Electron probe microanalysis

EPMA

Trace Element Analysis

Mod 1/10/2016
 Whats the point?
Whats the minimum detection limit for a
particular element or said otherwise, at what
point can be be sure that a small inflection above
the surrounding background really is a peak?
What kind of confidence level should be place on
such a number?
 Definitions
Generally, WDS can achieve limits of
detection of 100 ppm in favorable cases, Major >10 wt%
with 10 ppm in ideal situations where there
are no peak interferences and negligible Minor 1-10 wt%
matrix absorption.
Trace <1 wt%
(Goldstein et al., p. 341)

No Zn ... but at what

level of confidence?
 Trace elements .... and trace elements

In the real world, the definition of trace element

analysis is sometimes broader than the strict quantitative
analysis of ppm level elements in one microvolume
(~micron interaction volume). Many individuals desire to
use EPMA to tell them about the distribution of trace
elements in their materials, e.g. where the 30 ppm of Pb is
in a cast iron. There are two possibilities: the 30 ppm is
spread uniformly throughout the material, or in fact most of
the material has probably <1 ppm of Pb, but a small
fraction of the volume has phases that have Pb at major
element levels.The question is then, are they at least the
size of the interaction volume and if so, where are they.
Our discussion here will deal with all these aspects.
 A little background-1
Interest in trace elements dove tails with the develop of
techniques that could achieve better/quicker/cheaper/more
precise/small volumes of said elements.
From the 1960s on, geochemists and petrologists
developed increasing interest in trace element partitioning
between fluids/melts and minerals. The electron microprobe
became the instrument of choice for characterizing the trace
levels in doped experiments .
There has been an interest in trace elements in certain
minerals to assist in the search for ore bodies that contain
said elements. A related research field is locating the
naturally-occurring minerals that are responsible for certain
levels of groundwater contamination (e.g. As).
 A little background-2
Also
In both material science and geology, diffusion processes
are studied, and EPMA is a prime technique. As you go
further and further from the boundary between the two
phases, the elements drop to trace element levels. But where
do they drop below detection? Or how do you set up the
EPMA conditions to reach down to a desired very low level?
 How low can we go?

The USNM olivine standard above (San Carlos, Mg.9 Fe.1SiO4) has a
published Ca content of <0.04 wt% (= 400 ppm).
This scan was acquired at 20 keV, 30 nA, with 10 seconds per channel.
Clearly there is a peak at the Ca Ka position (24 cps), somewhat above
the background (~10 cps). At what point can we say with 99%
confidence that there is a statistically significant peak?
 MDL Equations - 1
The key concept here is minimum detection limit (MDL), i.e., what is the
lowest concentration of the element present that is statistically above the
background continuum level by 3 sigma (commonly accepted level).
There are (at least) two equations used to define the MDL:
the first* uses the Student t test values: a
CS 21/ 2 (t 1-
n-1 )SC
CMDL =
N S - NSB n1/ 2
where the detection limit CMDL is in wt%, CS=std wt %, bar NS=ave. peak
cts on std, bar NSB=bkg cts on std, SC= std dev of measured values and
n=number of data points
the second, which is probably more wider used, was developed by
Ziebold (1967): (3.29) a
CMDL =
(nTP PB )
1/ 2

where n=number of measurements, T=seconds per measurement, P=pure

element count rate, P/B= for pure element, and a=matrix correction (a -
factor or ZAF).
* Goldstein et al., p. 500, equation 9.84 Goldstein et al., p. 500, equation 9.85
 MDL Equations - 2
There are several points to be made about these two equations:
the first (Student t test) equation only works for the average of several
measurements, since it uses SC, the average of several measurement. This
calculation is useful in that special case.
however, as many times as not, a specific area or region is only measured
once (e.g., a linear traverse across a zoned crystal), and the second
equation is the appropriate one to use.
note in the second equation, the term P times P/B appears in the
denominator. As P2/B increases, the MDL decreases (the lower, the
better!). This P2/B term is called the figure of merit for trace element
work.
following some discussions with John Valley about the traditional
(second) equation and how the peak and background used in it were from
the pure element standardnot the unknown, I went back to first
principles and derived the equation.
 Deriving the MDL equation-1
1. We need to determine the precision of the background value for the
unknown, i.e. for a given background value, how big is the statistical error
bar (counting statistic, 3 sigmas) above it. So here, is it large as on the right
below, or is it small as on the LEFT?
 Deriving the MDL equation-2

2. Let us consider Ca Ka peak on our olivine. We measure the background

and get 9 cts/sec. The 1 sigma value however is calculated from TOTAL
counts, NOT count rate. So we must multiply 9 cts/sec by the time, 10
seconds, and we get 90 counts. 1s=Sq.Rt. of 90 =9.5 counts, so 3s =28.5.
Well use 3 s for now, the 99.7% confidence level. Ergo, our MDL for Ca in
the olivine is 29 counts above background, over 10 seconds (or if plotted on
the wavescan where data are in cts/sec, it would be a value of 3 cps (the left
purple marker).
Note: we havent said one word about count rate on a standard, and we have
figured out the minimum detection limit for Ca in our unknown -- though we
dont know what that mdl of 3 cts/sec translates to in ppm or wt%).
 Deriving the MDL equation-3
3. However, we usually want to translate those raw counts into a more
usable number, i.e. so many ppm. For that, we need some reference
intensity counts for Ca Ka. We then count Ca ka peak and backgrounds for
the same time (10 sec) on CaSiO3 (38.6 wt% Ca) and find a count rate of
6415 cts/sec on the peak and 16 cts/sec on the background.
4. So what is 2.9 cts/sec equal to in elemental wt%? We create a pseudo k-
ratio where we take the statistical uncertainty of the background counts
(square root, i.e. 1 sigma) divided by the Peak-Bkg of the standard counts
on the element peak of interest

bkgcts unk
Ca ZAFCunk std
KCa-mdl = 3 std a
std CCa
(pkcts - bkgcts)C a ZAFC a
and multiply by 3 (for 3 sigma, 99% confidence) and the ZAF of each and
then by the composition C of the standard.The mdl will be in whatever
units C is in.
 Deriving the MDL equation-4
ol
ZAFC a = 1.1087
a = 1.080
ZAFCstd

ol90 1.1087
MDL = 3 Ca 38.6 = .017wt%Ca
66250 1.080

This is virtually the same result as the single line detection limit provided by
Probe for Windows (0.015 wt%, shown on next slide), derived from the Ziebold
equation.
It would appear that the Ziebold equation is not exactly correct, for we must
really be concerned with the background precision of the unknown, and the
background level of the standard could be several times higher or lower. Going
back and re-reading Ziebold, we find two interesting statements: that the
equation gives a measure of the detectability limit and there is more than one
way to define a detectability limit. Both are correct, and yes, the equation gives
an approximation of the detection limit -- but not the limit per se.
MDL in olivine - single line

Good totals

Excellent
stoichometry

These are the single line

detection limits, calculated
with Ziebolds equation
(Goldstein, eq 9.85, p. 500)
MDL in olivine - average
For a homogeneous sample, it is legal to
add together all the counts, which gives
greater precision and a lower detection
limit, e.g. 110 ppm here for Ca at 99% ci.

This is a handy chart that shows what kind

of counting time would be required, under
the same analytical conditions, to achieve a
lower detection limit. For example, to get a
mdl of 25 ppm, youd need to count for ~5
minutes on the Ca peak and then
background (for each of 10 spots). The
current analysis here was a little over 1
minute per spot (thus, about 12 minutes for
a mdl of 110 ppm. For 25 ppm, it would
add an additional 100 minutes to the
analysis time.
 Figure of Merit

Variation of figure-of-merit (P2/F) with accelerating voltage for various

elements in different matrices. Scaled so 15 kV=1, no ZAF corrections.
Variation of figure-of-merit with accelerating voltage, each element relative to
its level at 15 kV. Detection limits (3 sigma) calculated for 100 sec counts, 50
kV, 450 nA. Data are all k-ratios, not ZAF corrected.
Probers in Australia have much interest
in pushing the lower limits of EPMA They utilize a figure of merit of
detection, for mineral exploration P2/B as a measure of how to achieve
research.Utilizing extreme operating lower mdl (the higher the P2/B ).
conditions (50 kV, 475 nA, 10 minute From our first principles derivation,
counts) they have achieved mdls we can see that the P comes from the
below 5 ppm for some elements. standard, the B from the unknown.
From Advances in Electron Microprobe Trace-Element Analysis by B.W. Robinson and J. Graham, 1992, ACEM-12
 Keys to low detection levels
Maximize counts by utilizing
Highest currents feasible (concern: beam damage)
Highest E0 as feasible (concern: increased
penetration/range)
Longer count times
Correctly determine background locations
Be 100% aware of n>1 peaks occurring in neighborhood
Correct for unavoidable on-peak interferences within the
matrix correction*
*Donovan, Snyder and Rivers, 1993, An improved interference correction for trace element analysis, Microbeam Analysis, 2, 23-28.
 Silicate Glass with 90 ppm P

P Ka peak = red line position. But n=2 Ca Kb1,3 also very close!

BIR =Icelandic Basalt with 9.5 wt% Ca (USGS

reference material)
Silicate Glass with 90 ppm P

n=1 Si Kb1,3

n=1 P Ka1,2

n=3 Fe Ka1,2 n=2 Ca Kb1,3 n=3 Ca Ka1,2

 Backgrounds: traces can overlap traces
Correct locating of
background
positions is
particularly
important in trace
element work, as
both first order and
higher order peaks
can cause incorrect
assessment of
background level.
Here, scans of the 3
Caltech/MAS trace
element glass
standards are
overlain. (Xe L
edge present as a
Xe gas sealed From Carpenter, Counce, Kluk, and Nabelek, Characterization of Corning Standard
Glasses 95IRV, 95IRW and 95IRX: NIST/MAS Workshop, April 2002.
counter used.)
Backgrounds ... holes
Probers in Australia,
interested in
detecting trace levels
of gold in certain
minerals, discovered
a hole in the
Au La background about
200 sin theta units
below the Au La
position.
(This scan was on
SrTiO3, on the LIF
crystal).
 2 Examples
1. Ti in quartz
2. Monazite
 Ti-in-quartz
Multi-point Background Modelling
 Ti-in-quartz
Multi-point Background Modelling
 Ti-in-quartz
2 important options: Aggregate (Sum Up) >1
spectrometer; Blank Correction
 Ti-in-quartz
After collecting Assign Blank Correction
Ti on 4 spectrometers: no blank correction
Ti on 4 spectrometers: with blank correction
Ti: All 4 spectrometers aggregated;
blank corrected
 Monazite
Important mineral for age-
dating by EPMA

But

Low amounts of Pb;

complicated background
Monazite
Monazite
Monazite
Monazite
Monazite
 Monazite EPMA
procedure
Julien Allaz at University of Colorado
has a detailed procedure
contact him
Julien.allaz@colorado.edu
Best Trace Element
EPMA needs:
1. Strong, flexible, background
modelling
2. Interference correction within the
matrix correction
3. Ability to add up counts from
many spectrometers
4. Blank correction within the matrix
correction
 Standards: validating trace
element procedure

There is an issue of trace element accuracy on unknowns,

where the standard for the element of interest was at a high
level. Such a standard should be used for peaking the
spectrometer and acquiring standard counts, but it is
recommended that a secondary trace level standard be also
analyzed to validate the procedure.
Such secondary standards could be
Synthetic glasses such as the Caltech/MAS 95IRV,W
and X glasses; NIST glasses and metals; Ni-Cr
diopside glass, etc.
Minerals and glasses analyzed by ion probe
 Comparison:
Trace elements by WDS vs EDS

WDS is clearly the better method for acquiring trace element data, by
an order of magnitude or so compared to EDS.

Goldstein et al, 1992, p. 501