X-ray Fluorescence #2

Matrix Effect Corrections

X-ray fluorescence analysis is typically subject to severe matrix effects. This effect arises
because the rest of the sample (matrix) affects the analyte signal. One cause of this effect is the
fact that the fluorescent photons from the analyte can be absorbed by the atoms in the matrix and
the extent of this absorption is dependent upon the matrix composition. Evidence for the
presence of a matrix effect can include a nonlinear calibration curve.

In this experiment you will examine the matrix effects for one element in two different matrices.
You will also attempt to correct for the matrix effect by mathematically compensating for the
matrix composition.

You will use the binary mixtures assigned to your group as the standards in setting up methods for the
measurement of an element using the empirical assay mode. You will set up two methods, both for the
measurement of your analyte element and specific to the matrix element. Note that you will need count
data from both elements in all the standards so enter assays for both elements. Follow the directions in
section 14.0E (provided separately) of the instrument manual.

Use a 180 sec test time for each standard.

Use the following parameters when creating the calibration curves: Fit type = linear, Background = Raw
Rates.

When viewing the curve for each element, click on each point and record counts data for each standard.

Note that the analysis time for this lab is short, but the data analysis is relatively extensive. It is suggested
that you start the data analysis during the lab period the data is collected.

The data analysis required will be illustrated using an example from the analyses of binary mixtures of
elements A & B. You will follow this procedure for both of your matrix specific calibrations.

1
The raw data:

%A Counts (A) Counts (B)

0.00 52.909 6798.224
25.40 6326.923 3603.646
50.07 9427.112 1798.282
75.10 11889.312 608.452
100.00 13383.743 8.112

and the corresponding plot for element A:

The nonlinear plot is evidence that the response factor of A is changing as a function of concentration.
That is, the signal measured per %A changes as the total % of A changes.

%A %A/Counts(A)
25.40232 0.004014957
50.07245 0.005311537
75.1026 0.006316816
100 0.007471751

A plot of this data is then made:

2
 0.008
"Response Factor of A" vs. %A
0.007

0.006

0.005

0.004

0.003

0.002

0.001

0
0 20 40 60 80 100

While the response factor is not constant, it does appear to be well behaved; the response factor is directly
proportional to the %A of the standards. Notice that since the y-axis is the response factor of A it is not
appropriate to include any standards which contain 0% A.

Since we are dealing with a binary mixture (only elements A & B are present) it can be shown that
𝐼𝐴 (𝑠𝑎𝑚𝑝𝑙𝑒)
𝐶𝐴 (𝑠𝑎𝑚𝑝𝑙𝑒) = ( 1 + 𝐾𝐴𝐵 𝐼𝐵 ) (1)
𝑚𝐴

where CA(sample) is the concentration of A in the sample

IA(sample) is the intensity of the signal due to A in the sample

mA is a factor equal to IA(100% A)/100%

KAB is influence factor

IB is is the intensity of the signal due to B in the sample

Equation (1) can be rearranged:

𝐶𝐴 (𝑠𝑎𝑚𝑝𝑙𝑒)∗ 𝑚𝐴
= 1 + 𝐾𝐴𝐵 𝐼𝐵 (2)
𝐼𝐴 (𝑠𝑎𝑚𝑝𝑙𝑒)

From this it can be seen that a plot of the left hand side of the equation vs. IB should yield a straight line
with a slope of KAB.

Using the data above:

3
 m(A)= 133.83743 cps/% from 100% A
C(A) I(A) [C(A)m(A)]/I(A)
0.00 52.909 0.00000
25.40 6326.923 0.53735
50.07 9427.112 0.71088
75.10 11889.312 0.84543
100.00 13383.743 1.00000

Points to be plotted, note that 0% A data is not included

I(B) [C(A)m(A)]/I(A)
3603.646 0.537351484
1798.282 0.710882436
608.452 0.845426414
8.112 1

The resulting plot where slope = KAB

[C(A)m(A)]/I(A)
1.2
y = -0.000121767x + 0.9776
1

0.8

0.6

0.4

0.2

0
0 500 1000 1500 2000 2500 3000 3500 4000

The influence factor (KAB) determined from the slope of the plot can be used to correct the intensities of
the standards to account for the matrix effect that element B has on element A.

IA(corrected) = I(A) * [1 + KAB * IB] (3)

4
 I(A) I(B) Corrected I(A)
52.909 6798.224 2.559411599
6326.923 3603.646 3135.344197
9427.112 1798.282 7054.059399
11889.31 608.452 10876.67464
13383.74 8.112 13368.54535

Plotting the corrected intensities vs. the standard concentrations yields a linear calibration curve:

Corrected A Calibration Curve

16000
14000
12000
10000
I(A) corrected

8000
6000
4000
2000
0
-2000 0.00 20.00 40.00 60.00 80.00 100.00
%A

Lab Report

Lab Report

For this experiment the lab report will consist of the following parts:

Title

Abstract (Rubric Row 1)

Introduction (Rubric Rows 2 & 3)

Purpose (Rubric Row 4)

Experimental (Rubric Row 6)

5
Results (Rubric Rows 7 & 8) – Data shall include tables listing concentration and X-ray count data for
standards run, this should include the concentration and X-ray counts data for both elements. Results
should include the following plots for both sets of standards: (1) analyte counts vs. analyte concentration
(2) analyte response factor vs. analyte concentration (3) plot used to determine K AB (4) corrected analyte
calibration curve.

Discussion (Rubric Row 10 & 11)

Conclusion (Row 12) State a hypothesis in response to this question at the conclusion of your report:
What is giving rise to the matrix effect, in other words why does the signal from a given wt% of your
analyte element also depend upon the identity and wt% of the matrix element? Answer this question
specifically for your analyte element.

References (Rubric Row 14)

Sample Calculation (Rubric Row 15) These can be included in your results and/or discussion section or in
an appendix.

Rubric Rows 16 & 17 apply throughout.