XRF 1085
Trace Element Analysis for Water
Solution by Micro-Droplet Method Using
“Ultra Carry®” Filter Paper
water solution
environment
Introduction
Influence of trace heavy elements in water, such as Cd,
Pb, As, Cr, Se, etc., on the environment is treated as
serious social problem. In order to control this
problem, it is essential to monitor water quality.
Considering the large number of test samples required
for assessment of water quality, the test method should
be simple, rapid, and reproducible.
X-ray fluorescence (XRF) analysis have a lot of
features, such as simple sample preparation, short
analysis time, and high repeatability with small human
error, compared to other elemental analysis methods,
such as ICP-OES or AA. XRF is the best method for
the above test.
Concentrations of some trace heavy elements are too
low for XRF analysis in direct liquid analysis, where
water solution is poured into a liquid cell with analysis
thin film. In this application note, the micro-droplet
method was used. An improved filter paper “Ultra
Carry®” for the micro-droplet method achieved the LLD
lower than 0.1 ppm.
This note demonstrates the analysis results and the
performance of the micro-droplet method with Ultra
Carry.
“Ultra Carry®”, unique filter paper
Figure 1 shows a photo of Ultra Carry, a unique filter
paper for the micro-droplet method. A thin paper pad is
Wavelength dispersive micro-droplet method
X-ray fluorescence filter paper
spectrometer Ultra Carry
ZSX Primus, ZSX PrimusIII+, water solution
ZSX Primus IV
ZSX Primus IV
Figure 1 Photo of Ultra Carry
placed on very thin polymer film supported by a plastic
ring.
This Ultra Carry is designed to analyze trace elements
in water solution. Since the paper pad and the film are
very thin, background observed at measurement is
very low, which allows significantly excellent
peak-to-background ratio (signal/noise). The paper
pad contains a reagent that captures water on the pad,
which enables a drop of 500 μL at a time. After drying,
the specimen is measured under vacuum.
The above features result in very low LLD, lower than
0.1 ppm, or ppb level for most of heavy elements.
Table 1 shows typical LLD for water solution by the use
of Ultra Carry.
Since the specimen is measured under vacuum, boron
and fluorine in water solution also can be analyzed.
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 XRF 1085

These spectrometers are equipped with a Rh target

Table 1 Typical LLD for water solution by the use of Ultra Carry X-ray tube and the maximum tube power is 4 kW for
Element LLD (ppb) Element LLD (ppb) ZSX Primus IV/Primus and 3 kW for ZSX PrimusIII+,
B 30 ppm* Zn 18
respectively. Up to 10 analyzing crystals can cover
from beryllium to uranium.
F 1 ppm* As 16
The instruments also have a built-in intelligent auto
Na 76 Se 24
sample changer (ASC). The ASC is upgradable to 48
P 56 Sr 25
and 96 samples, respectively.
K 12 Mo 27
Operation software provides inexperienced users with
V 34 Ag 152
easy-to-use operation. The flowbar system fully
Cr 26 Cd 182
supports operation on the setting-up of qualitative and
Mn 16 Sn 40
quantitative analysis in particular. The standardless
Fe 18 Sb 43
analysis program “SQX” is highly usable to determine
Co 17 Ba 105 quickly which elements and how much of elements are
Ni 20 Tl 81 contained in unknown sample without preparation of
Cu 19 Pb 76 suitable reference materials.
Counting time: 100 seconds for each element
*Only for B and F, the unit is ppm.
Measurement
The ZSX Primus IV was used for measurement.
Sequential scan analysis from fluorine to uranium was
Sample and sample preparation
performed followed by semi-quantitative analysis
A standard solution “SPEX LPC Standard 1” was used
(SQX).
for the demonstration.
In SQX analysis, a qualitative scan is run, and the
On an Ultra Carry, 500 μL of the standard solution was
detected elements are then quantified by the
dropped (Figure 2 [a]) and dried overnight. The dried
fundamental parameter (FP) method without the use of
Ultra Carry was placed on the backscatter elimination
reference standard samples. In the quantifying process,
cup made of aluminum (Figure 2 [b]) and then set into
a sensitivity library is used which has the FP
the sample holder for ZSX Primus IV.
sensitivities for all elements that can be analyzed by
Since Ultra Carry is very thin, backscatter from the
XRF and which has been calibrated using pure metals
inside of the sample holder passes through Ultra Carry
and reagents.
and is observed. The backscatter elimination cup
SQX has a fixed angle measurement function. Using
blocks backscatter from the sample holder.
this function, the X-ray intensity is collected at a fixed
two-theta angle for a user defined given time, usually
much longer than the time for a step in scanning;
therefore, precision is improved and superior results
can be obtained for trace element analysis. In this note,
the fixed angle measurement was applied for each
trace element.
Sequential qualitative scan and semi-quantitative FP
[a] [b]
calculation are programmed and executed in a
Figure 2 Sample setting for Ultra Carry successive process.
[a] Drop 500 μL of the solution on the center (paper pad) of
Ultra Carry Results
[b] After drying, place the Ultra Carry on the backscatter SQX results for the standard solution “SPEX LPC
elimination cup (aluminum).
Standard 1” by the use of Ultra Carry, with the
reference standard values, are listed in Table 2.
Instrument Table 2 shows that the SQX results are in good
The ZSX Primus IV, ZSX PrimusIII+ and ZSX Primus agreement with the reference values.
are floor-standing sequential wavelength dispersive SQX analysis program has a function of “Automatic
X-ray fluorescence (WDXRF) spectrometers, which theoretical overlap correction”, which automatically
have advantages in high spectral resolution and high corrects for influence of overlap of element lines. It is
sensitivity from light to heavy elements. The not necessary to manually separate overlapping peaks.
instruments are designed to provide reliable analysis In this analysis, As-Kα, Na-Kα, and P-Kα are
results and their high flexibility provides versatility for a overlapped by Pb-Lα, Zn-Lβ1, and Mo-LL respectively.
wide range of applications. For As, Na and P, excellent analysis results were
obtained without any manual handling for the data.

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Table 2 SQX analysis result (unit: ppm) Conclusions

SQX Standard SQX Standard A unique filter paper, Ultra Carry, enables an analysis
Element Element
result value result value
of trace elements lower than 0.1 ppm, or at ppb level,
Na 18 20 As 21 20
in water solution. Since sample preparation is very
P 72 100 Se 19 20
simple and easy, it is possible to reduce analytical error
K 92 100 Sr 20 20
derived from sample handling and also to shorten the
V 18 20 Mo 19 20 total analysis time.
Cr 20 20 Ag 3 5 A water solution sample, typically 500 μL, is dropped
Mn 21 20 Cd 20 20 on to Ultra Carry and then dried; therefore, a specimen
Fe 20 20 Sn 18 20 can be measured under vacuum. Using Ultra Carry, it
Co 20 20 Sb 22 20 is possible to analyze from boron to uranium and also
Ni 21 20 Ba 18 20 no helium gas is required.
Cu 19 20 Tl 20 20 Ultra Carry, with thin paper pad on very thin polymer
Zn 19 20 Pb 18 20 film, gives excellent peak-to-background ratio
(signal/noise), which achieves significantly low LLD,
Ultra Carry is very thin, its thickness does not reach lower than 0.1 ppm, or at ppb level.
saturated thickness (or bulk thickness). In SQX A standard-less analysis program, SQX, for water
analysis program, the FP method is employed. In the solution by the use of Ultra Carry was demonstrated,
process of theoretical X-ray intensity by the FP method, which shows this analysis method allows excellent
not only concentration of each element but also weight results for trace elements in water solution.
per area (or thickness) of the sample are considered.
Therefore, it is possible to apply SQX to film, coating
(single layer/substrate), filter and sample whose
thickness is not enough. The excellent SQX results for
Ultra Carry were obtained owing to the FP calculation.

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