Ap

at
plic

ion Note

Chemistry
ICP-OES
ICP56

High performance analysis of Boron with ICP-OES

Boron is a low abundance element in both the solar system and the Earths crust. It is concentrated on Earth
by the water-solubility of its more natural-occuring compounds, the borate minerals. Such minerals are mined
industrially as evaporate ores such as borax and kernite.
Boron is used for several applications in industry. Its main use is in the form of sodium tetraborate pentahydrate
for making insulating fiberglass and sodium perborate bleach. Borax is used in detergents formulation and
bleaching agents. Boron is also used as a dopant in the semiconductor industry and the high-hardness Boron
compounds are used as abrasives.
Boron is also well known for its ability to capture thermal neutron due to its high cross-section and it is then
widely used in the nuclear industry where it acts as a shield. In nuclear reactors, boron is used for reactivity
control and in emergency shutdown systems. For such applications boron is in the form of borosilicate control
rods or as boric acid. Boric acid is also added to the reactor coolant when the plant is shut down for refueling.
For such application, monitoring the concentration of boron is more than necessary to prevent any issue.
Boron content of glass used for nuclear waste vitrification has also to be monitored to prevent from any issue as
it ensures security of the storage.
Inductively Coupled Plasma Optical Emission Spectrometry is well suited for boron analysis as it allows
reaching low detection limits but main issue is related to memory effects occurring. Since years, it has been
reported that high concentration of boron are creating memory effects due to boron that literally sticks on all
surfaces which are in contact with the solution or the aerosol. It means the whole introduction system, i.e.
tubing, nebulizer and spray chamber, but also the injector of the torch.
This application note evaluates the performance of HORIBA Scientific ICP-OES instruments for boron analysis.
Several parameters are evaluated such as sensitivity, linearity, accuracy, repeatability, robustness and memory
effects.

Operating conditions
All analyses were done using the ULTIMA 2 ICP-OES. The
characteristics of this spectrometer are given in table 1.
Table 1. Characteristics of the ULTIMA 2

Parameters

Specification

Generator

40.68 MHz
Solid state, water cooled

Optical system

Czerny Turner (1 m focal length)

Grating

2400 g/mm

Thermoregulation

+32C

Nitrogen purge

3 L/min

Resolution

< 5 pm in the 120 320 nm range (1st order)

< 10 pm in the 320 800 nm range (2nd order)

Plasma observation

Vertical torch
Radial viewing with Total Plasma View*

Introduction system

Inert parallel flow nebulizer

Cyclonic glass spray chamber

Pump tubing

Black-black pump tubing for sample

Grey-grey pump tubing for drain

An inert parallel flow nebulizer was used to allow handling high

concentrations of boron that may crystallize at high concentration.
This nebulizer was associated with a cyclonic glass spray chamber.
The ULTIMA 2 is equipped with the unique fully demountable
torch, the 3 mm i.d. alumina injector and the original sheath gas
device. The 3 mm i.d. injector increases the residence time of
the sample into the plasma leading to enhanced sensitivity and
reduced matrix effects while the sheath gas reduces the contact
between the injector and the sample, eliminating deposits issues
and memory effects.
All plasma parameters, power, gas flows, are optimised to get
sensitivity along with long term stability and are given in Table 2.

* Total Plasma View: measurement of the whole Normal Analytical Zone of the plasma for enhanced
sensitivity

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Table 2. Operating conditions

Parameters

Specification

Power

1100 W

Plasma gas

12 L/min

Auxiliary gas

0 L/min

Sheath gas

0.2 L/min

Nebuliser gas

0.65 L/min

Sample uptake

1 mL/min

All measurements are performed using a 20/80 m slit combination

with 4 seconds integration time for the line and 2 seconds for the
background.

Analytical results
Sensitivity
Sensitivity is important as Boron should be analyzed at low
concentrations for some samples.
Sensitivity was determined using a 3 points calibration curve:
a blank, a 2.5 mg/L standard and a 5 mg/L standard. A blank
was then analyzed with 10 replicates. The limits of detection and
quatification were calculated using the formulae below:
LOD = 3 x s.d.
LOQ = 10 x s.d.
Where LOD is the limit of detection, LOQ the limit of quantification,
s.d. the standard deviation obtained for the blank.
Detection and quantification limits obtained are given in Table 3 for
a sensitive and a non sensitive line.
Table 3: Detection and quantification limits for Boron

Element

LOD (g/L)

LOQ (g/L)

B 206.665

46

153

B 249.678

1.1

3.8

Linearity
Linearity means reduced analysis time as it implies that a single
line can be used to cover a wide range of concentration, thus a
reduced number of standards can be used.
Linearity was evaluated using several calibration standards from
50 to 2000 mg/L. The measurements were done 3 times to check
for accuracy of data.
Standards used for calibration are given in Table 4.
Table 4: Standards for linearity evaluation

Elt

Std 0
(mg/L)

Std 1
(mg/L)

Std 2
(mg/L)

Std 3
(mg/L)

Std 4
(mg/L)

Std 5
(mg/L)

50

100

250

500

2000

Calibration curves obtained are displayed below. Linear regression

was used without any weighting procedure for B 206.665 nm. For
B 249.678 nm that is more sensitive, weighting procedure was
applied to improve the fitting for low concentrations (weight of
1/c was used, where C is the concentration).

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Figure 1: Calibration curves obtained for B 206.665 nm

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All correlation coefficient are better than 0.999 for both B 249.678
nm and B 206.665 nm. Residuals are always less than 2% for
B 206.669 nm and less than 5% for B 249.678 nm, showing an
excellent agreement between given concentrations and calculated
concentrations.
Linearity is obtained on a wide range of concentration, proving that
analysis of low and high concentrations can be performed on a
single line.

Accuracy
For accuracy evaluation, a Reference Material was used, prepared
at various concentrations (10, 25, 50, 100, 500 and 1250 mg/L),
and analyzed using the calibration curves previously established.
To match customers expectations, the instrument should allow
determination of Boron with less than 1% for concentrations lower
than 100 mg/kg and less than 0.5% for concentrations less then
100 mg/kg.
Lithium was added to all samples (10 mg/L Li) and used as internal
standard to correct for small drifts and improve accuracy.
Results obtained are presented in Tables 5 and 6 below for the 2
selected lines. For improved accuracy, low concentrations (lower
than 50 mg/L) are determined using B 249.678 nm and weighted
fit with calibration standards ranging from 50 to 250 mg/L. For
high concentrations, B 206.665 nm was used with unweighted
calibration and standards ranging from 50 to 2000 mg/L.
Table 5: Results for low Boron concentrations with B 249.678 nm

Theoretical
conc (mg/L)

Measured
conc (mg/L)

SD
(mg/L)

RSD
(%)

Specification

10

9.99

0.05

0.54

9.9 - 10.1

25

25.05

0.09

0.36

24.75 - 25.25

50

49.97

0.26

0.53

49.5 - 50.5

Table 6: Results for high Boron concentrations with B 206.665 nm

Theoretical
conc (mg/L)

Measured
conc (mg/L)

SD
(mg/L)

RSD
(%)

Specification

100

99.79

0.50

0.50

99 - 101

500

501.64

2.76

0.55

497.5 - 502.6

1250

1250.78

7.31

0.58

1243.75 -1256.25

Excellent accuracy is obtained for both B 249.678 nm and B

206.665 nm lines, meeting expectations.

Repeatability
To evaluate the repeatability, the 50 mg/L and 250 mg/L standards
were analyzed 10 times using 5 replicates with rinse between each
sample. A stability test over 1 hour is then obtained.
Results obtained are displayed in Table 7 for 50 mg/L using B
249.678 nm and in Table 8 for 250 mg/L using B 206.665 nm.
Figure 2: Calibration curves obtained for B 249.678 nm

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Table 7: Repeatability test for 50 mg/L using B 249.678 nm

Sample

Time

B 249.678

50 mg/L

15:42

Table 9: Robustness results for the 50 mg/L standard

Conc (mg/L)

RSD (%)

Sample

Time

Conc (mg/L)

RSD (%)

49.6

0.4

B 206.665

50 mg/L

15:05

50.0

0.4

50 mg/L

15:47

49.6

0.6

50 mg/L

16:12

49.5

0.4

50 mg/L

15:51

49.5

0.4

50 mg/L

17:13

50.0

0.4

50 mg/L

15:56

50.3

0.5

50 mg/L

18:54

50.0

0.5

50 mg/L

19:34

49.5

0.4
0.4

50 mg/L

16:01

50.3

0.3

50 mg/L

16:05

50.2

0.3

50 mg/L

16:10

49.7

0.3

Mean

49.8

50 mg/L

16:15

49.5

0.3

SD

0.3

RSD%

0.5

50 mg/L

16:19

49.6

0.5

50 mg/L

16:28

49.9

0.2

50 mg/L

16:33

49.9

0.6

Sample

Time

Conc (mg/L)

RSD (%)

0.4

B 249.678

50 mg/L

15:05

50.3

0.5

Mean

49.8

SD

0.3

50 mg/L

16:12

50.5

0.3

0.6

50 mg/L

17:13

50.1

0.5

50 mg/L

18:54

49.8

0.5

50 mg/L

19:34

49.6

0.2
0.4

RSD%

Table 8: Repeatability test for 250 mg/L using B 206.665 nm

Sample

Time

B 206.665

250 mg/L

17:26

Conc (mg/L)
250.8

RSD (%)
0.5

Mean

50.1

250 mg/L

17:32

249.5

0.4

SD

0.4

250 mg/L

17:39

250.6

0.4

RSD%

0.7

250 mg/L

17:46

251.8

0.2

250 mg/L

17:53

250.6

0.6

250 mg/L

17:59

250.6

0.5

RSDs obtained on 4.5 hours for Boron analysis show excellent

robustness of the method, ensuring quality of the results over
hours.

250 mg/L

18:06

248.2

0.4

250 mg/L

18:13

248.4

0.6

Memory effects

250 mg/L

18:20

248.3

0.5

250 mg/L

18:27

248.7

0.5

Mean

249.8

0.5

SD

1.3

RSD%

0.5

As Boron is known for memory effects and issues with rinsing

time, it was mandatory to include it in the study as it will affects
the analysis time and the accuracy of the results.
A calibration was done using a blank and a 250 mg/L standard.
A 2000 mg/L sample was then analyzed during 2 minutes and
the calibration blank was then measured every 2 minutes until it
reaches the initial calibration blank value. For this test, the most
sensitive line was used.

Excellent repeatability was obtained on both short and long

term with all RSDs lower than 0.7% over 1 hour. RSDs of each
measurement are also lower than 0.7% showing the stability of
each measurement and then the ability of the spectrometer to
stabilize within few seconds after introduction of the sample into
the introduction system.

Robustness
The robustness was evaluated as the capability of the spectrometer
to give a concentration over a long period of time, with natural
variations of measurement conditions (temperature of the
laboratory). The 50 mg/L standard was then analyzed just after
calibration and then measured again after 1 hour, 2 hours, 4 hours
and 4.5 hours without any recalibration.

Rinsing was done using acidified water without any other reagent.
It is reported than mixtures of ammonia and D-Mannitol help to
reduce rinsing time with creation of a complex of Boron with
D-Mannitol in Ammonia. However, such mixtures imply higher
stabilization time due to the stabilization of the spray chamber
that is necessary between acid samples and ammonia. Careful
optimization of amounts of reagents is also required as the
formation of the complex may continue if too high amounts are
used, inducing a bias on the result.
The results obtained are displayed in the Table 10 and Figure 3.

Results are given in Table 9 for both B 249.678 nm and B 206.665 nm.

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Table 7: Repeatability test for 50 mg/L using B 249.678 nm

B 249.678

Sample

Time

Net Intensity

Comments

Blank

15:52

1048.788

I0: Calibration blank value

250 mg/L

15:55

2833394.048

250 mg/L standard

Blank

15:59

1243.536

Calibration blank value

after 250 mg/L standard

Only 20 minutes are necessary to rinse the system and reach the
calibration blank value after the analysis of a 2000 mg/L Boron
sample. This performance is possible due to the reduced sample
path between the spray chamber and the torch and also thanks
to the original sheath gas device that insulates the aerosol of the
spray chamber from the inner walls of the injector.

and reduced rinsing time

16:24

21063757.938

Blank

16:26

6469.925

Blank

16:35

1621.799

Blank

16:37

1378.476

Blank

16:40

1236.595

Blank

16:42

1116.513

Blank

16:44

1046.264

Blank

16:47

1030.333

Blank

16:49

1033.233

Blank

16:51

1032.072

I < I0

Conclusion
The performances obtained with the ULTIMA 2 ICP-OES
spectrometer for Boron analysis are excellent. Unrivaled
sensitivity and linearity are achieved thanks to the optical quality
of the monochromator, the PMT detection device and the radial
viewing mode with Total Plasma View allowing the measurement
of the whole Normal Analytical Zone. The combination of this high
quality optics and the introduction system design with a reduced
path between the spray chamber and the plasma as well as the
original sheath gas device allows exceptional performances in
terms of accuracy, repeatability, robustness and memory effects.

Figure 3: Rinsing time for Boron using B 249.678 nm line

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This document is not contractually binding under any circumstances - Printed in France - HORIBA Jobin Yvon 02/2011

2000 mg/L

2000 mg/L Boron sample