with a Mo
secondary target, in reality it is possible, because the secondary target scatters also
continuum radiation from the x-ray tube.
For a correct calculation run the number of iterations will briefly be displayed, ending with a
screen named: Results of analysis:
The concentration values are given as weight fraction. E.g. 2.500E-0002 is equivalent to
2.5%). Unfortunate for the user all results have to be checked so that the standard deviation
(Std. Dev.) does not exceed the corresponding concentration value, which would mean the
respective result is below the detection limit. U_Tot stands for the total absorption correction
for the line of interest, F_Enh_Tot for the inter-element plus enhancement by scattering
correction and F_Enh_Scat for the enhancement by scattering. For the two last two columns
values close to 1 will correspond to small correction (less important enhancement by other
elements, or scattering).
The line Save peak ratios? (Y/N): aims to the fact that improvements in the peak fitting
(AXIL) will have a (positive) effect on the quantification. When the question is answered
with “y” , files with the extension .RAT will be created which can be used for the model file
(*.INP) of AXIL peak fitting (manual input by copy and paste only!). This slightly will affect
the intra-line peak ratios of K- and L-lines for a given element (different sample self-
absorption for different energies). With these improved fit results the quantification should be
repeated.
For samples measured under the same conditions the calculation can be repeated (Next
sample? (Y/N): answer with <y>.
4. Demonstration
The calibration of the system was performed with only 2 standards for fluorescence lines
(appendix, table: Standards): SD0018.spe (pure Fe) and SD0012.spe (pure Pb). For these 2
102
spectra the scatter peaks were not fitted. (Answer to the question: Scatter peak intensity
from different ASR-file? (Y/N): N ).
The experimental conditions as needed for this METHOD are found in the table:
Experimental conditions.
Mo secondary target, current 5mA for all measurements

Average excitation energy: weighted Mo-Kα+Kß
Scatter peak energy: Mo-Kα
Incident angle = exit angle = 45o
Mylar foil thickness:0
Air path:0.5cm
Si(Li) detector 3mm thick, with 8µm Be window.
For the scatter calibration the Mo scatter peaks ROI was fitted for a standard with similar
average atomic number like the sample (SD0030.spe, spectrum of a fused quartz disk -
usually used as sample reflector for TXRF). Because of the already complex task to fit scatter
peaks adequately, no effort was made to include Si-K in the ROI. Under X-lines
MO-KA,coh MO-KA,inc MO-KB,coh MO-KB,inc
and also several lines only in order to reduce the Chi Square value (without physical
relevance) at selected energies, defined as incoherent peaks of 15.3 keV, 14keV and
13.8keV:
15.3,inc 14.0,inc 13.8,inc
were included into the model. The ROI was defined from approximately channels 650 to
1000 and as background model linear with order 0 was used.
For the blank spectrum the above described *.asr file was edited manually (the peak areas of
the elastic and inelastic scatter peaks were set to zero and saved under a different file name
(e.g., blank.asr)).
The unknown sample - C0001.spe – had been prepared from the IAEA reference standard
SOIL7. It was mixed with a binder and pressed to an intermediate thick pellet, representing
87.06% of the total sample mass (dilution factor of 1.149) with a total aerial density of
0.0354 g/cm2. For the fit Si was not included in the ROI and Zr was excluded, although
present in the sample (see remarks above).
103
them with the dilution factor. The estimated mass was found as 43.7 mg/cm2, which is close
to the known 35.4 mg/cm2.
104
105
Fundamental Parameters – monochromatic
excitation - NBS alpha coefficients
1. Introduction
The NBS alpha coefficients METHOD is restricted to thick samples containing only
elements of relatively high atomic number Z (metallic or bound as oxides) where there is a
detectable fluorescence signal from every constituent (no dark matrix). The method was
developed by the National Bureau of Standards (now NIST) and the Geological Survey of
Canada for wavelength dispersive spectrometers. It was adapted by the IAEA for energy
dispersive devices. Only monochromatic excitation can be treated. The theory of this method
is described in the appendix of this manual and more details can be found in references
/TAO85/ and /LAC95/.
For this METHOD samples are classified into three types:

1. Element system
2. Oxide system
3. Fused disk system
The term element system refers to samples where the analytes are present as unbound
chemical elements and, as stated above, all of them produce a detectable peak in the
spectrum. (Examples are stainless steel or brass alloy where low Z components or impurities,
like C or P, can be neglected).
For oxide sample systems the analytes are present as oxides with known stochiometry, which
is usually the case for minerals and many geological materials.
Fused disk samples had been diluted with a suitable chemical (flux) and then melted together
at high temperatures producing a glass bead. (This option, although implemented, has not
been tested.)
The analysis of samples using this METHOD should be performed in three stages:
1. Create standard (*.std) file
2. Prepare the α-coefficients file (*.alp)
3. Analyze unknown samples
The first stage is not necessary and can be omitted, if the user will base the analysis on the
sensitivity calibration of the spectrometer (same as described in Incident- and take-off
angles, Geometry constants, *.sen files, found in Utilities). The (*.sen) files that contain the
sensitivity data can be used instead of the *.std files. The standardless method is applicable
only for pure element samples (not for oxides or fused disks).
For the case of mistakes during the use of the METHOD, at certain points in the course of the
programs, the user will not be able to <ESCape> from a sequence; in that case <ctrl> and
“C”, pressed simultaneously, will terminate the respective program.
2. Creating the standard file
106
A standard description file is prepared for all the standards, entering into Prepare standard
concentrations file. and the following screen appears:
A standard has to be selected and will be processed, but only one at a time. (This MENU has
to be passed again as many times as many standards will be included.) After the selection a
prompt for an output file name (*.std) will appear.
The default name can be selected by with RETURN, but may be altered. The type of
specimen composition must be selected at this stage (element, oxide, or fused disc system),
according to the unknown sample!
Then the concentration (in weight percent) of each element/oxide and for oxides its chemical
formula, e.g. Fe2O3, describing the standard, must be entered.
Each element of the unknown sample must be present in - at least – one of the standards.
E.g.: Fe - Cr - Ni – Co – Cu – Mn in the sample.
Ö Fe, Cr, Ni, Co, Cu, Mn will need minimum 1 standard with a known mixture of all
elements,
Ö or minimum 6 single element standards
Ö or more standards,
Ö or different combinations of elements in several standards
107
The spectral fits of all spectra will have to include all elements to be quantified in the
unknown sample, irrespective, if certain standards contain these elements or not
(concentration 0 in this case).
In order to succeed one should fit the spectra of all the standards with the same list of
elements (same model file: *.inp), and the unknown samples will dictate the selection.
After the regular termination of AXNBS.exe a *.std file will have been created.
3. Creating the α-coefficients file
With Prepare alpha coefficients file a file, that contains the coefficients that represent the
influence between all analytes of a sample, (both absorption and enhancement) is created.
These coefficients depend on the analytes (elements or oxides) and do not depend on their
concentrations (except for the fused disk model). Consequently the standardless creation of
α’s is possible. The operation is done by the program CALCO.exe.
The first screen allows the operator to load the list of analytes from a *.STD file (YES), or to
edit the analyte composition list manually (NO, standardless mode).
108
In both cases the data may be edited. If necessary the user has to enter the data manually in
agreement with the later to be analyzed unknown sample. One should notice that the
composition of all analytes should be specified, even when they are not present in the
selected standard, (the case of Fe2O3 in the example shown). With <ESCape> the data is
accepted.
The Normalize of concentrations option is irrelevant, except for the fused disk system,
however should not be selected if the concentrations are all zero.
Warning: Selecting normalization with all concentrations set to 0 will produce an
error in the program.
After having passed the question Finished? with YES, a file describing the excitation
spectrum (*.sou) must be selected (SCROLL BOX Select excitation source data file).
Examples of *.sou files are found in the directory SPECT and in the appendix the relevant
information is described, in order to tailor such files to the personal need).
The mass absorption coefficients are calculated by the XPARAM library using McMaster’s
compilations /MAS68/.
109
The results will be saved with an extension *.alp (Chose an alpha coefficients data file (to
be created)), the overwriting of old files is allowed. It is possible to get a list of the old *.alp
files by entering “?” instead of a file name.
The screen Do you want to display alphas? will permit to display the calculated alpha
coefficients (Yes). If then this screen will not show up this indicates that inconsistent data
prevented the computation.
In the positive case the results will be saved in the file specified by the analyst before exiting
the program with <ESCape>.
110
4. Quantitative analysis of unknown samples
The last step is performed by the program CALCOMP.exe.
One has to select the calibration mode for the calculations using:
Standards, or
previously stored intensity calibration coefficients, or
sensitivity calibration (element model only).
As next step, the α-coefficients file must be selected, and a list of the analytes is shown so the
operator can assure the proper file selection. (Answer: Yes), because the given system must
match the sample. Selecting No will prompt for another α-coefficients file.
The next step (assuming that “Standards” had been the calibration mode previously) is to
select the *.std files (up to 20).
111
These standards will be checked for consistency with the α-coefficients file, some might be
rejected, if the analytes or model (e.g. element or oxide system) are not appropriate.
When a sufficient number of standards matches (at least one relation of intensity and
concentration per element is available) then the analysis can continue.
The analyst will be prompted to select the sample files ( *.asr files) in a similar way. Up to 20
may be simultaneously selected for batch processing). If the display of intermediate results is
enabled, the next screen will show a table of the Calculated relative intensities of the
analytical lines in the standards.
Then a table with the calculated intensities for (sometimes hypothetic) pure standards from
the intensities measured in each standard will be shown, together with the average for each
analyte.
112
Finally the analyst has to select a function that will represent the evolution of the calculated
intensity versus its concentration in the standards. If only one point is available (like in the
case of the example for TiO2 and Fe2O3), only the simplest function y = a*x may be
selected.
When the iterative procedure to calculate the concentrations in the sample begins, again some
intermediate results like the relative intensity calibration coefficients may be optionally
displayed.
113
Finally the results (concentrations) of all the samples selected are displayed
The user may then normalize the results, if applicable, so the concentrations add up to 100%
for each sample, or print or save the results, save the relative intensity coefficients for later
use and, if applicable (more than one concentration is available for every analyte in the
standards) perform the analysis again with a different function for fitting the relative
intensities versus the concentrations.
114
5. Demonstration.
A set of 4 standards was prepared by mixing oxides of Ti, Fe and Zn. These elements were
chosen to explore the capability of the NBS algorithm to correct for the strong enhancement
effects.
The weights (in grams) and concentrations for the pellets are given in the following table:
Sample #1543 #1544 #1545 #1546
Spectrum TU2425 TU2427 TU2426 TU2428

Weights in g
TiO2 0.6345 1.0223 0.8369
Fe2O3 0.67 1.0359 0 0.2008
ZnO 0.6905 1.0079 1.0162 1.0293
Total 1.995 2.0438 2.0385 2.067
Sample 1.9051 2.0309 1.9913 1.9812
Concentrations
TiO2 31.80% 0.00% 50.15% 40.49%

Fe2O3 33.58% 50.68% 0.00% 9.71%
ZnO 34.61% 49.32% 49.85% 49.80%
The pellets were measured in a secondary target system, using a Mo anode and Mo as
secondary target. The X-ray tube was operated at 40kV and20 mA, the spectra were collected
for 500 s each. The spectrum analysis was performed with the Kα and Kß lines placed in
different groups.
The results show maximal uncertainties below 5 % and in most cases the uncertainty is below
1 % (see following table). The concentrations were also calculated using the Full
Fundamental Parameters METHOD with the same standards for determining the Average
instrumental constant.
115
Calculated Concentrations: NBS program, normalization not applied
SAMPLE: #1543 SAMPLE: #1546
Samples #1544 & 1545 used as standards (in all cases).
conc. err (%) conc. err (%)

TiO2 30.75% -3.3% 39.82% -1.7%
Fe2O3 34.18% 1.8% 10.06% 3.6%
ZnO 36.14% 4.4% 50.12% 0.6%
Total 101.07% 100.00%

Calculated Concentrations: NBS program, normalization applied

TiO2 30.42% -4.3% 39.82% -1.7%
Fe2O3 33.82% 0.7% 10.06% 3.6%
ZnO 35.76% 3.3% 50.12% 0.6%
Total 100.00% 100.00%

Calculated Concentrations: Full Fundamental Parameters program,

normalization not applied

TiO2 30.77% -3.3% 39.65% -2.1%
Fe2O3 30.35% -9.6% 8.32% -14.4%
ZnO 33.14% -4.3% 49.85% 0.1%
Calculated Concentrations: Full Fundamental Parameters program,
normalization applied
Total 94.26% 97.82%
Norm. applied
TiO2 32.98% 3.7% 40.64% 0.4%
Fe2O3 32.12% -4.4% 8.49% -12.6%
ZnO 34.90% 0.8% 50.78% 2.0%
Total 100.00% 99.91%
116
117
Full Fundamental Parameters
1. Introduction
Full Fundamental Parameters is the most versatile METHOD for quantification in the
QXAS package and suited even for completely unknown samples. Practically all modes of
excitation with electromagnetic radiation in the range of X-rays can be covered and many
more parameters can be selected to match the assumptions needed for the calculations with
the experiment. The basis of this METHOD is reference /HE91/.
The Fundamental Parameters approach calculates concentrations from measured intensities of
characteristic lines of elements and takes several theoretical values into account: The spectral
distribution of the excitation source, the fundamental parameters, various absorption
corrections, the inter element (enhancement) effect, and the detector efficiency. The sample
self absorption by the dark matrix can be corrected by the use of the scatter peaks. Standards
are used to determine the geometry factor (average instrumental constant).
The range of elements that can be analyzed by this METHOD is not limited or correlated to
any range defined by the elements of the standards.
2. Calibration
In the MENU Set-up instrumental parameters (program ECON.exe) the calibration of the
system for this quantitative program can be established. If the system does not allow to Select
instrument parameter file, with an error message No files (*FPC) found, no such file
exists. Another explanation could be, that such a .FPC file is stored in another sub-directory,
than the default one, proposed by Search in directory (default C:\AXIL\SPECT). For the
second case try to match the directory that contains such an *.FPC file with the directory
under Search in directory, or copy the existing *.FPC file to the directory of your choice.
The first case can be assumed for the first run of this program. As solution choose Create
new instrument parameter file. One should enter a meaningful file name for the ITEM File
name (the extension FPC is added automatically).
without any warning!
118
Several FORMs will follow that describe the excitation and detection system as well as the
geometry. For each ITEM (highlighted line) one option has to be selected from at least two
possible ones. Switch between these options by the use of the arrow left/right keys, +/- keys,
or <SPACE BAR>. After such a selection continue with either arrow up/down keys,
<ENTER>, or one can click the highlighted line with a mouse. From one FORM to the next
<ESCape>.
With Select instrument parameter file all existing *.FPC files can be edited and any
changes can be made at any stage of this METHOD.
Define experiment:
MENU Set-up instrumental parameters
Enter standards:
MENU Specify standard/sample information
Calculate average/individual instrument constants:

MENU Calculations of Geometry constants/Analysis of unknown s.
Enter average instrument constant:

MENU Set-up instrumental parameters
(Don’t change anything else!)
Enter samples:
MENU Specify standard/sample information
Calculation of concentrations:
MENU Calculations of Geometry constants/Analysis of unknown s.
119
2.1 FORM Excitation conditions
Mode: As source of primary radiation are available (5 options): radioactive source, primary
radiation of an X-ray tube, secondary target excitation, synchrotron radiation, (all those have
to be defined more detailed later), and, if non is suited, one can create a user defined
excitation source.
Atmosphere: The path between X-ray tube / sample / detector could be evacuated or not.
Flushing of the sample chamber with Helium or Nitrogen can be described (4 options).
Collimator: The users of a Tracor Spectrace 5000 spectrometer will know what kind of
collimator they use; otherwise No collimator is the appropriate choice.
The next FORMs vary according to the Mode of excitation one selected.
2.1.1 Radioisotope excitation
FORM Radio-isotope
The six options are Fe-55, Cd-109, Am-241, Co-57, Gd-153, and if no is appropriate:
User defined. For all of them the next FORM is displayed:
FORM Parameters for radio-isotope
The highlighted line is the one to be edited. Do not forget to finish each correct entry
with <ENTER>. Switch between different lines using the arrow left/right, or +/- keys.
The example is a fictitious source XY-99, with a half-life of 100 days and 3 lines with
above energies and emission probabilities. Usually it will not be necessary to edit any
of the 5 already specified sources.
2.1.2 X-ray tube excitation
FORM Parameters for X-ray tube
If the primary beam of an X-ray tube is used for excitation, its characteristic lines as
well as the continuum (Bremsstrahlung) will contribute. The calculations of this
120
program adopt the algorithm given in reference /PEL85/. The actual anode material
has to be entered simply by its element name. Use upper and lower case characters
correctly.
E.g. the anode material rhodium will be entered as Rh. Do neither enter RH,
nor rh, nor rH.
The anode take-off angle is defined between the X-ray direction and the anode
surface. Values of 20 for fluorescence tubes and of 6 for diffraction tubes are usual.
The operating voltage heavily determines the shape of the continuum. This continuum
is represented by discrete values for the sake of calculations. The greater this number
(stay below 200) the more precise the model will shape the calculated
Bremsstrahlungs contribution.
Hint: When working with secondary target arrangements the Number of

continuum intervals may be set to 0.
If X-ray tube plus secondary target was selected another FORM might appear:
FORM Parameters for secondary target
Warning: The Incident angle is defined between surface normal and incident
beam. The Emergent angle is defined between surface normal and the
direction of the emerging X-rays. This is not in accordance with the usual
definitions in XRF, nor with the other quantitative METHODs of QXAS.
2.1.3 FORM User defined excitation
If none of all those excitation modes does fulfill the requirements, one can create a
custom source. In the first run one has to Edit a new file, which can be reload later on
by toggling to Input from data file. According to the number of intervals selected,
energy (wavelength) values have to be entered as well as their respective intensities.
121
2.1.4 FORM Parameters for Synchrotron
Users of the radiation from a Synchrotron storage ring (plus monochromator) as

excitation source will maybe appreciate this option. Operating voltage is the central
energy of the energy band as provided by the monochromator. FWHM is the full
width at half maximum in (eV), and the Number of continuum intervals are used for
the accurate description of the intensity distribution within this energy band.
2.2 FORM Detector characteristics
This FORM is common for all the supported excitation modes. Si(Li) and Ge
detectors are supported. The specification of the detector (Be window, Au layer, dead
layer) is not to crucial for the analysis of conventional elements (in terms of XRF),
but if one is interested in elements with lower atomic numbers one should be aware of
their influence. The active depth of the detector is responsible for the decrease of the
efficiency for higher energies.
2.3 FORM Excitation - detection geometry
The description of the geometry is used for the fundamental parameter calculations.
The path lengths (Dist. source-sample, Dist. sample-detector) are needed for
absorption corrections, if the radiation is has to cover distances in air, helium, or
nitrogen - according to the previously selected Atmosphere. Any distances covered in
vacuum should not be included.
E.g.: The radiation has to travel in air 0.45 cm from the X-ray tube to the sample
chamber, that can be evacuated, and from the sample chamber to the entrance window
again 0.45 cm in air. Enter these distances and do not care about the path inside the
sample chamber.
Warning: The Incident angle is defined between surface normal and incident beam.
The Emergent angle is defined between surface normal and the direction of the
emerging X-rays. This is not in accordance with the usual definitions in XRF.
2.4 FORM Filter between source and sample
122
If a filter between the excitation source and the sample is used, in order to change the
primary spectral distribution, 4 of the options should be selected only by users of the
Tracor Spectrace 5000 analyzer (no aerial density specified), whereas No filter and a
User defined filter are meaningful for other instruments, too.
2.5 FORM Average instrumental constant
The average instrumental constant for fluorescence is directly proportional to any final
concentration of interest. The two constants for scattering are needed for the evaluation of the
dark matrix in unknown specimens. They will not be used during the calculations of samples
with no matrix, or if the matrix composition is known.
For the determination of the constant for fluorescence the concentrations values of well
specified standards and the respective *.ASR result files of AXIL are needed. The elements
should cover a wide range, because the constant for fluorescence shows usually some
dependence on the atomic number.
In the first run one leaves those 3 entries empty (0.0), continues through the program, as
described below (the *.ASR files of the standards are to be used), and obtains finally 2
average values for scattering (if there are entries in the *.ASR files that contain scatter peaks)
and individual constants for fluorescence for each element and standard. After a careful
inspection of the individual constants (outliners can be eliminated, but also could indicate
experimental problems) an average value can be calculated.
Starting from Set-up instrumental parameters continuing to Select instrument parameter
file where one has to load the same *.FPC file, that was used to determine the individual
instrument constant with the standards - no changes should be made in the above described
FORMs, because this would influence the instrument constants - finally enter in the FORM
Average instrumental constant the value for fluorescence.
The values for coherent scattering and incoherent scattering can be edited too, if needed.
Their values are calculated theoretically or can be determined by measurement.
In the first case it is assumed that the values for the average instrumental constants for
coherent and incoherent scattering ( Gscatter ) are identical and are simply related to the
fluorescence constant ( G fluorescence ) by the formula
Gscatter = 4 ⋅ π ⋅ G fluorescence (1)
That will be the internal default value of the program. If the instrument constants for
scattering should be determined experimentally, at least some of the standards should contain
light elements in a sufficient amount, because (infinitely thick) samples with lower average
atomic number have better scattering abilities. Of course the scatter peaks must have been
evaluated during the fitting procedure of AXIL.
The last <ESCape> will initiate the calculations and finally return to the MENU Set-up
instrumental parameters. By then the file FPC.MOD will contain all the information
entered of the successfully passed MENU. If no further changes are desired, <ESCape > to
the main MENU.
123
2.6 Libraries
All fundamental parameters as absorption coefficients, fluorescence yields, scattering

coefficients, etc., are stored in binary format files: The mass attenuation coefficients and the
photoelectric mass absorption coefficients, as tabulated in reference /MAS68/, are contained
in MCMAST.LBR. The differential and total scattering coefficients (/HUB75/) for elastic and
inelastic scattering are read from SCATPAR.LBR. All other fundamental parameters are
stored in KRAUSE.LBR. The fluorescence yields and the Coster-Kronig transition
probabilities are taken from reference /KRA79/, the emission probabilities for the K-lines
from /SCO74A/ and for the L-lines from /SCO74B/.
This program will access those libraries and the current *.XRL library during the
calculations. Usually they are found in the directory C:\AXIL . If, for any reason, the path has
to be altered, or one intends to use other *.LBR files than those default ones, such changes
can be made in the sub MENU Set up fundamental libraries found the MENU Set-up
instrumental parameters.
3. Specification of standards for calibration + Specification of unknown samples
Under Specify standard/sample information (program FUNA.exe) the determination of the

instrument constants continues, or, if that is already known and was entered as described
above, spectra of unknown samples can be processed. The next MENU displays already a
Current instrument parameter file. If needed, another *.FPC file could be loaded by Select
instrument parameter file. At least the current file must be contained in the default
directory. With the next SELECTOR BOX Select samples for quantitative analysis *.ASR
files of either standards or unknowns are loaded.
124
3.1 FORM Select calculation mode
In the FORM Select calculation mode one either has to choose Instru. constants for
fluorescence or Instru. constants for fluorescence & scatter, if one is about to determine
these constants. The second option refers to the above-mentioned case where one likes to
establish the constants for scattering experimentally. The third option, namely Sample
concentrations, is obviously used to calculate the concentrations in unknown samples.
Warning: If no *.FPC file exists, that describes the users experimental set-up, one
must establish the instrumental constant for fluorescence before one can analyze
unknowns, i.e. choosing Sample concentrations.
3.1.1 Type of instrument constants for standards
If one is about to determine the average instrumental constant with one or more standards
with known concentrations, no difference will be found in the coming result sheet for both
options of the MENU Type of instrument constants (Average and Individual and/or
average). The difference could only be found in the appertaining *.FPC file. For a selection
Individual and/or average all individual instrument constants for fluorescence will be
stored. If one chooses Average they will not be stored, i.e. they also cannot be used for
further calculations of unknown samples. It is recommended to select Individual and/or
average for the standards, because for unknown samples there is no must to use this extra
information.
3.1.2 Type of instrument constants for unknown samples
For unknown samples the same MENU has to be passed. Its relevance for the further
calculations depends on the selection in this MENU for the standards: As outlined above, if
Individual and/or average had been selected, the individual values were stored. One can use
them with the same option Individual and/or average in this sample run. As a consequence
concentrations of elements with a known individual instrumental constants for fluorescence
(elements present in standard and sample) will be calculated with this value, for all other
elements still the average instrumental constant applies.
Warning: If one wants to exploit the individual instrumental constants for

fluorescence for unknown samples, the standards must have been evaluated with
Individual and/or average option.
Be careful about the use of individual instrumental constants: when their values are far away
from the average instrumental constant. They are usually excluded from the calculations of
the average with good reasons (one can assume problems with the preparation, etc.). The
option Average in this MENU for unknown specimens might provide more consistent
concentration results - under the aspect of an overall accuracy for all detectable elements. If
information about only a few elements in a sample is needed, well-established individual
125
constants are to be preferred. An experienced user might edit the *.FPC file, eliminating the
out-layers in the individual instrument constant list.
3.2 FORM Information on sample
Various information of either standard or sample is needed and displays the name of the
accompanying AXIL result file.
As Sample type thin, intermediate thick, or thick can be selected. For a selection
Intermediate thick the aerial density (Sample mass) in milligrams per must be entered.
Any such entry for Thick standards/samples will be ignored during the calculations. For the
two other types the Full Fundamental Parameters METHOD can determine the aerial density
with the use of the scatter peaks. (Must be available in the *.ASR file!) No absorption
corrections will be calculated for Thin samples.
As Concentration units usual Weight percents will be convenient; Mass per unit area for
the aerial density can be practical for air filters, thin samples, etc.
Thin samples, as e.g. evaporated standard solutions, can have a foil as support. As such
Supporting material 5 options are available with the default: No support. If any other is
chosen, its thickness has to be specified in the same line.
Pressed pellets sometimes are prepared with some kind of Backing material (usually of disk
like shape of, e.g., pressed boric acid, or an aluminum cup). If needed, enter its thickness in
the same line.
The possible contributions to the scatter peaks from supporting as well as backing materials
can be corrected specifying the above-mentioned options.
During the final calculations (FUND4.exe) the concentrations (unknown samples) are
computed in iterations. If the difference in the concentration values (between two loops) stays
below a certain Convergent value, the program terminates the iteration (3 options). The
smaller this value the longer the computation time will be. Under realistic conditions the
default value of 0.1% is usually already unnecessarily low in comparison to all other
uncertainties involved.
All ITEMs, where numerical values had been changed, must be reconfirmed with <Enter>.
When the FORM finally fits ones needs <ESCape> to the next FORM.
126
3.2 FORM Menu for setting up options
All 9 ITEMs will offer 2 or more options.
ITEM 1, options: low Z matrix, high Z matrix, no matrix

Define a matrix, if necessary (otherwise toggle to no matrix). Be aware, that for low Z
matrix the *.ASR file must contain information about the scatter peaks, or either the sample
matrix composition is known (ITEM 3), or another spectrum result file with scatter peaks
information is available (ITEM 5). The term low Z matrix refers to elements in a sample that
are not represented by characteristic lines in the spectrum, e.g. C, O, H, N in organic
specimens.
For, e.g., steel samples, where one is interested in the trace elements only and knows the
content of iron, the Fe represents a high Z matrix.
Warning: For samples with dark matrix (option low-Z matrix) it is recommended to
prepare them in intermediate thick form. For thick samples results may be not
accurate.
Warning: For samples with dark matrix the scatter peaks must mainly originate from
the sample itself. The contribution to the scatter peaks from the sample chamber, air,
etc. can hardly be determined adequately and therefore should be small compared to
the contribution from the sample. In case of problems, evacuation of the sample
chamber or use of small collimators might help. The estimation of the dark matrix
does usually not work when the sample is excited by an extended isotopic source, e.g.
annular sources, due to scatter in the source holder.
ITEM 2, options: elements, oxides, compounds.

Oxides can be selected, if it is know that some of the elements are present as oxides and one
prefers to find this information in the sheet Analyzed elements (see later). The third option
has no effect, as for any of the 3 options the user will be able to enter compounds later.
ITEM 3, options: known, not known.

The selection should be consistent with the selection made in ITEM 1.
Warning: The experience was made, that the option matrix composition is known
does not provide correct results for standards containing a low Z matrix in form of
127
binders. For the specification of any known elements or the matrix of standards use
(7) instead.
ITEM 4, options: used, not used.

When the original sample/standard was diluted with a binder, or the fusion technique applied
to prepare glass bead samples, etc., a dilution factor (identical for all elements) will correct
the results.
Warning: The option Dilution material is used does not work, the corrections have
to be computed manually.
ITEM 5, options: the same spectrum, the other spectrum. A sample/standard can by
measured with optimized conditions for the characteristic lines of interest and the information
about scattering can be extracted from measurements of the same specimen with different
conditions.
E.g. one can measure the fluorescence peaks with Cu-anode excitation (*.ASR file for
concentrations), but in order to obtain separated elastic and inelastic scatter peaks a
Mo tube is used (*.ASR file for the scatter peaks).
ITEM 6, options: corrected, not corrected.

From the theoretical point of view one always should include the enhancement correction.
For the sake of computation time or to avoid uncertainties due to inaccuracies in the
calculations the correction might be disabled.
ITEM 7, options: known compositions, no known compositions

Any matrix (e.g.: other elements of a compound of the element of interest, binders) can be
specified. Even for unknown samples some detected elements (represented by information
about their characteristic line intensities in the *.ASR file) might have known concentrations.
ITEM 8, options: applied, not applied

The normalization of the concentrations to 100% must be applied whenever a dark matrix has
to be evaluated. I.e. samples with low Z matrix, or intermediate thick and thin samples with
unknown aerial density.
For all other cases it is recommended to have at least a first run of any unknown sample
without it. If the sum of all concentrations in a sample in the final report is, e.g., 275%, the
normalization may hide the otherwise obvious problems (e.g. wrong instrument constants).
ITEM 9 Options: not surely done, printed only, saved only, printed & saved
There still will be the opportunity to store (and print) after the display of the report SCROLL
BOX, also if not surely done is selected. The other options will print and/or save
automatically.
128
3.3 FORM Analyzed elements
In this FORM one can edit the constituent of any of the elements; for the probably above
selected oxides still the opportunity for changes exists.
Warning: Use upper and lower case characters correctly. E.g.: For calcium carbonate
one has to enter the compound CaCO3. Do neither enter CACO3, nor CaCo3, nor
caco3 instead!
The element under investigation must be found at the leading position. E.g.: If the
element chlorine of the compound sodium chloride is of interest, enter it as ClNa, not
as NaCl !
Also the net peak area (counts) can be altered. Good reasons might exist to do so, but be
careful about this option. Any information Det.Lim. in a line indicates that the observed peak
area is below a certain value, which usually is dictated by the background under this peak. As
a consequence this line will not be used for the further calculations. In case, one selected the
calculation mode Instrument constants for either fluorescence or scattering, i.e. one is
about to evaluate standards, a column compositions is awaiting entries for the concentration
values. For standards with impurities, that had to be included in the fitting procedure of
AXIL for the sake of acceptable fitting results, one can suppress these elements, if the
corresponding entries for composition are left at the default 0.0.
Depending on the choices in the FORM Menu for setting-up options several more FORMs
can appear:
3.4.1 Known elements
If in line (7) known composition was chosen, in a FORM Input known compositions one
either has to Edit a new file or one can toggle to Input an old data file.
For the first run of this program one will have to create such a new file. Later on an old data
file can be simply loaded. Within this file only entries for elements are allowed. Compounds
have to be split. After editing this sheet one will be prompted for a file name (and the
extension *.REB is added automatically).
129
Warning: Be aware that entries for (fluorescing) elements of this sheet might be in
conflict with results in the final report, if the same elements are treated as unknown,
too.
3.4.2 Known matrix
With the knowledge of the matrix in a sample one might have toggled to Matrix
composition is known in line (3). In that case one will enter a compound that does represent
it.
Warning: Problems with standards have been encountered for this option.
3.4.3 Scatter peaks
With a low or high Z matrix, as selected in line (1) a FORM Information on scatter peaks
is displayed. When the fields for the scatter peak areas are zero, one should reconsider the
choices in line (1), (3), or (5), or the *.ASR file did not contain scatter peaks.
The abbreviation Std means standard deviation of the scatter peak area. The hypothetical
matrix will consist of 2 elements that give the best results for the iteration process. The
difference in atomic numbers is by default 2. All values of this FORM can be edited.
Hint: If convergence problems in the later calculations are observed with 2 as

difference in atomic numbers, try with 1.
If repeating this part of the program in loops, because more than one file was loaded in Select
samples for quantitative analysis, the selected options and entered data will be kept as
default for the next run. So <ESCaping> from one of the above icons will either start a new
cycle or return to the MENU Full Fundamental Parameters.
By then a file FUNDP.TMP has been created and can be found in the same sub-directory
where all other files mentioned before were stored. Any time the program FUNA.exe
(Specify standard/sample information) was passed successfully the up-dated information is
written to this file.
130
4. Calculate Instrumental constants + Analysis of unknown samples
Attempting to <Enter> the ITEM Perform calculations (program FUND4.exe) prior to any
calibration will give an error message.
A different error message
Program: C:\AXIL\BIN\FUND4.EXE
cannot be started! Press any key to continue
is displayed, when there is a lack of memory available to DOS (see the point 5 of this
chapter, “Problems related to memory space”). For some computers there will be no error
message at all, instead there only will be a brief flashing of the screen.
After the successful run of all the above-mentioned MENUs a blue icon with Reading and
processing original data . . . as last line, and a small flashing rectangle behind it, will
appear.
If any inconsistencies or errors were found in the FUNDP.TMP file, that contains the
information of all the previous steps, error messages and the DOS prompt appear. E.g.
run-time error F6101: Read (FUNDP.TMP)

- invalid INTEGER
was generated by selecting low or high Z matrix in line (1) of the FORM Menu setting up
options, but the *.ASR file did not contain information about the scatter peaks. Solution: Fit
the scatter peaks with AXIL and include the results, or choose the option from another
spectrum in line (5).
Several similar error messages can appear. Start from the beginning and check all steps.
After this loading phase (assuming that nothing went wrong) a blue icon Display of the
calculated concentrations will appear and the intermediate results are displayed on-line. For
uncomplicated assumptions the computation time will be too short to perceive the icons,
because they will be overwritten by the final black result sheet (SCROLL BOX). The blue
icon rather serves as indicator of the progress for more complicated calculations (which may
take considerable time even on relatively powerful computers).
4.1 Average instrumental constants
When the option Calculate instrument constants has been enabled, the final SCROLL BOX
holds 2 values for scattering (if there are entries in the *.ASR files used, that contain scatter
peaks) and individual constants for fluorescence for each element and standard at disposal.
After a careful inspection of the individual constants (outliners can be eliminated, but also
could indicate experimental problems) an average value must be calculated by the user.
Starting from Set-up instrumental parameters continuing to Select instrument parameter

file where one has to load the same *.FPC file, that was used to determine the individual
instrument constant with the standards - no changes should be made in the above described
FORMs, because this would influence the instrument constants - finally enter in the FORM
Average instrumental constant the value for fluorescence.
131
When there is an overall bias in the concentration values for all elements in several samples,
usually the average instrumental constant for fluorescence may have to be adjusted.
The ITEMs for coherent scattering and incoherent scattering can be edited too, if needed,
otherwise the theoretical default values (as given by formula (1)) are used.
It is recommended, if individual instrument constants were determined from the standards,

that the user should edit the *.FPC file (for its structure see the appendix) and delete the
outliners that were rejected for the calculation of the average instrument constant.
4.2 Analysis of unknown samples
The Report of calculated concentrations can be printed and/or stored. The default report
name is the same as for the *.ASR file, used for the calculations, and carries the extension
ARP.
If the sample had been diluted, all concentration values have to be multiplied with a dilution
correction factor (not featured by this program).
5. Problems related to memory space
The relevant programs ECON.exe and FUND4.exe are quite big and run in the Conventional
memory of the computer. QXAS is already placed there. So users may encounter the error
message
Program: C:\AXIL\BIN\ECON.EXE
when they try to <Enter> the sub-MENU Set-up instrumental parameters. For some
computers there will be no error message at all, instead there only will be a brief flashing of
the screen.
And also
Program: C:\AXIL\BIN\FUND4.EXE
at Perform calculations, even when a correct FUNDP.TMP file had been created (or again
hardly any response).
At other stages of the programs problems with the memory size will be indicated by jumps
back to the main MENU, etc.
One approach to overcome this problem is the termination of all not absolutely necessary
open programs. The programs ECON.exe, FUNA.exe, and FUND4.exe are also running
without the environment of QXAS. As a consequence one must not start QXAS, if one wants
to run the quantitative METHOD Full Fundamental Parameters. After any other
132
calculations had to be done within QXAS, one terminates the package with the repeated use
of <ESCape> until the DOS prompt appears again. (Quit also programs like the Norton
Commander, etc.)
Start ECON.exe by typing ECON and <Enter> after the DOS prompt, to use Set-up
instrumental parameters. All MENUs and FORMs as described above will appear and one
should proceed as described above. <ESCaping> from the last FORM will not return to
QXAS, but instead a dark screen without even a DOS prompt will appear. Simply use the
DOS command CLS and <Enter> to refresh the display.
Continue by typing FUNA and <Enter>. (This starts FUNA.exe, which is the program behind
the MENU Specify standard/sample information). One proceeds as usual through all
FORMs. The last <ESCape> will result in a dark screen as described above. Clear the screen
with CLS and type FUND4 to start the program FUND4.exe.
Other sources of troubles are maybe certain Time Stay Resident (TSR) commands usually
started in the AUTOEXEC.BAT and CONFIG.SYS files in older versions of Windows
6. Demonstration
The *.spe files, as found in the directory C:\AXIL\SPECT, and listed in the table: Standards
(appendix), are spectra measured under the conditions as given in the table: Experimental
conditions. The twenty-five SD00*.spe files represent the standards, covering a wide range of
K- as well as L-lines. Several of them are metallic foils (thick samples), the others are
pressed pellets, usually with binders added.
Warning: Several of the pure standards contain contaminations, like Cu, Fe, etc. The
lines had been included for the sake of the fitting procedure only; their concentration
values should be set to zero.
After the peak evaluation with AXIL the standards (not necessarily all of them) can be used
to establish the average instrument constant for fluorescence. No effort was made to establish
experimentally determined instrument constants for scattering. The secondary target set-up
and the Si(Li)-detector can be described with the help of the table (Experimental conditions).
For the elements with low energetic characteristic lines it turns out, that acceptable
contributions to the average instrument constant only can be generated with an accurate
description of the attenuation along the path from the sample to the active volume of the
detector. Too high a value is usually found for elements, which had to be prepared as pressed
pellets with binders added. With the exclusion of the elements: Si, Ce, Sm, Dy, and U an
average instrument constant for fluorescence of G = 1.25*10-7 was found and used for the
calculation of the “unknown” specimen.
133
The “unknown” sample - C0001.spe - was prepared from the IAEA reference standard
SOIL7. It was mixed with a binder and pressed to a pellet, representing 87.06% of the total
sample mass (dilution factor of 1.149) with a total aerial density of 0.0354 g/cm2.
No supporting or backing material was used. Of course the sample contains a low Z matrix.
The scatter peaks were evaluated by AXIL from the same spectrum and the matrix was
represented by two elements differing in their atomic numbers by 2.
Ag X-ray tube: 60 take-off angle, 45 kV high Voltage, 5mA current,

Be-window = 0.127mm, no filter.
Mo secondary target: incident angle = take-off angle = 450.
Si(Li)-detector: 3mm thick, Be window = 8µm,
Au-layer ≈ 20-50nm, Dead-layer ≈ 20-100nm.
Atmosphere: 0.45 cm in air for exciting and fluorescence radiation.
Inside the sample chamber: vacuum 4mbar.
Angle between secondary target and sample surface =
angle between sample surface and detector = 450.
134
them with the dilution factor. The consideration of the enhancement effect will change
certain concentration values by up to 50%, and all concentrations were normalized.
135
Utilities
136
137
Fundamental parameters’ tables
The program FPT.exe enables the user to calculate and list explicitly the absorption edge
energies, fluorescence yield, mass absorption coefficients and x-ray production cross-sections
(both as function of the energy in keV) for elements with atomic number Z.
Termination of the program will be achieved with <break> (some computers

<ctrl>+<break>) or input “0” for the atomic number. From the line Enter photon energy E
(1keV<E<200keV): also enter “0” to return back to further calculations with a different
absorber.
138
139
Calculation of average atomic number
The program ZMEAN.exe will allow the calculation of the average atomic number of
mixtures of chemical compounds (also elements are permissible).
It is important to enter, e.g., H2O as H2O1, or CaCO3 as Ca1C1O3, or Hg as Hg1. To forget
any number after a formula entry, will result in the error message: Overflow!
After the last element/compound weight (% or weight fraction, but consistent throughout)
one has to leave the next entry for formula empty. With <return> the result will be displayed.
140
141
Spectral distribution of X-ray tubes
The program XTUBE.exe will enable the user the explicit calculation of the spectral
distribution for x-ray tubes. The input parameters are the atomic number of the anode
material Z, the applied high voltage in kV, the take-off angle from the anode, and the Be exit-
window thickness in µm.
Furthermore also a filter/absorber (thicknesses in µm), a secondary target set-up, and an air
path (length in cm) between x-ray tube and the place of the sample can be defined. For the
suppression enter “0” in the respective lines. The result of the calculations will be found as
ASCII file (SPECTRUM.DAT), which is accessible by any text editor.
142
143
Absorption coefficients, absorption corrections
It is possible to calculate, depending on energy and the atomic number of the absorber, the
incident and take-off angles and the incident energy:
*) Attenuation coefficients (a or χ in cm2/g)

*) Absorption correction factors (A, unitless), with the limiting value of 1 for thin samples
*) Absorption factors (unitless), (1 minus the absorption factor equals the transmission
factor)
by toggling with the space bar in Type of data under Define sample composition, geometry
and energies.
Warning: Unfortunately the absorption factor is named wrongly Transmission

factor. Also it should be rather absorption correction factor (normalized to 1 for thin
samples) instead of absorption correction (following the definitions of Emission
Transmission and Full fundamental parameters METHODs). Also the terms
attenuation coefficient and mass attenuation coefficient are not handled strictly.
It is also possible to calculate
*) Mass attenuation coefficients (µm in cm2/g, do not depend on angles nor the incident
energy).
In order to compute mass attenuation coefficients from (instead of) attenuation coefficients,
one leaves the Angle of incidence 0 and the Take-off angle at 90.0 and the Primary energy
(keV) also 0 (default settings).
A help menu is available (F1=HELP) with <F1>. It also contains the actual definitions of the
functions.
144
145
Incident – and take-off angles, Geometry
constants, *.sen file
1. Introduction
This program will be most helpful for source excitation where the average incident and take-
off angle for the sample cannot a priori be known. There is rather a range of angles
(maximum and minimum values) and the average angle can be evaluated best by Mont-Carlo
simulation. For tube excitation many systems will have typical values of 45o /45o for
incident/take-off angle, and there will be no need to run the program for this purpose.
The input is restricted to 3 annular source type products (a point source will have a geometry
that can be determined as for an X-ray tube), and 5 isotopes. Fe-55, Cd-109 and Am-241 the
typical proponents.
The excitation source as well as the detection system has to be specified.
Warning: For the calibration the relevant *.ASR standard files cannot be loaded. The
user has to note down the net intensities of the elements of interest and the acquisition
time (live time). One either has to inspect the file with a suited text editor program or
with a DOS command (e.g. TYPE).
As excitation source basically 2 ITEMs are available: Annular source and X-ray tube.
2. Calibration
2.1 Excitation with an annular source
Only certain products are accessible (MENU Source selection). This is due to the integration
procedure of the source geometry for the calculation of the incident and take-off angles
(Monte Carlo simulation). The MENU Isotope selection will pose more restrictions.
The next MENU Spectral lines selection asks, if the following MENUs and FORMs are
applying to K-alpha lines, or L-alpha lines. The whole MENU System sensitivity must be
edited in accordance with this selection. It must be worked out in a second, independent run,
if K as well as L lines of an unknown sample are of interest. For both of them the FORMs
Enter tube data, Enter experimental setup parameters, and the ITEM in the SELECTOR
BOX Select source description files must be identical.
The MENU Data input selection simply offers the possibility to fill in the following FORMs
with the values of an already existing sensitivity file (extension SEN) as default (Enter data
from old file), or all ITEMs of the FORMs will be blank (Enter data from keyboard). For
any of the 2 options it is possible to edit ITEMs. For the first option all existing *.SEN files
will be listed in a SELECTOR BOX.
146
Warning: Chose only a file that describes source excitation, otherwise several ITEMs
will not be accessible. For the first run of this METHOD no file might be available.
The information about the geometry of the system (FORM Enter experimental setup
parameters) is needed for the Monte Carlo calculation of incident and take-off angle
(/BER94/). For the significance of the various ITEMs refer to the sketch in figure 1. Some of
the ITEMs are not needed for the calculations (N/A) and cannot be accessed. The parameter
Collimator-source distance influences the calculations considerably and should be
determined with utmost care.
The more accurately the data entered for the Si(Li)-detector describes reality, the better will
be the relevant corrections for lower Z elements.
The calculate incident and take-off angle can be checked later on in the appertaining *.SEN
file (see appendix), and are given as 1/sin(incident angle) and 1/sin(take-off angle). Their
accurate values are needed for the absorption corrections of unknown specimens.
Hint: Point sources are treated better as X-ray tube excitation source, because the
incident and take-off angles are accessible directly (and maybe will be more
accurate). In that case a *.SOU file containing all line energies and intensities must be
created.
147
B
Sample
C K
Annular Collimator H D
source
J
Detector
L
F
Figure 1: Definition of parameters for annular source excitation
A Source inside radius

B Source outside radius
C Source-sample distance
D Sample-detector distance
E Detector -Be window distance
F Detector radius
G Collimator radius
H Collimator height
J Top collimator-detector distance
K Collimator-source distance
L Detector sensitive depth
2.2 Secondary target excitation
The ITEM X-ray tube is referring to a secondary target equipment. Spectral lines selection
asks, if the following MENUs and FORMs are applying to K-alpha lines, or L-alpha lines.
The whole MENU System sensitivity must be edited in accordance with this selection. It
must be worked out in a second, independent run, if K as well as L lines of an unknown
sample are of interest. For the FORMs Enter tube data, Enter experimental setup
parameters, and the ITEM in the SELECTOR BOX Select source description files must be
identical.
The MENU Data input selection simply offers the possibility to fill in the following FORMs
with the values of an already existing sensitivity file (extension SEN) as default (Enter data
from old file), or all ITEMs of the FORMs will be blank (Enter data from keyboard). For
148
any of the 2 options it is possible to edit ITEMs. For the first option all existing *.SEN files
will be listed in a SELECTOR BOX.
In the consecutive FORMs one must describe the experimental set-up. In the FORM Enter
tube data the angles are defined between beam and sample surface.
Warning: The ITEMs Tube anode material, Secondary target material, Tube
voltage, Tube current of this FORM have informative value only (and are included
in the result sheet) and are not used for the calculations. The data of a *.SOU file is
used instead.
For a secondary target several of the ITEMs of the FORM Enter experimental setup
parameters cannot be accessed (N/A); this information is needed for source excitation only.
The more accurately the data entered for the Si(Li)-detector does describe reality, the better
will be the relevant corrections for lower Z elements. For Sample-detector distance the
length of the path in air is meant. Any distances covered in vacuum, etc. should be excluded.
2.3 Source files
The actual description of the spectrum of primary radiation (for tube as well as source
excitation) will be accomplished by a *.SOU file, found in the SELECTOR BOX Select
source description files. Only a few are available. The files are described in table 1.
For the advanced user the creation of other *.SOU files, describing also other sources of
primary radiation is possible, if the structure is preserved (see appendix 6). There is no need
to edit the values for the incident and take-off angles (in case they are not matching with the
sensitivity file), because this METHOD extracts their values from the appertaining *.SEN file
directly. The angles typed into the *.SOU file are however used by the NBS method.
149
Table 1: Description of source files
*.SOU file name Description of the excitation source incident / take-off angles
for the sample in degrees
AGTAR50K.SOU Ag secondary target, 45 / 45
excited with an X-ray tube at 50kV
CD109.SOU Cd-109 source 49.76 / 74.05
CDTAR45K.SOU Cd secondary target, 45 / 45
FE55.SOU Fe-55 source 49.76 / 74.05
FETAR20K.SOU Fe secondary target, 45 / 45
MOTAR35K.SOU Mo secondary target, 45 / 45
MOTAR45K.SOU Mo secondary target, 45 / 45
ZRTAR30K.SOU Zr secondary target, 45 / 45
2.4 Addition of Standards
The FORM Enter compound must be fed with elements of suited standards and their net
intensities.
Warning: Be aware of the separation of K- and L-lines. Select only standards with
characteristic lines in accordance with this separation
The basic idea is, to have pressed pellets (no binders, etc.), or pure metals as standards. They
can be thick, intermediate thick, or thin. If needed the compound can be taken into
consideration.
150
Warning: Each element symbol must consist of 2 letters. For such ones that consist of
only a single letter a blank is needed. Numbers are permissible instead of the blank. If
the standard contains e.g. calcium carbonate, enter the compound as:
CaC_O_3, or CaC_O3 , or CaC1O3.
Any inputs not in accordance with the above constraints or containing not existent
element symbols will result in an error message:
Error in formula [ ], please reenter
After this entry an icon will display the element of the above compound that can be evaluated
by fluorescence lines, i.e. an element with an atomic number higher than 11 (Na). If more
than one element fulfills this condition, one must select and type the element name (in
accordance with the compound) manually. This procedure can be repeated with the same
standard, but for another element, if one wants to evaluate more than one element.
The third icon will need as entry the net intensity of the fluorescence peak divided by the live
time in (counts/second).
Warning: Any wrong inputs, noticed only after the closure of an ITEM with
<ENTER>, will result in repeating the procedure for the whole FORM for all
elements - there is no further editing option-
Warning: After the evaluation of all elements of the standards the user should type a
forward slash, i.e. the < / > character, in the ITEM Formula.
2.5 Sensitivity
The FORM Description of sensitivity calibration simply enables the user to write a text for
the first line of the result sheet. The last MENU Output selection offers the option to display
a SCROLL BOX List of data and results and/or save this sensitivity file.
For explanation of the column headings see the appendix. Of practical importance in that
SCROLL BOX will be the Average geometrical factor (G), the Variation coefficient of G
(%), and in comparison the individual values in the column Geo-fac. The column Sen-cal
151
contains the calculated sensitivities for those elements that can be accessed with this *.SEN
file (also elements not covered by standards can be found here).
Of most importance are of course the Cosecant for primary X-ray and the Cosecant for
secondary X-ray namely: 1/sin(incident angle) and 1/sin(take-off angle).
The procedure cab be repeated a second time, if K and L lines for standards are available.
If no result sheet is displayed, some of the options previously selected are not matching and
no *.SEN file can be created.
One has to Save results on disk as sensitivity file with the automatically added extension
SEN in the FORM Output file name. The ITEM Exit program can be used instead of
<ESCape>.
152
153
Appendix 1
154
155
Theory of non-linear function fitting
Reference /ESP02/
1. Least squares fitting method
Assuming we have a set of experimental data pairs:
( x1 , y1 ,σ 1 ),(x2 , y2 ,σ 2 ),(x3 , y3 ,σ 3 ),.....(xn , yn ,σ n ) (1)
where xi is the independent variable, yi is the dependent (measured) variable, and σ i is the
uncertainty of the particular method (if the data follows Poisson statistics σ i2 ≈ yi ). We
assume that we know a function F(xi) so that
F(xi ) = F(xi ,a1 ,a2 ,.....am ) (2)
where the aj are parameters. It is possible to determine the numerical values of the parameters
aj that fit the function F(i) best to the experimental data. We define a reduced Chi-square
function that has to be minimized:
1 n [ yi − F(xi )]
2
χ =
2
∑ σ2
n − m i =1
(3)
i
The number of data points n minus the number of parameters m, estimated during the fit, is
called the number of degrees of freedom. In order to find this minimum we must calculate its
derivates in respect of the parameters aj and equate it with zero. This results in m equations
for the unknown aj :
∂χ 2
= 0 ∀ j...1 ≤ j ≤ m (4)
∂a j
Unfortunately this system of m equations cannot be solved explicitly for the general
(nonlinear) case:
∂χ 2 2 n yi − F(xi ,a1 ,a2 ,.....am ) ∂F

∂a j
=− ∑
n − m i =1 σ i2 ∂a j
=0 (5)
156
2. Linear function
The situation changes, if one can assume the function F(xi) to be linear in its parameters aj.
This means we can write
m
F(xi ) = F(xi ,a1 ,a2 ,.....am ) = ∑ g j (xi )a j (6)
j =1
and
∂F
= g k (x) (7)
∂ak
The equation for the derivate of Chi-square in respect to the kth parameter becomes
 m 
 yi − ∑ g j (xi )a j  g k (xi )
∂χ 2 2 n  
∑
j =1
=− (8)
∂ak n − m i =1 σ i2
and rearranging and equating to zero:
∂χ 2 2 n  yi g k (xi ) m g j (xi )g k (xi )a j 

∂ak
=− ∑
n − m i=1  σ i2
−∑
σ i2
=0 (9)
j =1 
Finally we obtain the linear equation system
n
yi g k (xi ) m n g j (xi )g k (xi )a j
∑ =∑∑ (10)
i =1 σ i σ i2
2
j = 1 i =1
This also can be expressed in matrix notation:
b = α • a⇒a = α -1 • b (11a, 11b)
where
n
yi g k (xi ) n g j (xi )g k (xi )
bk = ∑ and α jk = ∑ (12a, 12b)
i =1 σ σ i2
2
i i =1
157
2.1 Uncertainty in the calculated coefficients
The uncertainty saj in the estimate of aj is due to the uncertainty of each measurement
multiplied by the effect of measurement on aj. So the variance (square of the uncertainty) can
be defined as:
2
 ∂a 
n
s = ∑ σ  j 
2 2
(13)
 ∂yi 
aj i
i =1
The elements of the inverse matrix α -1 are independent of yi , therefore the partial derivate is
∂a j 1 m
= 2 ∑ α −jk1 g k (xi ) (14)
∂yi σ i k =1
Inserting (14) into equation (13) results in the variance
m m
 n g (x )g (x ) 
sa2 j = ∑∑ α −jk1α −jl1 ∑ k i 2 l i  (15)
k =1 l =1  i =1 σi 
The last sum between the brackets is equivalent to equation (12b) and can be written as α jl .
We can contract to the final result
m m
sa2 j = ∑∑ α −jk1α −jl1α kl =α kk−1 (16)
j =1 l =1
which is a property of symmetric matrices. So the variance of a fitted parameter is given by

the diagonal element of the inverse matrix α −1 .
3. Description of fluorescence lines and appertaining peaks
3.1 Single Gaussian
The response function of a Si(Li) detector is nearly Gaussian due the fact that Poisson
statistics applies (the natural line with is usually neglected). A single Gaussian peak is
described as
G(Ei , E) =
GAIN
S 2π
[
(E - E ) 2
exp − 2 S i2 ] (17)
with E being the characteristic energy of the line in (eV). The energy calibration is given by
the energy ZERO in (eV) at channel 0 and the spectrum GAIN in (eV/channel) for the
energy Ei of channel i
Ei = ZERO+ GAIN⋅ i (18)

158
The peak width S is given by
2
 NOISE
S =
2
 + 3.85 ⋅ FANO⋅ E (19)
 2.3548 
NOISE is the electronic contribution to the peak width (typically 120eV), FANO is the Fano
factor (typically around 0.114), and 3.85 is the average energy required to produce an
electron-hole pair in silicon.
Usually fluorescence peaks are governed by Poisson statistics. In semiconductor devices, the
details of the energy-loss process are such that the individual events are not strictly
independent and a departure from Poisson behavior is observed. This departure is taken into
account by the inclusion of the Fano factor in the expression for the detector contribution to
the peak width.
The so defined Gaussian peak is normalized, so that the sum over all channels is unity.
3.2 Response function for an element group
The spectrum of an element group (e.g. K-line group) can be represented by
FP (Ei ) = A∑ R j G(Ei , E) (20)

j
The parameter A equals the total number of counts in all the lines of a group. The summation
runs over all lines in the group. Rj represent the (absorption corrected) relative transition
probabilities of the lines. In order to correct for the (energy dependent) absorption, the
transition probabilities pj must be weighted with the absorption correction term
T(E) = Tdetector + T path + Tsample (21)
It is composed of contributions from the detector (Be window, gold contact layer, Si dead-
layer, and thickness of the detector crystal), any air path between sample and detector,
detector filters, funny filter (an absorber with a small hole - additionally described by the
fraction of the detector solid angle subtended by the hole), and last but not least the sample
self absorption. This sample self-absorption only can be calculated accurately, if all elements
of the sample are taken into account. A rough estimate of the sample composition is often
sufficient. For other cases the fitting procedure must be repeated with the results of the
quantitative evaluation as input for the absorption correction term. One will have to redo the
quantification procedure with the updated peak areas.
159
3.3 Peak shape correction, escape peaks and sum peaks
When fitting Gaussians to very large peaks, the deviation from the pure Gaussian shape
becomes evident. One observes a tailing on the low-energy side of the peaks and the
background is also higher in front of e.g. the Kα peak than behind the Kβ. The reasons for that
are incomplete charge collection, satellite peaks due to radiative Auger transitions, etc.
Badly adjusted detector electronics are another self-made source for this effect, but cannot be
considered.
The AXIL program uses a stored table of experimentally determined values, representing the
difference between the observed shape and the pure Gaussian. Thin film samples had been
measured in order to generate spectra with very good counting statistics (Kα ≅ 107 counts).
Only the K-lines from Mg to Br are included.
Escape peaks can be modeled by a Gaussian with an energy 1.750keV below that of the
parent peak. The area relative to the area of the parent peak (η) can be calculated. Including
both effects the fluorescence peak of an element becomes
FP (Ei ) = A∑ R j [G(Ei , E) + S(i) +ηG(Ei , E - 1.75)] (22)

j
Pileup peaks, attributed to the finite shaping time of the detector electronics, can be included
for the total region of interest.
4. Background models for least squares fitting
Various analytical functions are in use in order to model the background.
4.1 Linear polynomial
A linear polynomial of the type
FB(Ei )= a0 + a1(Ei - E0 )+a2(Ei - E0 )2 +...+ak (Ei - E0 )k =∑ak (Ei - E0 )k (23)

k
is useful to describe the background over a region of a few keV. Expressing the polynomial
as function of Ei - E0 rather than as function of the channel number is done for computational
reasons. E0 is a suitable reference energy in the middle of the fitting region. For values of the
order of the polynomial in excess of four (which number heavily depends on the ROI),
physical unrealistic oscillations might occur.
160
4.2 Exponential polynomial
An exponential polynomial of the type
FB (Ei ) = ∑ a k (Ei - E0 )k +b0 ⋅ e [b1 (Ei - E0 )+b2 (Ei - E0 ) ]

2
+...+bl (Ei - E0 )l
(24)
k
can be used to describe the entire spectrum. This function is non-linear in the parameters
b1 , .... , b l .
Because of the non-linearity in the fitting parameters bl some initial values of these parameters
are requested.. AXIL automatically initializes the parameters by estimation of the background
and performing a linear fit of the logarithm of the calculated background:
[ ]
n
ln ybackgr (i) = ln(bo )+∑ bl ∆E l (25)
l =1
to obtain starting values for the parameters bl which are then further optimized in the fitting
procedure.
The high degree of non-linearity of the background parameters puts high requirements on the
non-linear fitting algorithm. When fitting a large number of similar spectra it might be
advantageous to get a good estimate of all the background parameters using one representative
spectrum and to treat the higher order terms as constant for the remaining spectra, only
optimizing lower order terms of the exponential polynomial, e.g. b0, b1 and b2. The number of
the higher order terms to be kept constant may be set, together with their values. This working
method aims at fitting the background over the entire spectrum or regions of high positive or
negative curvature.
4.3 Bremsstrahlung background
For electron-and particle-induced X-ray spectra the background is radiative in nature and
shows large curvatures. The slope of the emitted continuum is essentially an exponentially
decreasing function. At low energies the emitted photons are strongly absorbed in the sample
itself and by the detector window, etc. So the exponential polynomial is corrected with a
function T(Ei) describing the absorption (see formula (21)).
FB (Ei ) = ∑ ak (Ei - E0 )k +b0 ⋅ e [b1 (Ei - E0 )+b2 (Ei - E0 ) ] ⋅ T(E )

2
+...+bk (Ei - E0 )l
i (26)
k
161
4.4 Background estimation methods
Applying background estimation methods, the background is estimated and then subtracted
from the original spectrum prior to the least squares fitting of the resulting spectrum. The
procedures are simple from the users point of view, but sometimes do not provide optimum
results.
Applying the Orthogonal Polynomial Background method, the background is estimated by a
linear combination of orthogonal polynomials:
m
ybackgr (i) = ∑ c j Pj (xi ) (27)
j =0
where Pj(xi) is an orthogonal polynomial of degree j. The basic idea of this method is to fit
background channels as good as possible. For this, the background function is used to minimize
the Chi-square, which is the weighted sum of squares, over the background, of the differences
between the background polynomial and the measured spectrum yi:
χ2 = ∑ w (y − y
background
i i backgr (i))2
(28)
1
with wi =
ybackgr (i)
The crucial step in this method is the decision whether a channel is a background channel or not.
A channel i does not belong to the background, if its counts yi is statistically higher than its
approximation ybackgr(i):
IF yi > ybackgr (i)+ rٛ ybackgr (i)

(29)
THEN i is NOT a background channel
r is an adjustable parameter, which must be set when selecting the background during spectrum
analysis.
The order j of the orthogonal polynomial should depend on the shape of the background. High
numbers of fluctuations or oscillations, and higher curvatures request higher orders.
5. Non-linear least squares fitting
Several functions, representing the physical phenomena being responsible for the typical
shape of energy dispersive XRF spectra, are non-linear in the parameters. An example is
already a single Gaussian imposed on an exponential background of the order one:
F(Ei ) = A
GAIN
S 2π
[
(E - E ) 2
]
exp − 2 S i2 + b0 ⋅ eb1 (Ei − E0 ) + a0 + a1(Ei - E0 ) +... (30)
Considering the definitions for the energy calibration and the peak width, the function is non-
linear in the parameters ZERO, GAIN, NOISE, and FANO, as well as b1.
162
For such cases the parameters can be found by iterative procedures. The different algorithms
operate according to the following:
1. Give some initial set of values for the parameters aj (parameter vector a) and evaluate χ 2 .
2. Find a new set of values for the parameters aj so that χ new
2
< χ old
2
.
3. Test, if χ new
2
is a true minimum. Else repeat step 2.
Methods differ in the implementation of step 2.
5.1 Gradient method
The gradient of χ 2 in the m-dimensional parameter space is given by
∂χ 2
∇χ = ∑2
j (31)
j ∂a j
where j is the unit vector along the axis j and with the components of the gradient
∂χ 2 n
y − F(xi ,a) ∂F
= −2∑ i (32)
∂a j i =1 σ i2 ∂a j
The gradient gives the direction in which χ 2 increases most rapidly. A new parameter vector
a is calculated
a new = aold − ∆a ⋅ ∇χ 2 (33)
with an appropriate step size ∆a . This method is efficient quite well away from the minimum
to be found, but near the minimum the gradient becomes very small.
5.2 First order expansion method
The fitting function can be approximated by a first order Taylor expansion
∂F0
F(x,a j ) ≅ F0 (x,a j ) + ∑ ⋅ δa j (34)
j ∂a j
and is linear in the parameter increments δa j . Using this function we can express χ 2 as
2
1  ∂F 
χ = ∑ 2  yi − F0 (x,a j ) − ∑ 0 ⋅ δa j 
2
(35)
i σi 
 j ∂a j 
163
and can find the parameters δa j by use of the linear least squares fitting method. One has to
fit the difference yi′ = yi − F0 (x,a j ) with the derivates as variables and the increments δa j as
unknowns. In an analogous way to equations (12a) and (12b)
1 ∂F0
bk = ∑ yi′ (36)
i σ i
2
∂a j
and
1 ∂F0 ∂F0
α jk = ∑ (37)
i σ i2 ∂a j ∂ak
are defining a set of m normal equations in the unknowns δa j .
b = α • δa (38)
With the solution
δa j = ∑ α −jk1bk (39)
k
Near the minimum the first order expansion of Chi-square is a good approximation.
5.3 Marquardt algorithm
Based on the observation that away from the minimum the gradient method is effective and
near this minimum the first order expansion is useful, Marquardt /MAR63/ developed an
algorithm that combines both methods using a scaling factor λ which moves the algorithm
either in the direction of the gradient search or in the direction of the first order expansion.
The diagonal terms of equation (37) are modified in the following way:
α jk (1 + λ ) j = k
α ′jk =  (40)
 α jk j ≠ k
For λ >>1 the diagonal elements of α dominate which brings this method close to the
gradient method; for λ <<1 the solution is very close to the first order expansion method.
The algorithm proceeds as follows:
1. An initial value is given to the parameter vector a, the scaling factor λ is initialized with a
low value of λ = 0.0001 and χ 2 (a ) is calculated.
2. b and the matrix α are calculated by use of equations (36) and (37).
3. Modify the diagonal elements according to equation (40) and calculate δa .
4. If χ 2 (a + δa) ≥ χ 2 (a) increase λ by a factor of 10 and repeat step 3.
5. If χ 2 (a + δa)〈 χ 2 (a) decrease λ by a factor of 10. Accept new parameters a new = a + δa
and repeat step 2.
164
The algorithm thus performs 2 loops, the inner one incrementing λ until χ 2 starts to
decrease and the outer loop calculating successive better approximations to the optimum
values of the parameters. The outer loop is halted when χ 2 decreases by a negligible
absolute or relative amount (Minimum chi-square or Minimum difference in chi-square in
the MENU Set fitting control parameters).
Once the minimum is reached the diagonal elements are an estimate of the uncertainty in the
fitting parameters just as in the linear least squares procedure:
sa2 j = α −jj1 (41)
What, among others, provides the most important uncertainties for the net peak areas.
6. Criteria for the quality of the fit
The reduced χ 2 value is an indicator for the goodness of a fit and has an expectation value of
1 for a perfect fit. When fitting complex spectra with high count rate much higher Chi-square
values are obtained due to small imperfections of the peak or background model.
Another indicator is the residual, defined as
yi − F(Ei )
RES = (42)
σi
observed for each individual channel (after a successful fit MENU Display, command
Residual). Residuals in excess of +3 or -3 then indicate regions of bad fit. With a 99.7 %
probability any data points outside this range can not be explained with statistical
fluctuations, but indicate problems with the model.
It is the sum of the squares of these residuals that are minimized for the least squares method.
165
Appendix 2
166
167
Theory of the Emission Transmission method
For a sample of intermediate thickness the intensity of a characteristic line can be expressed
as a function of the sensitivity Si and the aerial density (thickness d)
1 − e− a( ρd )
I i = S i ⋅ c i ⋅ ( ρd ) ⋅ (1)
a( ρd )
The attenuation coefficient a is defined as a function of incident and take-off angles and
excitation energy (E0) and energy of the characteristic line of interest (Ei) of element i
µsample ( E 0 ) µsample ( E i )
a( E 0 , E i ) = + (2)
sinΨ1 sinΨ2
and µsample ( E ) is the energy dependent total mass attenuation coefficient of the sample.
Rearranging (1) we obtain
1 − e− a ( ρd )
Ii = Si ⋅ c i ⋅ (1a)
a
With the definition of the absorption correction
1 − e−a( ρd )
A = '
i (3)
a
Ii = Si ⋅ c i ⋅ Ai' (1b)
the concentration ci of an element i can be expressed as
Ii
ci = (4)
Si ⋅ Ai'
Practically Ii is obtained from the AXIL fit, Si from the METHOD Elemental sensitivities
and the absorption correction will have to be determined as follows.
When the element j of the target is measured with ( I target +sample ) and without the sample ( I target )
in the beam path, the attenuation caused by the sample can be described by absorption factor
target + sample
⋅ e− a( ρd )
target
Ij = Ij (5)
With some rearrangement
I target + sample − a( ρd ) j
target
=e (5a)
I
168
 I target + sample 
− a j ⋅ ( ρd ) = ln target  (6a)
 I 
the attenuation coefficient at the energy of the characteristic line of the target element j is
expressed as function of measured intensities
1  I target 
aj = ln target + sample  (6b)
( ρd )  I 
Practically the attenuation coefficient can be determined for the various energies of the
characteristic lines of the target and ln(a) will be plotted versus ln(E). On the other hand a (2)
can be expressed as a function of the energy (for the target radiation E0=Ei)
 1 1 
a( E j ) = µsample ( E j ) +  (2a)
 sinΨ1 sinΨ2 
Combining (6b) and (2a) the attenuation coefficient (still limited to the energies Ej as given
by the target) is
 1 1  1  I target   1 1 
µsample ( E j ) = a( E j ) ÷  +  = ln target + sample  ÷  +  (7)
 sinΨ1 sinΨ2  ( ρd)  I   sinΨ1 sinΨ2 
In order to interpolate for other energies (E0, and the various Ei ) as an assumption of this
METHOD the mass attenuation coefficient can be expressed by the relationship (Bragg-
Pierce law)
µ( E ) = A ⋅ E −B (8)
where A and B are constants. It will be good enough for samples where the “dark matrix”
governs the sample absorption behavior. A and B are estimated from the least square fit of
the plot ln(µ) versus ln(E).
From the so described total mass attenuation in the general form µsample ( E ) valid for a range
of energies the sample attenuation coefficient (2) can be calculated and the absorption
correction (3) used to calculate (4).
As another assumption it is necessary that to work with (1) the exciting radiation has to be
monoenergetic, otherwise the equation would contain an integral over the energy.
169
Appendix 3
170
171
Theory of the Alpha coefficients method
Reference /TAO85/
The general formula used in the Fundamental Parameters – monochromatic excitation –

NBS alpha coefficients METHOD, describing the desired concentration as function of the
measured net intensity and the concentrations of the other elements in the sample, is defined
as:
 
cx = Rx ⋅ 1 + ∑ α xj ⋅ c j + ∑∑ α xjk ⋅ c j ⋅ ck  (1)
 j j k 
with
cx analyte weight fraction (concentration normalized to 1)

cj , ck corresponding weight fraction of elements j and k, respectively
Rx Ratio of the net intensity of the analyte and the net intensity of the same line,
but from a sample consisting only of this element.
α xj alpha coefficient
α xjk “crossed” alpha coefficient
The coefficient α xj quantifies the effect of element j on analyte x and is equal to
α 2 ⋅ cm
α xj = α1 + (2)
1 + α 3 ⋅ cx
with
cm = c j + ck +... and cm + cx = 1 (3a,3b)
The three constants α1 , α 2 , and α 3 are calculated from hypothetical binary samples. α1 is
the value of the coefficient α xj near the cx = 1.0 limit (in practice computed at cx = 0.999; cj =
0.001). The value for α 2 is the range within which α xj will vary when the analyte decreases
to the cx = 0.0 limit (in practice computed from two binaries cx/cj = 0.001/0.999 and cx/cj =
0.999/0.001). The α 3 coefficient expresses the rate with which α xj is made to vary
hyperbolically within those two stated limits. Generally it is computed from three binaries
cx/cj = 0.001/0.999, cx/cj = 0.5/0.5 , and cx/cj = 0.999/0.001 .
The α xjk coefficients are included, on order to compensate for the fact that the total inter-
element correction cannot be only represented by a sum of binary matrix effects, with the
definition
1  cx 
α xjk =  − (1 + α xj c j + α xk ck  (4)
c j ck  Rx 
172
A value for the “crossed” coefficient is computed from a ternary with cx/cj/ck =
0.30/0.35/0.35, where the binary coefficients αxj and αxk are calculated at cx/cj = cx/ck =
0.30/0.70
173
Appendix 4
174
175
Theory of the Full Fundamental Parameters
method
Reference /HE91/
For a flat homogenous sample the relation between the concentration ci of an element x and
the net count rate N of a characteristic line l can be written for the general case of
polychromatic excitation as
N xl
cx = (1)
Gε (Exl )∑ I(En )[Qxl (En )Axl′ (En ) + H xl (En )]
n
For the explanation of symbols see table1. The summation accounts for the polychromatic
nature of the excitation source, with I(En) being the intensity distribution of the excitation
spectrum. G is an element and sample independent instrument constant (geometry factor).
ε (Exl ) is the relative detection efficiency for the characteristic radiation and Qxl(En)
represents the production cross section of the characteristic line l of the element x for the
excitation with photons of the energy En . Axl′ ( En ) is the absorption correction and Hxl(En) the
enhancement correction factor, both depending on the sample composition and the energies
of the incident and emergent X-rays, i.e., En and Exl.
1. Absorption correction
Both incident X-ray beam and fluorescence lines suffer an intensity decrease due to the
absorption in the sample. The absorption correction can be given as
1 − exp[− χ (Exl , En )ρd ]

Axl′ = (2a)
χ (Exl , En )
with
µ (En ) µ(Exl )
χ (Exl , En ) = + (3)
cosθ1 cosθ 2
The absorption correction factor, as found in the final report of Full Fundamental
Parameters and also used throughout the other quantitative METHODs is defined:
1 1 − exp[− χ (Exl , En )ρd ]

Axl = Axl′ = (2b)
ρd χ (Exl , En )ρd
and has the limiting value of 1 for thin samples.
176
The incident and emergent angles θ1 and θ 2 are measured relative to the normal of the sample
surface. (Not in accordance with the usual definition!) The total mass attenuation coefficient
µ(E) is defined as
µ (E) = ∑ c i µi (E) (4)

i
with the normalization of the concentrations
∑c
i
i =1 (5)
The attenuation coefficients of reference /MAS68/ are used.
2. Production cross section
For the case the characteristic line K α is chosen as analytical line, the production cross
section is given by
 S x,K − 1
ω x,K px,K a S τ x (En ) for En ≥ Ex,K
 x, K
Qxl (En ) =  (6)
 0 for En 〈 Ex,K


For the fundamental parameters as needed for the computations see /KRA79/. If the Kβ line
must be used for the quantification procedure, only the emission probability for a Kα line pKα
has to be replaced by pKβ , (pKα+pKα =1).
For the L-lines the interested reader is referred to references /HE91/ and e.g. /RAN89/.
3. Enhancement correction factor
The measured characteristic line intensity of the element x can be enhanced by secondary
excitation by another element j , if the characteristic photons of element j (originating from
excitation by the primary photons with En) have sufficient energy to expel an inner electron
of element x. This results in an addition to the primary characteristic line intensity, which
needs to be taken into account in quantitative analysis. The enhancement factor can be
calculated as
1
H xl (En ) = ∑ c j ∑m Qxl (En )Q jm (E jm )Yxl
2 χ (Exl , En ) j
(7)
177
where the element j is the element whose characteristic line m can excite the characteristic
line l of element x. The term Yxl is rather complex, especially for intermediate thick samples
(see reference /HE91/, /BOE90/), and is given here only for thick samples
cosθ1  µ (En )  cosθ 2  µ (Exl ) 

Yxl = ln 1 + + ln 1 +  (8)
µ (En )  cosθ1µ (E jm )  µ (Exl )  cosθ 2 µ (E jm ) 
4. Instrument constant
The instrument constant G is related to the geometry arrangement and theoretically equals to
dΩ1dΩ 2
G= (9)
4πcosθ1
In practice, however, the value for G is obtained by measuring standards. Thus, it also
includes a scaling factor for the excitation source and regulates uncertainties in theoretical
and experimental values (e.g. solid angles).
5. Detector efficiency
The detector efficiency for a Si(Li) detector is calculated from
ε (E) = exp − [µ Be (E)tBe + µ Au (E)t Au + µdl (E)tdl ]⋅ {1 − exp − [µ Si (E)tSi ]} (10)
where tBe , tAu , tdl , and tSi are the aerial density in (g/cm2) of the Be window, the gold contact
layer, the silicon dead layer, and the crystal, respectively.
Practically these values are usually specified rather poorly. So the quantitative determination
of light elements will be hampered by this fact. Sometimes it is possible to shift this problem
into element specific (thus energy dependent!) individual instrument constants.
6. Scatter radiation
For the calculation of the absorption as well enhancement corrections the concentrations of
all elements in a sample should be known prior to the computation of the concentration of an
element. This contradiction can be overcome by a suitable iterative procedure. Still there can
be elements in a sample that will not emit detectable characteristic lines. The composition of
this so-called dark matrix needs nevertheless to be known in order to calculate the absorption
correction factor. Use can be made of the scattered excitation radiation to estimate the
composition or the mass of the dark matrix in the sample, if elastic and inelastic scattered
peaks of a line used for excitation are well separated. The count rates of these two peaks are
respectively given by
178
dσ coh,i
Ncoh = Gcohε (E)Acoh(E)I(E)∑ ci (E,θ )≅ 4coh ε (E)Acoh(E)I(E)∑ ciσ coh,i (E)
G
π
i dΩ i
(11)
and
dσ inc,i
Ninc = Gincε (Einc )Ainc(E)I(E)∑ci (E,θ )≅ 4incπ ε (Einc )Ainc(E)I(E)∑ciσ inc,i (E)
G
i dΩ i
(12)
with the scattering angle θ = θ1 + θ 2 . The theoretically calculated values are in accordance
with reference /HUB75/.
With this assumption the instrumental constants for scattering can be derived from the one
for fluorescence:
Gcoh = Ginc = 4πG (13)
Separating the contribution of the high atomic number (fluorescent) elements from the dark
matrix elements, the scattering coefficients of the latter can be calculated from
dσ coh,i N coh dσ coh,i

lowZ
S coh = ∑c
lowZ
i
dΩ
= − ∑ ci
I(E)Gcohε (E)Acoh (E) highZ dΩ
(14)
and
dσ inc,i N inc dσ inc,i

lowZ
S inc = ∑c
lowZ
i
dΩ
= − ∑ ci
I(E)Ginc ε (Einc )Ainc (E) highZ dΩ
(15)
where the concentrations in the summation over the high Z elements are assumed to be
known from the fluorescence intensities. All values on the right hand side can be accessed
either by measurement or theory. As a result the dark matrix can be represented by two
elements, e.g., Z and Z+2, where Z is calculated in such a way that
dσ coh,Z + 2 Scoh
lowZ
dσ coh,Z
≥ lowZ ≥ (16)
dσ inc,Z + 2 Sinc dσ inc,Z
and the concentrations of these two representative elements are calculated by solving the
system of the 2 equations in 2 unknowns cZ and cZ+2 :
dσ coh,Z dσ coh,Z +2
lowZ
S coh = cZ + cZ + 2 (17)
dΩ dΩ
and
dσ inc,Z dσ inc,Z +2
lowZ
S inc = cZ + cZ + 2 (18)
dΩ dΩ
These two concentrations can now be used for the calculations of the absorption correction
factors in order to obtain correct results for concentrations of the fluorescing elements. The
179
second representative element is specified as Z+2 instead of Z+1 in order to reduce
oscillations in the iterative calculation procedure.
180
Table: Definition of symbols
Symbol Definition
cx concentration of element x
Nxl net count rate of line l of element x in (s-1)
G instrument constant in (sr)
Exl energy of characteristic line l of element x in (keV)
En central energy of an energy interval n of the primary radiation in (keV)
ε ( E xl ) relative detection efficiency for the characteristic radiation Exl
I(En) primary intensity at energy En (a.u.)
QxlEn) production cross section of the characteristic line l of the element x for the
excitation with photons of the energy En in (cm2/g)
Axl′ ( En ) absorption correction for the line l of element x excited with En in (g/cm2)
Axl(En) absorption correction factor for the line l of element x excited with En
Hxl(En) enhancement correction factor for the line l of element x excited with En
ρ sample density in (g/cm3)
d sample thickness in (cm)
θ1 , θ 2 incident and take-off angle, relative to the normal of the sample surface
µ x (E) mass attenuation coefficient of element x for the energy E in (cm2/g)
ω x,K fluorescence yield of K-shell of element x
p x , Kα emission probability for a K α line of element x
Sx,K absorption edge jump ratio of K-shell
τ x (E) mass absorption coefficient of element x for the energy E in (cm2/g)
Ex,K energy of the K absorption edge for element x in (keV)
Ω1 , Ω 2 incident and take-off solid angles in (sr)
Ncoh net count rate of the coherent scatter peak (s-1)
Ninc net count rate of the incoherent scatter peak (s-1)
dσ coh ,i
(E,θ ) coherent differential scattering coefficient at a scattering angle θ for the energy E
dΩ
and element i in (cm2/(g.sr))
dσ inc ,i
(E,θ ) incoherent differential scattering coefficient at a scattering angle θ for the energy
dΩ
E and element i in (cm2/(g.sr))
θ scattering angle
σ coh ,i ( E ) coherent scattering coefficient for the energy E and element x in (cm2/g)
σ inc ,i ( E ) incoherent scattering coefficient for the energy E and element x in (cm2/g)
Gcoh instrument constant for coherent scattering (sr2)
Ginc instrument constant for incoherent scattering (sr2)
181
Appendix 5
182
183
User Interface
The QXAS package communicates with the user by means of menus, forms, scroll boxes and
selector boxes. A special command language is used by QXAS.
1. MENU
Menus, arranged in a hierarchical structure, are used to perform tasks within the package. The
top line is the menu's title, below it are all the choices one can make. One of the choices is
highlighted.
1.1 Input Rules
1.1.1 Keyboard
Using the up and down arrow keys one can highlight the other choices (items) of the
menu.
Pressing <ENTER> the highlighted item is selected and performed.
Pressing <ESCape> one leaves the sub-menu and returns to the menu from which this
sub-menu was selected.
1.1.2 Mouse
Putting the mouse pointer on the desired item and pressing the left mouse button selects
and performs the corresponding choice.
2. FORM
Forms are used to enter or alter data. The form can contain optionally a title and consists of pairs
of field label and input field. The field label explains the data of the corresponding input field.
One of the input fields is highlighted. Depending of the type of the input field one has to follow
certain rules to enter or alter data. Alphanumerical input fields accept both numbers and letters
(also special signs); numerical input fields only accept numbers; toggle input fields accept
predefined data and don't accept numbers or letters. The status line at the bottom of the screen
indicates what kind of input rules are available for the selected (highlighted) input field. The
cursor appears in the first input field.
184
2.1 Input Rules
Using the up arrow and down arrow keys one can move from one input field to another.
<ESCape> removes the form and continues the execution of the program.
NOTE: Temporary changes are lost using the up arrow, down arrow and <ESCape> keys.
2.1.1 Numerical & Alphanumerical Input Fields
Pressing <HOME>: the cursor moves to the beginning of the input field.
Pressing <END>: the cursor moves to the end of the input field.
Left arrow and right arrow keys: the cursor moves in the selected input field.
Typing letters, special signs and digits: one writes in the input field; the changes are temporary.
<DEL> deletes the character at the cursor position.
<BACKSPACE> the character in front of the cursor is deleted.
<ENTER> makes the change of the data permanent and the following input field is selected,
when the form consists of more than one input field. The form disappears, if there is only one
input field.
<INS> the insert mode or overwrite mode is selected. Being in the insert mode, the characters
entered are inserted before the cursor, characters dropping out of the field are lost.
2.1.2 Toggle Input Fields
Pressing - or + keys: one changes the data to the previous or next option out of a list of
predefined alternatives; the change made is permanent.
Pressing the left (right) arrow is equivalent to pressing the - (+) key.
<SPACE BAR> is equivalent to pressing the + key.
2.2 Mouse
Putting the mouse pointer on a not selected input field and pressing the left mouse button selects
(highlights) the pointed input field. The cursor appears at the beginning of the field.
In case of a form with only one input field, putting the mouse pointer in the "input-free" area of
the box and pressing the left mouse button is equivalent to <ESCape>. In case of a form with
more than one input field, putting the mouse pointer in the "input-free" area of the box and
pressing the left mouse button is equivalent to press the up arrow key.
Pressing the 2nd or the 3rd mouse button is equivalent to <ESCape>.
The mouse pointer on a selected numerical or alphanumerical input field and pressing the left
mouse button moves the cursor to the pointed position.
The mouse pointer on a selected toggle input field and pressing the left mouse button is
equivalent to pressing the + key.
185
3. SCROLL BOX
A scroll box is a window used for displaying a text. If the text is longer than the predefined size
of the scroll box, the text can be inspected by means of scrolling the text through the scroll box
window.
On the left side of the box arrows and triangles appear.
3.1 Input Rules
The up arrow, down arrow, <PgUp>, <PgDn>, <HOME> and <END> keys scroll the text in the
box..
<F10> gives a FORM, which asks the name of the text file to be created.
<ESCape> removes the scroll box and continues the execution of the program.
3.2 Mouse
The mouse pointer on the up or down arrow signs of the left side of the box and pressing the left
button of the mouse is equivalent to the up arrow or down arrow key (see SCROLL BOX : Input
Rules).
The mouse pointer on the up triangle or down triangle of the left side of the box and
pressing the left button of the mouse is equivalent to <PgUp> or <PgDn>.
The 2nd or the 3rd mouse buttons are equivalent to <ESCape>.
4. SELECTOR BOX
Selector boxes are used when the selection of one or a few things out of many is needed (e.g.
files from a directory). The box contains a list of items (e.g. list of files) and one of the items is
highlighted.
An "*" in front of an item indicates that the item is selected. On the left side of the box arrows
and triangles appear, and on the right side there is a filled rectangle. The position of the rectangle
gives information about the position of the selector box in the list of items (e.g. if the first (last)
item is highlighted, the rectangle appears at the top (bottom) of the right side of the box).
The length of the rectangle gives information about the amount of items displayed (e.g. when all
the items of the list are displayed in the box, the rectangle covers the whole right side of the box).
186
4.1 Input Rules
The up arrow, down arrow, <PgUp>, <PgDn>, <HOME> and <END> keys selector cause
movements in the box and the position of the rectangle on the right side of the box is adapted.
When necessary the list is scrolled in the box.
<ENTER> the highlighted item is selected and the selector box moves to the next item of the list.
When only one item can be selected, the selector box disappears and the program continues
execution.
<DEL> the highlighted item is unselected and the selector box moves to the previous item of the
list.
<ESCape> removes the scroll box and continues the execution of the program.
4.2 Mouse
The mouse pointer on an item line in the box and pressing the left mouse button, the
unselected (selected) item is selected (unselected).
Mouse pointer on the up or down arrow signs of the left side of the box and the left button of the
mouse is equivalent to the up arrow or down arrow.
Mouse pointer on the up triangle or down triangle of the left side of the box and the left button of
the mouse is equivalent to <PgUp> or <PgDn>.
The 2nd or the 3rd mouse button are equivalent to <ESCape>.
5. COMMAND LANGUAGE
The peak-fitting program AXIL uses commands.

A command line typically consists of a verb followed by a number of qualifiers. Which
commands and qualifiers can be entered, depends on the current state of the program. A
command menu displayed in the right hand part of the screen gives the commands and qualifiers,
which can be entered together with its format. Qualifiers are separated with spaces and
commands are entered after the command line prompt ">>". A cursor "_" appears on the
command line.
5.1 Input Rules
Typing a letter, a special sign or a number writes the corresponding character in the cursor
position.
<BACKSPACE> the character in front of the cursor is deleted.
<F1>, <Left Arrow>, <PgUp>, etc., may cause special actions, which are indicated in the
command menu.
<ENTER> performs the command on the command line.
<ESCape> removes the command partially or entirely.
187
5.2 Mouse
The mouse pointer on an item in the command menu and the left mouse button is equivalent to
typing the command or qualifier, or pressing the equivalent key. In case of keys with special
actions and also the command menu items "GO" and "CANCEL" nothing will be written in the
command line.
The "GO" command menu item is equivalent to <ENTER>. "CANCEL" is equivalent to
<ESCape>.
188
189
Appendix 6
190
191
Structure of files
Structure of SETUP.AX
The SETUP.AX file is a dynamic file that accepts certain information from QXAS programs.
This current information can be read by the programs and, if necessary, updated. It contains
the “menu tree” of all the installed programs in the package, the text and graphics mode, etc.,
and the names of the current data files in use.
The set-up file is a block structured data file, i.e. it is divided into blocks that are identified
by a header name, with < $ > as starting character and < : > as last character. The actual
position of a block of information within the file is of no importance.
library for energies

and rel. intensities
$AXIL$XRL:
C:\AXIL\AXIL.XRL library for peak
$AXIL$PSL:
C:\AXIL\AXIL.PSL shape corrections
$AXIL $PRNTYPE: printer information

MatrixP
$AXIL $PRNPORT: for AXIL used by
lpt1:
PLOT function
$AXIL$INP:
A:\AXIL\chris1a.INP
current *.INP file
$AXIL$FUNDLIBS:
c:\axil\krause.lbr libraries for
c:\axil\mcmast.lbr
c:\axil\scatpar.lbr Fundamental Parameters
$AXIL$FPC: current *.FPC

a:\SILPW.FPC file
$TEXT: definition of
3 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
241 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 background colors
192 193 194 195 196 197 198 199 200 201 202 203 204 205 206 207
208 209 210 211 212 213 214 215 216 217 218 219 220 221 222 223
$GRAPH:
16 0 7 15 definition of ASCII characters for line drawing
2 4 11 1 -1 -11 -4 -12
8 14 0 0 639 349
$NEW_COMM: parameters for

2 1
9600 0 8 1
COM ports
4800 0 8 1
$COMM:
1 15 0 8 1 needed for compatibility with old
2 13 0 8 1 MCA communication utilities
$AXIL$BIN:
C:\AXIL\BIN PATH for directories \BIN
$AXIL$INSTALL:
C:\AXIL\INSTALL
and \INSTALL
$AXIL$CAL:
C:\AXIL\SPECT\TEST2K.CAL current *.CAL file
$SEED:
123456792.000000
Seed for the random number generator
192 (Monte Carlo calculations)
continuation SETUP.AX
definition of programs to be used

$MENUTREE:
and their order of appearance
@AXIL HARDW "System hardware setup" AXSETUP.EXE
@AXIL DOSCMD "Execute DOS command" DOSCMD.EXE
@AXIL FITTING "Spectrum analysis"
@FITTING AXFIT2 "Perform spectrum fitting" AXFIT.EXE
@FITTING AXPAR "Specify parameters for spectrum analysis" AXPAR.EXE
@FITTING AXRLM "X-ray library management" AXRLM.EXE
@AXIL SPEDAC "Spectrum format conversion" RSPEDAC.EXE
@AXIL UTIL "Utilities"
@UTIL ET10 "Alternative Emission-Transmission method" ET10.exe
@UTIL MASABS "X-ray Absorption Calculations" MASABS.EXE
@UTIL ZMEAN "Mean Z and stequeometry calculation" zmean.exe
@AXIL FUND "Quant. analysis using fundamental parameters" text as found
@FUND ECON "Set-up instrumental parameters" ECON.EXE
@FUND FUNA "Specify sample information" FUNA.EXE
in the MENU
@FUND FUND4 "Perform calculations" FUND4.EXE
@AXIL QUANT "Quantitative analysis"
@QUANT ORGANIC "Quantitative analysis of light matrix materials" ORGANIC.EXE
@QUANT NBS "NBS quantitative analysis package"
@NBS AXNBS1 "Prepare standard concentrations file" AXnbs1.exe
@NBS calco "Prepare the alpha coefficients file" calco.exe
@NBS calcomp "Calculate concentrations" calcomp.exe
@QUANT SENSCAL "System sensitivity and efficiency calibration" SENSCAL.EXE
@QUANT SENST "Define calibration and standars (req. simple quant.)" SENSTD.EXE
@QUANT KLCAL "Create separate *.cal files for K and L lines" KLCAL.EXE
@QUANT SENSCALN "System sensitivity and efficiency from *.cal file" SENSCALN.EXE
@AXIL TRANSFER "Communication with MCA"
@TRANSFER CAN35ASC "Canberra 35 +" CAN35ASC.EXE
@AXIL SIMQANA "Simple quantitative analysis"
@SIMQANA DIRCOMP "Direct comparison of count rates"
@DIRCOMP DIRSTD "Define Calibration and Standards" DIRSTD.EXE
@DIRCOMP DIRCAL "Perform Calibration of X-ray System" DIRCAL.EXE
@DIRCOMP DIRANA "Quantitative Analysis of Unknown Samples" DIRANA.EXE
@SIMQANA REGANAL "Regression of Count rate vs. Concentration"
@REGANAL REGSTD "Define Calibration and Standards" REGSTD.EXE
@REGANAL REGCAL "Perform Calibration of X-ray System" REGCAL.EXE
@REGANAL REGEXT "Extend Calibration for not measured elements" REGEXT.EXE
@REGANAL REGANA "Quantitative Analysis of Unknown Samples" REGANA.EXE
@SIMQANA ELSENS "Elemental sensitivities"
@ELSENS SENSTD "Define Calibration and Standards" SENSTD.EXE
@ELSENS SENCAL "Perform Calibration of X-ray System" SENCAL.EXE
@ELSENS SENANA "Quantitative Analysis of Unknown Samples" SENANA.EXE
program, actually
executing a MENU
193
Structure of a *.SPE file (C0001.SPE)
Header live-, real time
$SPEC_ID:
Soil 7 Pellet# 474
1024 channels,
$DATE_MEA: starting with zero
10-22-1993 10:22:29
$MEAS_TIM:
1000 1028
$DATA:
0 1023
0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 2
22 9 20 18 14 29 24 23 24 23
23 25 29 27 21 30 14 19 21 22
17 14 23 14 17 20 18 17 19 10
16 17 15 15 16 13 27 20 23 29
20 20 26 24 29 36 52 71 69 112
108 100 70
channel number 78
contains 71 counts
194
Structure of an *.OUT file - Full report (SD0023.OUT )
The spectrum was fitted with the inclusion of the contaminations Fe, Ni, and Cu. As-Kα and
As-Kβ were treated independently with escape and peak shape corrections. For the input
model the composition of this standard was specified as As2O3. The background was
modeled as exponential polynomial, order 3, with Automatic region of interest.
+-----------------------------------------------------------------+
¦ AXIL IBM-PC V3.00 01-29-1995 18:04:40 ¦
¦ Spectrum: SD0023.SPE 500.s ¦
+-----------------------------------------------------------------+
+-----------------------------------------------------------------+ Lambda as defined
¦ Fitting Region: channels 232 - 668 5 iterations done ¦
¦ ChiSquare = 2.0 last change = -.42% lambda= 1.E+00 ¦ by the Marquardt
¦-----------------------------------------------------------------¦
¦ CALIBRATION DATA ¦ algorithm
¦-----------------------------------------------------------------¦
¦ ¦ Initial estimate ¦ Final estimate ¦
¦----------------+------------------------+-----------------------
¦ ZERO (eV) ¦ -7.7 ± 100.0 ¦ -7.7 ± .0 ¦ variation of parameters
¦ GAIN (eV/ch) ¦
¦ det NOISE (eV) ¦
21.600 ±
-63.1 ±
2.000
40.0
¦
¦
21.600 ±
-63.1 ±
.000
-.2
¦
¦
for energy calibration
¦ FANO factor ¦ .211 ± .050 ¦ .211 ± .000
+-----------------------------------------------------------------+
¦ and peak resolution
+-----------------------------------------------------------------+
¦ PEAK DATA ¦
¦-----------------------------------------------------------------¦ characteristic energy
of Fe-Kα1
¦ # Line E(KeV) rel. int. peak area st. dev chi-sq ¦
¦ chan# fwhm (eV) backgr tot. abs ¦
¦-----------------------------------------------------------------¦
¦ ¦
¦ 1 Fe-K
¦ KA1 6.399 .86046
571. ±
491. ±
13.
12.
¦
1.3 ¦ absorption correction
¦
¦
296.611 157.69 316. 2.47E-02 ¦ factor
corresponding
channel number
absorption corrected
transition probability total net peak area
for As-Kα
¦ 4 As-Ka * 1892429. ± 591. ¦ individual Chi-square

¦ KA1 10.544 .66016 1249307. ± 390. .8 ¦
¦ 488.514 208.69 22217. 5.28E-02 ¦ value for As-Kα1 = 0.8
¦ KA2 10.508 .33891 641359. ± 200. 1.1 ¦
¦ 486.847 208.30 23545. 5.27E-02 ¦
¦
¦
KA1 -esc 8.802
407.864
.00061
188.94
1161. ±
919.
0. 3.0 ¦
4.25E-02 ¦ net peak area
¦
¦
KA2 -esc 8.766
406.197
.00032
188.51
602. ±
909.
0. 3.2 ¦
4.23E-02 ¦
for As-Kα1
¦ ¦
¦ 5 As-Kb * 308634. ± 243. ¦
¦ KB1 11.724 .99931 308421. ± 243. 1.4 ¦ background of As-Kα1 ≈
BG of As-Kα2 ≈ BG As-Kα
¦ 543.145 221.07 12444. 5.84E-02 ¦
¦ KB1 -esc 9.982 .00069 213. ± 0. 8.6 ¦
¦ 462.495 202.53 5760. 4.98E-02 ¦
¦ ¦
+-----------------------------------------------------------------+
* Peak shape correction included
FWHM in (eV)
195
+-----------------------------------------------------------------+
¦ EXPONENTIAL BACKGROUND ¦
¦-----------------------------------------------------------------¦
¦ order ¦ linear param. ¦ exponential param. ¦
¦ ¦ E0 = 9.962 KeV ¦ init. estimate final estimate ¦
¦---------+-------------------+-----------------------------------¦
¦ 0 ¦ -1.604E+01 ¦ -- ¦ 1.944E+00 ¦
¦ 1 ¦ -- ¦ 2.383E+00 ¦ 2.383E+00 ¦
¦ 2 ¦ -- ¦ -7.096E-01 ¦ -7.096E-01 ¦
¦ 3 ¦ -- ¦ 6.777E-02 ¦ 6.777E-02 ¦
+-----------------------------------------------------------------+
Structure of a *.DMP file (C0001.DMP)
165 3.557 406.0 461.5 14.2

166 3.578 770.0 788.6 14.1
167 3.600 1142.0 1235.0 14.1
168 3.621 1756.0 1763.5 14.0
169 3.643 2248.0 2290.5 14.0
170 3.665 2711.0 2702.5 13.9
171 3.686 2841.0 2894.5 13.9
172 3.708 2811.0 2813.3 13.8
173 3.730 2403.0 2481.1 13.8
174 3.751 1967.0 1985.8 13.7
175 3.773 1377.0 1443.5 13.6
176 3.794 922.0 955.3 13.6
177 3.816 567.0 580.3 13.5
178 3.838 313.0 332.6 13.5
179 3.859 185.0 196.6 13.4
180 3.881 121.0 145.2 13.3
channel
number
background
fitted
spectrum
measured
spectrum
energy in (keV)
196
Structure of an *.ASR file (C0001.ASR)
Header copied
from *.SPE file
total number
$SPEC_ID:
Soil 7 Pellet# 474
of peaks
$DATE_MEA:
10-22-1993 10:22:29 net peak area
$MEAS_TIM: characteristic
1000 1028
Energy standard
$PEAKS:
19 deviation for
19 1 3.312 898. 39. 1.43 this peak
20 1 3.690 22216. 143. 1.08
22 1 4.509 697. 31. 1.04
24 1 5.412 18. 15. 1.21 chi-square for
25 1 5.895 630. 31. .70 the fit of this
26 1 6.400 34834. 177. 1.24 peak
27 1 6.925 114. 39. 1.12
28 1 7.472 68. 16. .54
29 1 8.041 175. 18. .86
30 1 8.631 456. 25. .53
31 1 9.243 45. 15. 3.58
33 1 10.532 -246. 167. 1.06
34 1 11.208 4. 11. 1.62
35 1 11.908 111. 17. 1.02 indicator for
37 1 13.375 747. 34. .90 K-lines
38 1 14.142 2052. 51. 1.32
39 1 14.932 528. 37. 1.15
40 1 15.746 676. 86. 1.11 indicator for
82 2 10.542 680. 169. .95 L-lines
$COH_SCAT:
1
42 1 17.443 33542. 311. 2.90 information
$INC_SCAT: about elastic
1 and inelastic
42 1 16.867 52711. 436. 14.55
scatter peaks
atomic number
197
Structure of a *.FPC file (TEST6.FPC)
$INDIV_INSTRU_CONSTS:
28 1 1.2553E-07 Individual instrument
29 1 1.2404E-07 constants for Ni, Cu, Zn
30 1 1.2871E-07
$EXCIT_MODE:
1 tube excitation
$EXCIT_DATA:
47 6.00 1.270e-002 45.00 0 Ag X-ray tube: take-off
42 45.00 45.00 12 angle = 60 , Be-
$EXCIT_SPECT:
1.7712E+010 17.479 window thickness,
9.2475E+009 17.374 45kV, number of lines
4.9358E+009 19.602
7.5492E+008 19.965 Mo secondary target:
5.0941E+007 2.468
5.1553E+006 2.831 incident -, take-off
3.5233E+008 2.395 angle = 60 ,
1.5350E+007 2.120 number of lines = 12
1.0238E+007 2.624
7.4821E+008 2.293
3.0047E+007 2.061 description of the 12
7.3220E+006 2.456 lines: relative intensity,
$DETECT_PARAM:
0 7.620E-004 2.000E-006 1.000E-005 3.000E-001 energy of K- and L-lines
$DETECT_GEOM:
1 0.45 45.00 0.45 45.00 description of the Si(Li)
$MEAN_INSTRU_CONSTS:
1.2500E-7 0.0000 0.0000 detector
$EXCIT_FILT:
0 Average instrument
$COLLIMATOR: constant f. fluorescence;
0
$REF_DATE: values for scattering
01-14-1995 20:41:09 constants will be set to
the default
(= 4π ⋅ fluoresc.const.)
198
Structure of a *.SOU file (MOTAR45.SOU)
text
$IDENT:
Mo secondary target at 45 V, Mo anode excitation, no filter Secondary
MO
45. target material
$GEOM:
45.,45. Voltage in kV
$CONTINIUM:
2 incident, take-off angles
1.,0.
1.2,0. of the sample
$CHARLIN: total number of characteristic lines
4
.713595,28.095 of the Mo-secondary target
.709308,53.969
.632486,15.544 relative intensity of Mo-Kβ2
.620987, 2.392 (corrected for self absorption)
wavelength in Angström of
Mo-Kβ2
199
SCROLL BOX: List of data and results
INT ⋅ ABS
SENS = (1)
W / W FRAC
SENS
EFF − EXP = (2)
Averagegeometrical factor ⋅ K ′ ⋅ ( EFF − EXP) max imum
SEN − CAL = K ′ ⋅ Averagegeometrical factor ⋅ EFF − REL (3)
SEN − CAL
I PURE = (4)
ABS PURE
Explanation of the column headings:
ABS Absorption correction factor

INT Intensity in (cps)
W/W FRAC Concentration, normalized to 1
SENS Experimental sensitivity
U0 Mass attenuation coefficient for primary radiation
U1 Mass attenuation coefficient for fluorescence radiation
EFF-EXP Relative Detector efficiency, normalized to the element with the highest of all
values.
EFF-CAL Relative Detector efficiency - calculated with data as entered in FORM Enter
experimental parameters + absorption by air. Normalized to the same
element.
EFF-REL Relative Detector efficiency - calculated with data as entered in FORM Enter
experimental parameters + absorption by air. Not normalized
K´ Product of fundamental parameters, see refs. /TAN85/, /TAN86/
GEO-FAC Geometrical factor
SEN-CAL Calculated sensitivity
ABS PURE Absorption correction factor for a thick sample consisting only of a single
element
I PURE Intensity for a thick sample consisting only of a single element
200
Structure of a *.SEN file (TEST4K.SEN)
air path: 0.45 cm
$DATA-CAL:
4.500001E-01
8.000000E-04 distance detector crystall -
5.000000E-06
2.000000E-06
Be window
3.000000E-01
5.000000E-01
$TITLE:
Demonstration
number of K standards
$SENS_EXP:
11
20 3.690000 39273.720000 1698.191000 162.227200
22 4.508000 71704.600000 3100.498000 379.300000
26 6.398000 176988.000000 7652.941000 1175.600000
27 6.924000 221343.800000 9570.881000 1534.500000
28 7.471000 275560.000000 11915.180000 1857.400000
29 8.040000 309130.200000 13366.750000 2217.800000
30 8.630000 388286.500000 16789.460000 2688.200000
39 14.931000 911331.600000 39405.870000 5539.356000
16 2.307000 6814.468000 294.656800 17.700000
16 2.307000 7006.967000 302.980400 18.200000
17 2.621000 11425.530000 494.038500 35.226700
$EX_COND:
1
$DATE:
1.414214 1.414214 count rate for pure,
01/22/95• thick standard
$ANODE:
Ag
1 / sinθ1
$TARGET:
Mo standard deviation
$KILVOL :
45
$MILAMP:
5• sensitivity
$AVE_ENER: weighted average
17.838970
$SENS_CAL: Mo-Kα, Kβ energy characteristic energy
24
16 7240.862000 313.094000 18.807520
17 12127.710000 524.400800 37.391640
18 16629.840000 719.072200 62.409230
19 26513.710000 1146.450000 100.732200
20 37307.340000 1613.165000 154.104700
21 50238.250000 2172.296000 238.710300
22 66073.220000 2856.998000 349.511400
23 83894.390000 3627.583000 492.687900
24 111455.500000 4819.324000 693.486600
25 136886.500000 5918.955000 913.776200
26 181313.300000 7839.967000 1204.330000
27 217830.800000 9418.979000 1510.146000
28 274567.300000 11872.250000 1850.709000
29 309015.500000 13361.790000 2216.977000
30 374552.800000 16195.620000 2593.118000
31 410562.200000 17752.660000 3009.988000
32 460720.600000 19921.500000 3371.412000
33 527128.800000 22792.980000 3766.847000
34 575829.600000 24898.800000 4124.848000
35 635851.900000 27494.160000 4408.561000
36 0.000000E+00 0.000000E+00 calculated count rate
37
38
757372.300000
823590.800000
32748.690000
35611.960000
5074.610000
5402.189000 for pure, thick standard
39 931617.100000 40283.010000 5662.658000
$GEO-FAC:
19877.850000 standard deviation
Average geometrical calculated sensitivity
factor
201
Structure of a *.STD file
sample type:
1- elemental system
2 - oxid system
3 - fused disk
total number of
elements
$SAMPLE:
3
$STDAT: number of atoms of the
6
25, 1, .0020, .0460, .00000000, 1, 0 element of interest
26, 1, 1.9980, .0820, .00084987, 2, 3
28, 1, 1.3740, .1000, .00159976, 1, 0 number of
29, 1, 1035.3680, 1.4480, .62690600, 1, 0 oxygen atoms
30, 1, 811.8560, 1.3240, .36894470, 1, 0
82, 2, 1.2180, .0440, .00169975, 1, 0
concentration
standard
deviation for
count rate count rate
Indicator for
atomic number K-line: 1 , L-line: 2
202
Structure of a *.CAL file (TEST2.CAL)
$EXP_COND:
0
12-29-1994
1 / sinθ2 secondary target
0 1 description
}
Mo secondary target
45.0 45.0 1.4142 1.4142
17.441 total number of
45.00 0.00
$STAND: standards
25
1 fluorescing element,
C:\AXIL\SPECT\SD0006.ASR
4 low-Z elements
Target
10-27-1993 m/F
1 4 0
200 5.00 4.1230E-001 information read from
58 2 2337 19 4.838
4.0820E-002 5.0000E+000 Ce
1.24 21 SD0006.ASR
9.2600E-003 H
1.5700E-001 C
4.4550E-001 O Ce: conc. = 4.082%
3.4740E-001 Na 5% rel. standard
deviation (default)
C:\AXIL\SPECT\SD0007.ASR
Target
10-27-1993 concentration of other
≈ elements
$EXP_SENS:
25
14 1 7.030E+002 5.116E+001
Sensitivity = 703 for Si
16 1 1.259E+003 6.335E+001 K-lines (for definition
16 1 1.295E+003 6.501E+001
17 1 2.184E+003 1.099E+002 standard deviation see chapter 2.2. of
≈ sensitivity Elemental sensitivities).
82 2 6.112E+004 3.064E+003
92 2 8.675E+004 4.349E+003
$CAL_SENS: total number of available
82
12 1 5.450E+002 2.018E+001 sensitivities
13 1 5.458E+002 2.021E+001
14 1 6.442E+002 2.385E+001
15 1 8.850E+002 3.276E+001 fitted sensitivity for
16 1 1.343E+003 4.974E+001
17 1 2.110E+003 7.810E+001 uranium L-lines = 88,650
≈
92 2 8.865E+004 3.518E+003
93 2 2.788E+004 1.106E+003
203
204
205
Appendix 7
206
207
Spectrum format conversion utilities
SOURCE FORMATS
Name File Extension Default Directory Conversion Program

APTEC *.S0 \APTEC APT1_SPE.EXE
APTEC Version 4.3 *.S0 \WINDOWS\APTEC APT_SPE.EXE
ASCII *.* \DATA ASC_SPE.SPE
CANBERRA S100 MCA *.MCA \WINDOWS\S100 S100_SPE.EXE
Card
CANBERRA Genie PC *.RPT GRPT_SPE.EXE
(RPT)
IAEA Ganaas *.SPE \GANAAS\SPECT SPE_SPE
IAEA Qxas *.SPE \AXIL\SPECT SPE_SPE
NUCLEAR DATA *.DAT \ND ACS_SPE.EXE
AccuSpec
NUCLEUS PCA *.SPM \NUCLEUS PCA_SPE.EXE
NUCLEUS/OXFORD *.SPT \PCAIII SPT_SPE.EXE
PCAIII *.CHN \ORTEC ACE_SPE.EXE
ORTEC ACE
SILENA EMCAplus *.DAT \SILGAMMA SIL_SPE.EXE
SILENA *.DAT \SILGAMMA SIL1_SPE.EXE
TRACOR (Spectrace 5000) SPECTRUM.* \EDXRF TRAC_SPE.EXE
TARGET FORMATS
Name File Extension Default Directory Conversion Program
ASCII *.ASC \DATA SPE_ASC.EXE

IAEA Qxas *.SPE \AXIL\SPECT SPE_SPE.EXE
208
209
Table: Standards
*.spe file Aerial density in Concentration of Other elements of compound/binder
Element- (g/cm2) element of concentration in %
line of compound interest in %
interest
SD0004 thick 100
Ag-L
SD0005 thick 100
Sn-L
SD0006 0.4123 4.082 H C O Na
Ce-L Ce2O+binder 0.926 15.696 44.551 34.745
SD0007 0.4042 4.458 H C O Na
Sm-L Sm2O3+binder 0.933 15.714 44.264 34.631
SD0008 0.4032 4.455 H C O Na
Dy-L Dy2O3+binder 0.954 15.833 44.25 34.508
SD0009 thick 100
Ta-L
SD0010 thick 100
W-L
SD0011 0.3389 42.391 H C O S
Hg-L HgSO4+binder 2.319 16.582 31.932 6.776
SD0012 thick 100
Pb-L
SD0013 0.2345 10.724 H C O
U-L U3O8+binder 5.43 38.824 45.021
SD0016 0.4579 40.044 C O
Ca-K CaCO3 12.0 47.956
SD0017 thick 100
Ti-K
SD0018 thick 100
Fe-K
SD0019 thick 100
Co-K
SD0020 thick 100
Ni-K
SD0021 thick 100
Cu-K
SD0022 thick 100
Zn-K
SD0023 0.2049 62.983 H C O
As-K As2O3 +binder 1.047 7.484 28.486
SD0026 0.2406 19.602 H C O Na
Y-K Y2O3+binder 1.569 16.867 40.327 21.636
SD0028 1.1588 100
S-K
SD0029 0.4886 100
S-K
SD0030 0.2211 46.747 O
Si-K SiO2 53.253
SD0031 0.2294 60.664 Na
Cl-K NaCl 39.336
SD0032 0.2065 33.17 H C O
Ca-K CaCO3+binder 1.067 17.569 48.194
SD0033 0.3934 5.825 H C O Na
210
Sr-K SrCO3+binder 1.246 17.654 44.844 30.43
211
Reference sheet for SOIL 7
212
References
/BER94/ G.Bernasconi, S.A.Bamford, B.Dosan, N.Haselberger, A.Markowicz,
A.Mahmoud and V.Valkovic - “Applicability of annular-source excited
systems in quantitative XRF analysis”, X-ray spectrometry 23, 65 (1994).
/BOE90/ D.K.G.deBoer - “Calculation of X-ray fluorescence intensities from bulk
and multilayer samples”, X-ray spectrometry 19, 145 (1990).
/ESP02/ P.VanEspen - “Spectrum evaluation”, Chapter 4 in Handbook of X-ray
Spectrometry, edited by R.E.VanGrieken and A.A.Markowicz, published by
M.Dekker, Inc. (2002).
/HE91/ F.He - “A generalized approach to quantitative EDXRF analysis using
Fundamental parameters”, Ph.D. Thesis, department of chemistry, University
of Antwerp (UIA), B-2610 Wilrijk, Belgium (1991).
/HUB75/ J.H.Hubbell, W.J.Veigele, E.A.Briggs, R.T.Brown, D.T.Cromer and
R.J.Howerton - “Atomic form factors, incoherent scattering functions, and
photon scattering cross sections”, J.Phys. Chem. Ref. Data 4, 471 (1975).
/KRA79/ M.O.Krause - “Atomic radiative and radiationless yields for the K and L
shells”, J. Phys.Chem. Ref. Data 8, 307 (1979).
/KRE91/ P.Kregsamer - “Fundamentals of total reflection XRF”, Specrochimica Acta
46B, 1333 (1991).
/LAC95/ G. R. Lachance and F. Claisse - “Quantitative X-ray Fluorescence Analysis”
pp 125-130 and 144-146, Published by John Wiley & Sons (1995).
/MAR63/ D.W.Marquardt - “An algorithm for least-square estimation of nonlinear
parameters”, J.Soc. Ind. Appl.Math.11, 431 (1963).
/MAR02/ A.A.Markowicz and R.E.VanGrieken - “Quantification in XRF analysis of
intermediate-thickness samples”, Chapter 6 in Handbook of X-ray
Spectrometry, edited by R.E.VanGrieken and A.A.Markowicz, published by
M.Dekker, Inc. (2002).
/MAS68/ W.H.McMaster, N.K.Delgrand, J.H.Mallet and J.H.Hubbell - “Compilation of
X-ray cross sections”, UCRL report 50174, Lawrence Livermore lab,
University of California, USA (1968).
/PEL85/ P.A.Pella, L.Y.Feng and J.A.Small - “An analytical algorithm for calculation
of spectral distributions of X-ray tubes for quantitative XRF analysis”, X-ray
Spectrometry 14, 125 (1985).
/RAN89/ A.Rani, N.Nath and S.N.Chaturvedi - “Effect of Coster-Kronig transitions on
L3 sub-shell XRF cross sections”, X-ray Spectrometry 18, 77 (1989).
/KRE02/ P.Kregsamer, Ch.Streli and P.Wobrauschek - “Total reflection XRF”, Chapter
9 in Handbook of X-ray Spectrometry, edited by R.E.VanGrieken and
A.A.Markowicz, published by M.Dekker, Inc. (2002).
/SCO74A/ J.A.Scofield - “Exchange corrections of K X-ray emission rates”, Phys.Rev.A
9, 1041 (1974).
/SCO74B/ J.A.Scofield - “Hartree-Fock values of L X-ray emission rates”, Phys.Rev.A
10, 1507 (1974).
/TAN85/ S.M.Tang, P.Kump, C.T.Yap and M.G.Bilal - “An XRF method for the
determination of the efficiency of Si(Li) detectors in an extended-source
geometry by using thick specimens”, Nucl. Instr. and Meth. A 241, 503
(1985).
213
/TAN86/ S.M.Tang, P.Kump, C.T.Yap and M.G.Bilal - “Calculation of relative XRF
intensity for annular-source geometry by the Monte Carlo method”, X-ray
spectrometry 15, 289 (1986).
/TAO85/ G.Y.Tao, P.A.Pella and R.M.Rousseau - “NBSGSC, a FORTRAN program for
quantitative X-ray spectrometric analysis using X-ray tube excitation”, NBS
technical note 1213, NIST, Washington DC., USA (1985).
/THI79/ T.P.Thinh and J.Leroux - “New basic empirical expression for computing
tables of X-ray mass attenuation coefficients”, X-ray Spectrometry 8, 85
(1979).
/WEG03A/ D.Wegrzynek, A.Markowicz, E.Chinea-Cano and S.Bamford- “Evaluation of
the uncertainty of element determination using the energy-dispersive x-ray
fluorescence technique and the emission-transmission method”, X-ray
spectrometry 32, 317 (2003).
/WEG03B/ D.Wegrzynek, A.Markowicz and E.Chinea-Cano - “Application of the
backscatter fundamental parameter method for in situ element determination
using a portable energy-dispersive x-ray fluorescence spectrometer”, X-ray
spectrometry 32 (2003).
/WOB89/ P.Wobrauschek - “Adjustment and working instructions for the totalreflection
attachment module (IAEA TXRF module)”, Internal report, Atominstitut der
Österreichischen Universitäten, 1020 Wien, Austria (1989).
214

QXAS Manual

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

QXAS Manual

Uploaded by

Copyright:

Available Formats

QXAS

Quantitative X-ray Analysis System

Documentation Version 2.0 (2005)

Any queries, comments, or suggestions for improvement may be directed to:

DIRECT COMPARISON OF COUNT RATES.............................................................................................. 56

FUNDAMENTAL PARAMETERS’ TABLES.............................................................................................. 138

CALCULATION OF AVERAGE ATOMIC NUMBER .............................................................................. 140

SPECTRAL DISTRIBUTION OF X-RAY TUBES...................................................................................... 142

ABSORPTION COEFFICIENTS, ABSORPTION CORRECTIONS........................................................ 144

INCIDENT – AND TAKE-OFF ANGLES, GEOMETRY CONSTANTS, *.SEN FILE........................... 146

THEORY OF NON-LINEAR FUNCTION FITTING ................................................................................. 156

THEORY OF THE EMISSION TRANSMISSION METHOD ................................................................... 168

APPENDIX 3 .................................................................................................................................................... 170

THEORY OF THE ALPHA COEFFICIENTS METHOD .......................................................................... 172

APPENDIX 4 .................................................................................................................................................... 174

THEORY OF THE FULL FUNDAMENTAL PARAMETERS METHOD............................................... 176

USER INTERFACE......................................................................................................................................... 184

STRUCTURE OF FILES ................................................................................................................................ 192

SPECTRUM FORMAT CONVERSION UTILITIES.................................................................................. 208

TABLE: STANDARDS.................................................................................................................................... 210

REFERENCE SHEET FOR SOIL 7 .............................................................................................................. 212

REFERENCES ................................................................................................................................................. 213

1. Introduction to the Spectrum Fitting (AXIL)

Table of File types

File Name File type File contents

SPE Spectrum Spectral data in AXIL standard format

2. Introduction to the Quantitative METHODs

3. Description of the main MENU

No files (*.xxx) found;

1995-96 Documentation of QXAS and implementation of the XPARAM library as a

Early 1990’s New Emission Transmission method ET-10 implemented by N. Haselberger.

1997 Voigt peak profile option for peak fitting written.

1999 Backscatter Fundamental Parameters method for source excitation developed.

2005 Revision of the documentation and rearrangement of the QXAS package.

From the Internet under the IAEA home page with

and the SET command that is included (in a new line).

Node: @<parent node> <actual node> <menu title/item>

Leaf: @<parent node> <actual node> <menu item> <program>

1. System hardware setup

1.1 Selection of graphics adapter and other hardware

1.2 Selection of communication parameters.

from the desktop.

1. Select format of spectrum to be converted from (source).

After starting the program, a full screen will be displayed.

Using table: C:\AXIL\BIN\SPEDAC.TAB

A frame labeled "Select SOURCE files" is displayed.

The next form sets the target directory.

The next form is displayed as shown below

The next line of the FORM holds three fields:

Copying from channel 0 to 1023 Squeezing factor 1

The final dialog determines the action to be taken.

Menu item Task

1. X-ray library management Edit or select *.XRL file

An overview of the commands is shown below. A detailed description can be found in

Overview of commands for Analyze Spectra

1.1. LOAD (*) Select *.SPE file,

1.1 MENU Load

1.2 Calibration (MENU Calib)

Overview of CALIB commands

CALIB ZERO=number Set energy of channel 0 (eV)

Example: CALIB ZERO=0 GAIN=20 NOISE=120 FANO_F=0.114

CALIB keyboard functions

1.1. LOAD () Select .SPE file,