VAEC-AR 06--31

THE DETERMINATION OF RARE EARTH ELEMENTS IN

GEOLOGICAL AND ENVIRONMENTAL SAMPLES BY
INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY
Nguyen Xuan Chien, Pham Ngoc Khai, Tran Duc Hien, Dao Nguyen, Dinh Cong Bot,
Thinh Van Trung, Nguyen Thi Cuc, Le Hong Minh, Nguyen Viet Thuc,
Bui Thi Ngan and Do Van Thuan
Institute for Technology of Radioactive and Rare Element
Abstract: A method for the determination of rare earth elements (REEs) (La, Ce, Pr,
Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) in geological and environmental samples
by inductively coupled plasma mass spectrometry (ICP-MS) has been developed. The
effect of ICP-MS operating parameters on the REO (H) +/RE+ production ratio was
studied in detail, and the optimal ICP operating conditions were established to minimize
spectral interferences of the polyatomic ions REO (H). The use of In as an internal
standard to compensate for the matrix suppression and signal drifts were investigated.
The method was applied to the determination of REEs in geological and environmental
samples, and the analytical results were in good agreement with the recommended
reference values.

Introduction
Information about the contents of rare-earth elements (REEs) in several kinks of
samples is very important in geochemical, biochemical and environmental studies. In
addition, nowadays REEs have been widely used in agriculture as a trace element
fertilizer in all over the world. The economic benefit of REEs fertilizer has set the
scientists a study on the mechanism for the output enhancement based on analysis of
REEs concentration at the cell and on the evaluation of environmental impact of REEs
fertilizer. Therefore the need for accurate trace analysis of REEs in environmental and
geological samples has increased. Because the content of REEs in natural biological
materials and geological samples is generally very low, it is very difficult to determine
them accurately by conventional analytical methods. Recently, the molecular activation
analysis (MAA) has been quickly developed and applied to the study on the chemical
species of trace elements in living bodies. This method combines the specific separation
techniques, chemical or biochemical, with highly sensitive nuclear analytical
techniques, such as neutron activation analysis (INAA) [1]. The determination of REEs
by ICP-AES especially ICP-MS have been applied widely in many laboratories. Being a
sensitive and high selective technique, ICP-MS permitted analysis of REEs
concentration in high pure materials and complex matrix samples without separation
steps. Method for the direct determination of trace quantities of rare earth elements
(REEs) in high purity erbium oxide dissolved in nitric acid by ICP-MS was developed.
Proposed method had been found to be suitable for the direct determination of trace
REEs impurities in 99.999-99.9999% high purity europium oxide [2].
REEs impurities in europium were determined by ICP-MS combined with ion
chromatography [3]. The determination of REEs in several kinds of samples of
environment, geology, marine sediment, granite, human serum, biology and minerals by
ICP-MS combined with various separation techniques or laser ablation was studied by
many authors [4,5,6,7,8,9,10,11,12,13].

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Instrumentation and reagents

1. Instrumentation
The ICP-MS instrument used was an Agilent model 7500a quadrupole mass
spectrometer. Standard operating conditions of ICP-MS system and the data acquisition
parameters were summarized in Table 1.
Tab 1. Operating parameters of ICP-MS system
Plasma condition
RF Power

1300 W

Sample depth

5.1 mm

Plasma gas

15l/min

Carrier gas

1.14 l/min

Aux gas

0,9 l/min

Peripump

0,1 rpm

Data acquisition:
Peak pattern

Full Quant(3)

Intergration time

0,1 s

Repetition

2. Reagents and calibration solutions

-

All reagents were Suprapure grade or for ICP-MS.

MiliQ water 18 M.

Multi element standard stock solutions of fourteen REEs 10 mg/l.

Calibration standard solutions of fourteen REEs were prepared by accurately

diluting 10 mg/l each element stock solution to give calibration solutions of
each element concentration range of 0,05; 1; 5; 10; 20; 30; 40; 50; 60 g/l
(calibration solution 1). In (internal standard element) was added to each
solution to obtain In concentration of 40 g/l (calibration solution 2).

3. Separation column of REEs

30 g Biorad AG 50W-X8 resins soaked in HNO3 5 M 12 h was loaded into glass
column (20 x 200 mm). Clean the resin with 120 ml water. Keeping resine submerged in
water of 120 mm depth.
Experimental, results and discussion
1. Study on the interference of polyatom ions, interference equation
Polyatomic ions which have the same nominal mass to charge (m/z) ratio as the
analyte elements caused spectroscopic interference. The interference of polyatomic ion
on REEs showed in table 2. In order to eliminate the interference of polyatomic ion, the
effect of ICP-MS operating parameters on the REO (H) +/RE+ production ratio was

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VAEC-AR 06--31

investigated and the optimal ICP operating conditions were established to minimize
spectral interferences of the polyatomic ions REO (H). In additional, isobaric
interference can be corrected by mathematical interference correction called interference
equation.
Tab 2. Interfering polyatomic species and interfered isotopes
No

Isotopes
139

Abundance
(%)

157
157
158

157

11,11

CeOH+

159

159

Tb

159

Tb

27,2

NdOH+

159

159

Tb

159

Tb

Tb

159

Tb
Dy
Dy

88,45
100

142

Ce

Nd

142
143

10

159
160

Nd
147
Sm

17,2
14,99

NdOH+
SmO+
SmOH+

163
163
164

163

Dy
163
Dy

163

5,7

NdOH+

165

165

Ho

165

Ho

165

165

Ho

165

Ho

SmO
SmOH+

165
166

165

Ho
Er

165

166

166

Ho
Er

11,24

SmO+
SmOH+

166
167

166

Er
167
Er

166

Er

Nd

5,7

NdO+
NdOH

166
167

166

166

Er

Sm

26,75

SmOH+

169

169

146

148
148

150

Nd

Sm
Sm
Sm

150

SmOH

13,82

13
152

153

Tm

169

Tm

Tm

169

Tm

100

EuO
EuOH+

169
170

Gd
156
Gd

14,80
20,47

GdOH+
GdO+

172
172

172

157

21,83

GdO+
GdOH+

173
174

173

Yb

24,84

GdOH+

175

175

Lu

175

Lu

100

TbO+

175

175

Lu

175

Lu

Eu

155

Gd

18

20

Er
167
Er

163

169

15

19

11,24

12

17

Gd+
157
Gd+

NdO
TbOH+

11

16

157

12,2

149

14

Gd+
157
Gd+

Nd

8
9

Gd+

159

6
7

Analytical
mass

CeOH+
PrO+
PrOH+

Ce
141
Pr

3
4

interfered
isotopes
155

99,91

140

Mass
155
156

La

1
2

Interfering
polyatomic
species
LaO+
LaOH+

158

Gd

159

Tb

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Yb
172
Yb

172
172

Yb
Yb

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The REO (H) +/RE+ production ratio depended on RF power (RFP), Ar carried
gas flow rate (CGFR) and sample depth (SDe). To establish the optimal ICP operating
conditions to minimize spectral interferences of the polyatomic ions REO (H), REEs
solution of 20 g/l of each was measured at various parameters of RFP, CGFR and SDe.
The relationship between polyatomic ions and RFP showed in figure 1 and 2.

SmOH/Sm

REOH+/RE ratio (%)

REO+/RE Ratio (%)

5.00

PrO/Pr
156GdO/Gd
CeO/Ce
TbO/Tb
NdO/Nd LaO/La

15.00

SmO/Sm
DyO/Dy

10.00
HoO/Ho
LuO/Lu
ErO/Er

5.00

TmO/Tm
EuO/Eu
YbO/Yb

0.00
600

1100
RF Power (W)

ErOH/Er

3.00

LaOH/La

2.00
1.00
0.00
600

1600

156GdOH/Gd
DyOH/Dy

4.00

LuOH/Lu
CeOH/Ce
NdOH/Nd
EuOH/Eu
YbOH/Yb
TbOH/Tb
HoOH/Ho
TmOH/Tm

800

1000 1200 1400 1600

RF power (W)

Fig. 2. Relationship between REOH+/RE+

ratio and REP

Fig. 1. Relationship between REO+/RE+

ratio and REP

Research results showed that polyatomic ions production ratio was very high at
low RFP (800 W), especially that with La (194.76 %), Ce (145.77 %) and Pr (102, 23
%). Upon the increase of RFP, polyatomic ions production ratio decreased and that
were minimum and then were constant from RFP>1300 W. Specific was following:
LaO+/La+ from 194.7593 % down to 0.5996 %; CeO+/Ce+ from 145.7750 % down to
0.5580 % and PrO+/Pr+ from 102.2322 % down to 0.4747 %. Like this, the increase
RFP permits limit of polyatomic ions production ratio.
The REO (H) +/RE+ production ratio increased upon increase of the CGFR. That
ratio was not much changed over CGFR range 1.05-1.15 l/min. From CGFR >1.15
l/min, that ratio increased rapidly, especially at >1.2 l/min.
Research results showed that upon increase of the SDe, the REO (H) +/RE+
production ratio decreased and that with sesitivity. At SDe of 4 mm, REO+/RE+ ion
ratio of La, Ce, Pr and Nd were >1. At SDe of 4.5 mm only oxide ratio of La and Ce > 1
and that of all REEs were lower than 1 at SDe >5 mm.
The optimal ICP operating conditions established to minimize spectral
interferences of the polyatomic ions REO (H) were showed in table 1. At this condition
oxide production ratio was low and that hydroxide was inconsiderable.
The calculated oxide spieces ratios of the measures at the optimal conditions
established above and the mathematical interference correction equations showed in
tables 2 and 3.
Tab 2. Interfering oxide species ratios and interfered isotopes
Interfered isotopes
157

220

Gd

Interferingoxides Measuringisotopes
(M+)
(MO+)
141

PrO+

141

Pr+

The Annual Report for 2006, VAEC

Ratios (%)
MO+/M+
0,475

VAEC-AR 06--31

159

Tb

143

163

Dy

Ho

NdO+

146

147

SmO+

149

Er

150

Er

150

Tm

153

165

166
166
169

172

157

Gd

147

Sm+

0,118

SmO

147

Sm

0,109

SmO+

147

Sm+

0,089

146

EuO

153

GdO+

157

159

NdO

159

Lu

Interfered isotopes

0,264

156

Yb

175

Nd+

0,123

Eu

0,014

Gd+

0,252

Nd

0,195

Measuringisotopes
(M+)

Ratios (%)
MO+/M+

TbO

Interferingoxides
(MO+)

Tb

141

PrO+

141

Pr+

0,475

NdO

146

0,264

159

Tb

143

163

Dy

147

SmO+

147

Sm+

0,118

Ho

149

147

Sm

0,109

147

Sm

0,089

NdO+

146

Nd+

0,123

EuO

153

GdO+

157

159

165

SmO

166

Er

150

166

Er

150

Tm

153

169

172

Yb

175

Lu

SmO

156

159

TbO

Nd

Eu

0,014

Gd+

0,252

Tb

0,195

Tab 3. Oxide species interference equations

Equations for obtaining intensities of
metal oxides

Corrected intensities

PrO (157) = 141Pro x [141PrO/141Pr]t

Gd (157) = 157Gdo - 141Pro x [141PrO/141Pr]

NdO (159) = 146Ndo x [143NdO/146Nd]t

Tb (159) = 159Tb - 146Ndo x [143NdO/146Nd]

SmO (163) = 147Smo x [147SmO/147Sm]t

Dy (163) = 163Dy - 147Smo x [147SmO/147Sm]

SmO (165) = 147Smo x [149SmO/147Sm]t

Ho (165) = 165Ho - 147Smo x [147SmO/147Sm]

SmO (166) = 147Smo x [150SmO/147Sm]t

Er (166) = 166Er - {147Smo x

[150SmO/147Sm]+ 147Smo x [150SmO/147Sm]}

NdO (166) = 146Ndo x [150NdO/146Nd]t

EuO (169) = 153Euo x [153EuO/153Eu]t

Tm (169) = 169Tm - 153Euo x [153EuO/153Eu]

GdO (172) = 157Gdo x [156GdO/157Gd]t

Yb (172) = 172Yb - 157Gdo x [156GdO/157Gd]

TbO (175) = 159Tbo x [159TbO/159Tb]t

Lu (175) = 175Lu - 159Tbo x [159TbO/159Tb]

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2. Determination of REEs in spiked samples and cetified referenced

materials (CRMs)
Analytical procedure was summarized as following:
Geological samples
Transfer 0.25 gr. of sample to 50 ml PTFE jar. Add 15 ml mixture solution of
HF + HClO4 + HNO3 (10+4+6). Heat to discompose the sample on electric stove at the
temperature not exceeds 300OC. Evaporate the sample solution to dryness. Add 10 ml of
HNO3 d=1.42 and evaporate to dryness. Dissolve salt in 20ml of 1M HNO3. Filter the
solution through fine paper and wash the residue with 1M HNO3. Transfer filter paper
and residue to a platinum crucible. Ignite at 800oC and then fuse at 850oC with KHF2 of
5 times more than the residue. Allow to cool. Add a few drops of concentrate HCLO4
and heat on electric stove to eliminate remain HF. Take this step one more time. The dry
precipitate was dissolved in 5 ml of 1M HNO3. Combine dissolve solution and filtrate in
total not exceed 40 ml. Place sample solution to the column and flowed at a flow rate of
2 ml/min. After all the sample solution was transferred to the column, 125 ml of 1M
HNO3 was added to the column then 20 ml water, 300 ml of 2 M HNO3 and 20 ml
water were flowed at a flow rate of 2 ml/min. Elute REEs with 200 ml of 5 M HNO3 at
flow rate of 2 ml/min. The REEs fraction thus obtained was evaporated to dryness, the
residue dissolved in 0.35 M HNO3. Transfer solution to mark volumetric flask, dilute
with 0.35 M HNO3 to mark. Obtained solution was measured by ICP-MS using
calibration solution 1.
Biological samples
1 gr of sample was transferred to a platinum crucible. The sample was ignited at
500 C for 5-6 h. The obtained ash was dissolved in 10 ml concentrate HNO3, 2 ml H2O2,
1 ml HF. Evaporate solution to dryness. Add 10 ml concentrate HNO3 and then
evaporate solution to dryness again. This step was done one more time. Dissolve the salt
and dilute to 10 ml with 0.35 M HNO3 + 40 ppb In. Obtained solution was measured by
ICP-MS using calibration solution 2.
o

The analytical results of spiked samples and CRMs were showed in tables 4
and 5.
Tab 4. Analytical results of spiked samples

Eleme
nts

Ion-exchange chromatography
separation
Added
(ppb)

Found
(ppb)

La

20

23.4

Ce

20

Pr

Recover
y (%)

Added
(ppb)

Found
(ppb)

16.8

116.8

20

20.0

24.2

20.8

120.8

20

14.0

-29.8

70.2

20

18.9

-5.6

94.4

20

19.3

-3.5

96.5

Nd

20

21.4

7.0

107.0

20

19.1

-4.4

95.6

Sm

20

18.8

-6.0

94.0

20

17.4

-12.9

87.1

Eu

20

20.0

0.1

100.1

20

19.9

-0.5

99.5

222

Bias
(%)

With internal standard, without

separation

The Annual Report for 2006, VAEC

Bias
(%)

Recover
y (%)

0.1 100.1

VAEC-AR 06--31

Gd

20

20.3

1.3

101.3

20

18.0

-10.0

90.0

Tb

20

19.9

-0.5

99.5

20

17.9

-10.5

89.5

Dy

20

19.7

-1.4

98.6

20

17.7

-11.4

88.6

Ho

20

19.8

-0.8

99.2

20

17.7

-11.4

88.6

Er

20

19.6

-2.1

97.9

20

17.8

-10.9

89.1

Tm

20

19.7

-1.5

98.5

20

17.7

-11.7

88.3

Yb

20

19.7

-1.7

98.3

20

17.0

-15.2

84.8

Lu

20

20.1

0.5

100.5

20

18.1

-9.6

90.4

Tab 4. Analytical results of IAEA Soil- 7 and IAEA-336 CRMs

IAEA-Soil 7
Elements
La

IAEA-336

Certified
value
(ppm)

Found
(ppm)

Bias
(%)

Certified
value
(ppm)

28

29.36

4.9

0.66

Found
(ppm)

Bias
(%)

0.59

-10.36

Ce

56.79

0.92

Pr

6.25

0.10

Nd

30

23.69

-21.0

0.6

0.52

-13.93

Sm

5.1

4.15

-18.5

0.106

0.100

-5.59

Eu

0.83

-17.2

0.023

0.017

-26.28

Gd

3.67

0.094

Tb

0.6

0.49

-19.0

Dy

3.4

2.74

-19.4

0.014

0.011
0.057

Ho

0.50

0.008

Er

1.46

0.028

Tm

0.20

0.003

Yb
Lu

2.4

2.02
0.18

-15.8

-21.43

0.037

0.029

-20.41

0.0066

0.0085

28.61

3. Determination of REEs in samples of geology and parts of tea, bassela Alba

and soybeens.
The analytical results of REEs content in samples of geology and parts of tea,
bassela alba and soybeens was showed in figure 1 and 2.

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1000
104QC
1013QC

Sample/Chondrite

1015QC

100

1016QC
1021QC

10

0
La

Ce

Pr

Nd

Sm

Eu

Gd

Tb

Dy

Ho

Er

Tm

Yb

Lu

Fig. 1. REEs content in geological samples

Research results showed that REEs content was highest in tea root and the
lowest in soybeans seed. REEs content in the parts of tea, bassela alba and soybeans
followed the order as following1: root (T) > root (B) > leaf (B) > leaf (T) root (S) >
stem (T) > stem (B) > young leaf (T) > leaf (S) > stem (S) > seed (S). REEs content in
stem, leaf and seed of soybeans were all smaller than those in the parts of tea and
bassela alba. REEs content in soybean seed were very low and were the smallest among
those in the parts of three kinds of plant.
100
Stem (S)

10

Leaf (S)

Sample/Chondrite

Seed (S)

Stem (B)
Leaf (B)

0.1

Stem (T)
Leaf (T)
Young leaf(T)

0.01

Root (S)
Root (B)

0.001

Root (T)

Lu

Yb

Er
Tm

d
Tb
D
y
H
o

Eu

Pr
N
d
Sm

La
C
e

0.0001

Fig. 2. REEs content in tea, bassela alba and soybeens

Conclusion
ICP-MS technique combines with chemical separation step permited analysis of
trace quantities of REEs in geological and environmental samples with high sensitivity
and precision. REEs in biological samples could be determined directly by ICP-MS
using internal standard without separation step with good precision satisfied the practical
requirements. Analytical results showed that REEs content in several kinds of interested
plant were concentrated mainly in their roots, then in their leaves. REEs content were
rather low in other parts, especially in soybeans seed.
1

(T): Tea; (B): bassela alba; (S): soybeans.

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