GEOL-4700/5700 Summer 2015

Lecture 14: Statistics

Accuracy & precision
Counting statistics
Detection limit (sensitivity)

14 1

X-Ray Microanalysis Precision and Sensitivity

Recall
K-ratio Element = [IElement)in)unknown)/)IElement)in)std.])x)CF

CF relates concentration in std to pure element

K x 100 = uncorrected wt.%, and
K x (ZAF) x 100 = corrected wt.%

Precision, Accuracy and Sensitivity (detection limits)

Precision:

- Reproducibility
- Analytical scatter due to nature of X-ray measurement
process

Accuracy:

- Is the result correct?

Sensitivity: - How low a concentration can you expect to see?

14 2

Accuracy and Precision

14 3

Accuracy and Precision

Measured
value
Std
error

20

25

Avg

Standard
deviation

Avg

30

35

Correct value
Wt.% Fe

Low precision, but

relatively accurate

20

Std
error

25

30

35

Correct value
Wt.% Fe

High precision, but low

accuracy
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Accuracy and Precision

Measured
value
Std
error

20

25

Avg

Standard
deviation

Avg

30

35

Correct value
Wt.% Fe

Low precision, but

relatively accurate

20

Std
error

25

30

35

Correct value
Wt.% Fe

Precise and accurate

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Characterizing Error
What are the basic components of error?
1) Short-term random error (data set)
Counting statistics
Instrument noise
Surface imperfections
Deviations from ideal homogeneity

2) Short-term systematic error (session to session)

Background estimation
Calibration
Variation in coating

3) Long-term systematic error (overall systematic errors that are

reproducible session-to-session)
Standards
Physical constants
Matrix correction and Interference algorithms
Dead time, current measurement, etc.
14 6

Short-Term Random Error - Basic assessment of counting statistics

X-ray production is random in time, and results in a fixed mean value follows
Poisson statistics
At high count rates, count distribution follows a normal (Gaussian) distribution

Frequency
of X-ray
counts

Counts

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The standard deviation is:

theoretical = N
99.7% of area
95.4% of area
68.3% of area

14 8

Variation in percentage of total counts

= 100 N / N = 100( theoretical / N )

6
5.5

So to obtain a result to 1% precision,

must collect at least 10,000 counts.

1-sigma error %

4.5

and for 0.5% precision, must collect

around 40,000 counts.

4
3.5

and for 0.1% precision = 1,000,000!

3
2.5
2
1.5
1
0.5
0
0

10000

20000

30000

40000

50000

60000

70000

80000

90000 100000

Counts
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Evaluation of count statistics for an analysis must take into account the
variation in all acquired intensities
Peak (sample and standard)
Background (sample and standard)
And errors propagated
Addition and subtraction

2
A

C = +
Multiplication and division

2
A

C = +

2
B
Relative std. deviation

2
B

C =
x

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Abbreviations used in the following

cps = counts per second

cps/nA = count per second per nanoamp

Current from the Faraday cup

tp

Counting time of the peak (p)

r+, r

Positive and negative offsets for the background measurement,

relative to the peak position
t = t + t+

tb

Total counting time on background

P(n)

Peak counts (for n-th measurement)

B(n)

Background counts:
- For n-th measurement;
- Assume LINEAR background.

Cs

Element concentration in the standard

Is

Intensity (Peak-background) in cps/nA of the element in the standard

Ce

Element concentration in the sample

Ie

Intensity (Peak-background) in cps/nA of the element in the sample

np, nb

Index of measurement on the peak and on the background

(B+r B r + )
B=
r r+

np_max, nb_max Total number of measurements on the peak and on the background
14 11

Mean and standard deviation for a series of

n measurements on STANDARD

(I )

s n

For the calibration

Mean =

np

n p _max

Sum of the
intensities divided
by the number of
measurement

1/2

#
2&
(P

P
+
B)
n
n
%
(
n p _max 1
%$ n p
('
measure =
it p

And standard deviation

NOTE: Pn, Bn = individual n-th measurement

P, B = average of n-th measurements

Values are normalized to

time (tp) and current (i)!
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Measured standard deviation

The larger of the two

represents the useful
error on the standard
calibration:

1/2

#
2&
(P

P
+
B)
n
% n
(
n p _max 1
%$ n p
('
measure =
it p

2s = max((measure)2,
(theoretical)2)

compared to
Theoretical standard deviation

theoretical =

"
$ 1
$ n p _max
#

% "
Pn ' $ 1
(t ) ' + $ n
p n &
np
# b _max
i

%
Bn '
(t ) '
b n &
nb

Theo.Dev(%) = 100 * theoretical/Is

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Mean and standard deviation for a series of

n measurements on SAMPLE
The intensity on the sample is

" P
%
B
n
n

$
$ (t ) (t ) ''
b n&
1 # p n
Ie =
in nmax
nmax

Or, in the case of a

single measurement
Pk Bkg [cps/nA]

nmax

For the sample, the variance for the

intensity can be estimated as
2
Ie

= nmax

(t p )n in
1

+ nmax

(tb )n in
1

N.b.: standard deviation = square root of variance

or (standard deviation)2 = variance

With

Pn
(t ) i
e = 1 p n n
n p _max
nmax

Bn
(t ) i
e = 1 b n n
nb _max

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The TOTAL count statistical error is then (3)

Ce

! Ce $ 2 ! I e $ 2
= 3# & I e + # & I s
" Ie %
" Is %

Standard deviation
from SAMPLE
concentration

Standard deviation
from SAMPLE
measurement
(counts)

Standard deviation
from STANDARD
measurement
(counts)

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An example of calibration
Point

Th Ma
(cps/nA)

154.6281

155.3082

154.8897

154.8656

156.4651

155.6509

156.8881

155.5401

154.8923

10

154.8614

Complete statistics given by

software (e.g. Cameca PeakSight)
X-Ray Th Ma
Pk-Bg Mean (cps/nA)
Std.Dev (%)

0.372

Theo.Dev (%)

0.136

3 Sigma (Wt%)

0.563

Pk Mean (cps)

3119.686

Bg Mean (cps)

34.455

Raw cts Mean (cts)

61657

Beam (nA)

19.87

SD measure

Average,
omitting #7

155.2335

156$

SD

0.5772

155$

SD%

0.3718

154$

155.2335

0.5775

157$

0$

2$

4$

6$

8$

10$

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An example of sample analysis

Sample Th data @ ~200 nA
Wt%

Current

Peak cps

Peak t (sec) Bkg cps

Pk-bkg cps

6.4992

200.35 nA

4098.57

800

3813.483

285.0897

Ie (net intensity for sample)

19.0337

e (peak int)

20.4567

e (bkg int)

1.4229

2e (sample variance)

0.000137

Is (net intensity for std)

155.2335

2s (std variance)

0.3335

0.0735
e (~ 0.39%)
This is a very precise number
Error on the
concentration
(including std)

Ce

! 6.50 $
! 19.03 $
2
2
= 3#
& (0.0735) + #
& (0.578) = 0.105
" 19.03 %
" 155.23 %

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Sensitivity and Detection Limits

Ability to distinguish two concentrations that are nearly equal (C and C );
95% confidence approximated by:

2.33 $ C '
C = C C '
&
)
n % N NB (

N Average counts
NB Average
background counts
n Number of analysis
points

Actual standard deviation ~ 2C, so C about 2x above equation

If N)>>)NB, then

2.33
C = C C '
nN

Sensitivity in % is then

Ziebold (1967)

2.33
C / C(%) =
x100
nN
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To achieve 1% sensitivity, must accumulate at least 54,290 counts.

As concentration decreases, must increase count time to maintain precision.

Wt% Ni

Example gradient:

1%
0

distance (microns)

25

If take 1 micron steps

o gradient = 0.04 wt.% / step
o Sensitivity at 95% confidence must be 0.04 wt.%
o Must accumulate 85,000 counts / step
If take 2.5 micron steps
o Gradient = 0.1 wt.% / step
o Must accumulate 13,600 counts / step
! So can cut count time by 6x
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Detection Limits
At low concentration N is no longer much larger than NB (rather N NB)
What value of N-NB can be measured with statistical significance?

Liebhafsky limit:
Element is present if counts exceed 3x precision of background: N > 3(NB)1/2

Ziebold approximation:

CDL

3.29a
=
P
nt p P
B

tp = measurement time
n = # of repetitions of each measurement
P = pure element count rate
B = background count rate on pure element
a = relates composition to intensity

14 20

Or

CDL

3.29(wt%)
=
I P (t pi) / I B

IP = peak intensity
IB = background intensity
tp = acquisition time
i = current

Ave Z = 79

Ave Z = 14

Ave Z = 14,
4X counts as b

14 21

Detection limit & counts

You can decrease the detection limit by increasing the total number of counts!
Several options to increase the number of counts:
Change the acceleration voltage to reach an optimum, both in term of
spatial resolution (volume increase with increasing voltage!) and
overvoltage (optimum usually around 2-3x);
Increase the current;
Increase the counting time;
HOWEVER, keep in mind that your sample might suffer from beam exposure, in
this case, you need to lower the energy density:
Increase the analytical volume:
o Increase the acceleration voltage (loss of depth resolution);
o Increase the beam diameter (loss of lateral resolution);
Decrease the current and/or the counting time.

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Microprobe dating of monazite

Monazite is a U-Th-bearing REE phosphate: can be dated by
measuring the quantity (NOT the isotopes!) of U, Th and Pb. This
assume no common lead (Pb present when the crystal form), which
is a reasonable assumption (typically ~2-3 ppm common Pb):

" Th 232 *t
%
Pb = $
(e
1)' * 208
# 232
&
" U
%
238 *t
+$
0.9928(e
1)' * 206
# 238
&
" U
%
235 *t
+$
0.0072(e
1)' * 207
# 235
&
+ 204 Pb

~ a few ppm in Mnz

208Pb

from 232Th

206Pb

from 238U

207Pb

from 235U

Common lead (assumed = 0)

Pb in monazite is often less than a couple thousands ppm of Pb

Age accuracy will depend on how accurate the Pb-content (and
actinide) can be measured ! TRACE element analysis
14 23

Detection limit for Pb

Pb M measured on VLPET
Can increase current and / or
count time to come up with low
detection limits and relatively
high precision

100
90
80

But is it right?

200nA, 800 sec

ppm

70
60
50
40
30
20
10
0
0

100000

200000

300000

400000

500000

current * time (nA * sec)

14 24

Accuracy

All results are approximations. Many factors

Level 1
Quality and characterization of standards
Precision
Matrix corrections
o Mass absorption coefficients
o Ionization potentials
o Backscatter coefficients
o Ionization cross sections
Dead time estimation and implementation

! Evaluate by cross
checking standards of
known composition
(secondary standards)

Level 2 inaccuracy due to sample

Inhomogeneous excitation volume
Background estimation
Change in peak position (peak shift) or change in peak shape
Polarization in anisotropic crystalline solids
Changes in (Z) shape with time

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ALL measurements include errors!

Measurement of time
Time-integral effects (*)
Measurement of current, including linearity, is a nanoamp a
nanoamp? Depends on measurement

(*) Time-integral acquisition effects

Drift in electron optics, measurement circuitry
Dynamic X-ray production
Non-steady state absorbed current / charge response in
insulating materials
o Beam damage
o Compositional and charge distribution changes
o Surface contamination

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Overall accuracy
Combined effect of all sources of variance.

T2)=)C2+I2+O2+S2+M2
T = total error
C = counting error
I = instrumental error
O = operational error
S)= specimen error
M = miscellaneous error
Each of which can consist of a number of other summed terms

Becomes more critical for more sensitive analyses

! trace element analysis

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Sources of measurement error:

Time-integral measurements and sample effects

Sample damage (especially with focus beam) can

alter the count rate! Change is apparently correlated
with abnormal behavior of the absorbed current
14 28

Sources of measurement error:

Extracting accurate intensities: peak and background measurements
Background shape depends on
Bremsstrahlung emission (background continuum)
Spectrometer efficiency

14 29

Sources of measurement error:

Background curvature, example in the Pb M region (PET crystal)
2 counting statistics
How (non-)linear is a background?

0.35
0.30

Cps / nA

0.25
0.20
0.15
0.10
0.05
0.00
54000

55000

56000

57000

58000

59000

60000

61000

62000

63000

64000

Wavelength (sin)

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Background: linear or not?

0.80

Pb-M region on GdPO4

Pb M

Intensity (cps/nA)

0.70

0.60

0.50
Gd L2 3rd order
59847
7.1 KeV

0.40

0.30

0.20
0.54

Exponential regression
y = 74.4951 e-8.465 E-05 x
0.56

0.58

0.60

0.62

0.64

Wavelength (sin)

14 31

Net intensity
(Pk Bkg)

0.2354

0.0592

Linear fit 1

0.2422

0.0524

Difference

0.0068

-0.0068

Actual bkg

% error

2.884

11.478

0.2327

0.0956

Linear fit 2

0.2426

0.0857

Difference

0.0100

-0.0100

% error

4.263

10.377

0.2498

0.1312

Linear fit 3

0.2583

0.1227

Difference

0.0085

-0.0085

% error

3.404

6.483

0.2971

0.3376

Linear fit 4

0.3047

0.3300

Difference

0.0075

-0.0075

% error

2.531

2.228

0.2637

0.2124

Linear fit 5

0.2719

0.2042

Difference

0.0082

-0.0082

% error

3.110

3.861

Actual bkg

Actual bkg

Actual bkg

Actual bkg

Background & Net Intensity:

linear vs. exponential bkg
14

Becomes 50% error at

~ 0.015 net intensity
Measured

12

% error of net intensity

Bkg

Theoretical based on run5

At ~1000ppm Pb, 10%

error can easily produce
an age error of 35-40Ma
(5 wt.% Th, 4000ppm U)

10

y = 0.679x-1

0
0.00

0.10

0.20

0.30

0.40

0.50

0.60

Net intensity (cps/nA)

14 32

Challenge of trace element analysis:

Background & peak interferences

We will come back later on the peak interference issue

14 33

Choosing the wrong background

Isotopic age: 394 Ma

Concentration (ppm)

fitted
bkg.

linear
bkg.

Th

Pb

Age (Ma)

Ave

19196

48043

1094

3984

400.2

S Std

3518

3043

119

1343

8.0

Std Err

1573

1361

53

601

3.6

Ave

19194

48007

996

3958

365.4

S Std

3519

3039

123

1340

10.1

Std Err

1574

1359

55

599

4.5

can results in an error of 10s to 100s ppm!

For U-Th-Pb dating of monazite, this can
represents 10s millions of years!
14 34