The sediment samples from river, pond, lake and

ocean have received great interest from the viewpoints

of geochemical and environmental sciences because
they often continuously record the past geological
events and environmental changes.
1
In general, the
sediment samples from river, lake or pond are investi-
gated to elucidate the environmental pollutions due to
heavy metals and some toxic organic substances. On
the other hand, the drilling sediment core samples from
the big lakes and oceans are analyzed to understand the
paleoenvironmental changes of the Earth. For exam-
ple, the drilling project of Lake Biwa was carried out
during the 1980s as a cooperative research project sup-
ported by the Ministry of Education, Science and
Culture of Japan.
2
In last decade, the Baikal Drilling
Project (BDP), started in 1989, has been performed as
an international cooperative research project among
Japan, Russia, USA, Germany and other countries.
3
In
these researches on the drilling sediment core samples,
the multielement information is very useful for investi-
gation of the paleoenvironment.
4
In order to promote
the geochemical and paleoenvironmental studies on the
sediment core samples, thus, it is still required to estab-
lish or develop the accurate and precise analytical
methods for the multielement analysis of sediment
samples.
Inductively coupled plasma atomic emission spec-
trometry (ICP-AES) and inductively coupled plasma
mass spectrometry (ICP-MS) have multielement detec-
tion capability with high sensitivity.
5
Furthermore,
ICP-AES and ICP-MS provide the wide linear dynamic
range of 4 6 orders of magnitude; in general, 100 g
ml
1
1 ng ml
1
for the former and 100 ng ml
1
1 pg
ml
1
for the latter. Thus, the elements in the major-to-
ultratrace concentration range can be determined by
both ICP-AES and ICP-MS, which are also applicable
to the analysis of the sediment samples. In the previous
paper
6
, the present authors reported the multielement
determination of major-to-ultratrace elements in lake
sediment reference materials by ICP-AES and ICP-MS,
where Lake Biwa sediment reference material (JLk-1)
and Lake Baikal sediment reference material (BIL-1)
issued by the Geological Survey of Japan (GSJ) and by
the Russian Institute of Geochemistry, respectively,
were used for analysis after alkali fusion. As a result,
43 elements in the lake sediment samples were deter-
mined with quite good reliability. In addition, we also
reported, as a short communication, the multielement
profiling analysis of Lake Baikal drilling sediment core
samples by ICP-AES and ICP-MS.
7
From these
studies, it has been found that use of ICP-AES and
ICP-MS makes it possible to obtain the multielement
data for the sediment samples. The numbers of the
multielement data obtained are almost comparable to or
often more than those obtained by neutron activation
analysis (NAA)
8
, which has been used as the most
powerful method for multielement analysis.
In the present study, hence, the multielement determi-
nation of major-to-ultratrace elements by using both
ICP-AES and ICP-MS is further performed to charac-
729 ANALYTICAL SCIENCES AUGUST 1999, VOL. 15
1999 The Japan Society for Analytical Chemistry
Multielement Determination of Major-to-Ultratrace Elements in
River and Marine Sediment Reference Materials by Inductively
Coupled Plasma Atomic Emission Spectrometry and Inductively
Coupled Plasma Mass Spectrometry
Rong WEI and Hiroki HARAGUCHI

Department of Applied Chemistry, Graduate School of Engineering, Nagoya University,

Furo-cho, Chikusa-ku, Nagoya 4648603, Japan
The multielement determination of major-to-ultratrace elements in river sediment reference material (NIES No.16) and
marine sediment reference material (NIES No.12) was investigated by inductively coupled plasma atomic emission spec-
trometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The sediment samples were decom-
posed by alkali fusion with lithium metaborate (LiBO2) in a platinum crucible, and the residues were dissolved in 1 M
nitric acid. The digested sample solutions were subjected to the analysis by ICP-AES and ICP-MS after appropriate dilu-
tion. In consequence, 42 elements were determined over a wide concentration range, for example, from Si 23.8% to Lu
0.29 g g
1
in the case of marine sediment reference material.
Keywords Sediment reference materials, multielement determination, major-to-ultratrace elements, ICP-AES, ICP-MS

To whom correspondence should be addressed.

terize the river and marine sediment reference materi-
als. The analytical results for these sediment samples
are compared with those for the lake sediment samples
reported previously.
6
Experimental
Instruments
The ICP-AES instrument of Model Plasma
AtomComp Mk II from Jarrell Ash (Franklin, MA,
USA), which includes a direct-reading polychromator
of PaschenRunge mounting with 40 channel detectors
(photomultipliers), was used for the determination of
major and minor elements in the sediment samples. A
cross-flow type nebulizer was used for pneumatic neb-
ulization in the ICP-AES instrument. In addition, sul-
fur was determined by another ICP-AES instrument of
Model SPS 1500V from Seiko Instruments Inc. (Chiba,
Japan), which allowed one to measure the emission of
sulfur at 180.73 nm in the vacuum ultraviolet region.
The ICP-MS instrument of Model SPQ 8000A (Seiko
Instruments Inc.) was used for the determination of
trace and ultratrace elements. This instrument consist-
ed of a quadruple-type mass spectrometer.
The operating conditions of the ICP-AES and ICP-
MS instruments are summarized in Table 1. These con-
ditions were obtained after optimization of the instru-
mental parameters in each instrument.
Chemicals and samples
Lithium metaborate used for alkali fusion was of
ultra-pure grade (Spectromelt), purchased from E.
Merck (Germany). Other chemicals used were of ana-
lytical reagent grade. The multielement standard solu-
tions for the ICP-AES and ICP-MS measurements were
prepared as the 10 multielement groups from the sin-
gle-element standard solutions for atomic absorption
spectrometry (Wako Pure Chemicals Ltd., Osaka), in a
similar manner to that described in the previous work.
6
The distilled-deionized water used throughout the pre-
sent experiment was prepared by a Milli-Q system
(Nihon Millipore Kogyo Ltd., Tokyo). River sediment
reference material (NIES No.16) and marine sediment
reference material (NIES No.12), which were issued
from the National Institute for Environmental Studies
(NIES), were used for analysis. These sediment refer-
ence materials were prepared from the sediments col-
lected near the Tama River Estuary and in the Tokyo
Bay, respectively.
Experimental procedure
The sediment reference sample (ca. 0.2 g) was
decomposed in a platinum crucible by alkali fusion
using LiBO
2
(ca. 0.5 g), as reported in the previous
paper.
6
The LiBO
2
fusion method provides an advan-
tage to determine Si, which is an indicator to examine
the environmental changes of the sediment samples.
After decomposition, the samples were dissolved in
100 ml of 1 M nitric acid solution, and subjected as the
analysis solutions to the following experiments. The
analysis solutions were diluted by 10-fold for the ICP-
AES measurement, and further by 20-fold for the ICP-
MS measurement. In the ICP-MS measurement, matrix
effects due to major constituents were corrected by an
internal standard method, using Ge, In, Re and Tl (10
ng ml
1
each) as the internal standard elements.
9,10
Results and Discussion
Analytical detection limits
The analytical detection limits obtained by the pre-
sent instruments are shown in Table 2, together with the
wavelengths of emission lines and m/z of ions. These
analytical detection limits were calculated as the con-
centrations of the elements in a unit sample amount (1
g) from the instrumental detection limits, which were
estimated as the analyte concentrations corresponding
to the 3-times the standard deviation (3) of the signal
intensities in the repeated measurements of the blank
solution. It is seen from Table 2 that ICP-AES is gen-
730 ANALYTICAL SCIENCES AUGUST 1999, VOL. 15
Table 1 Operating conditions for ICP-MS and ICP-AES
instruments
a) The plasma conditions were the same as those for ICP-MS.
erally suitable for the determination of the elements
above 1 g g
1
in the sediment samples, while ICP-MS
was suitable for the determination of those below 1 g
g
1
. In the following experiment, the elements in the
sediment samples were determined by ICP-AES or
ICP-MS, as is indicated in Table 2.
Analytical results for river sediment reference material
The river sediment reference material (NIES No.16)
was analyzed by ICP-AES and ICP-MS after sample
digestion using LiBO
2
. The analytical results for river
sediment reference material are summarized in Table 3,
together with the reference values.
11
The relative stan-
dard deviations (RSDs) of 3-times duplicate analysis
and the relative variances (%) are also shown in Table
3. The relative variances in Table 3 were calculated by
the following equation;
Relative variance(%)={(M
obs
M
ref
)/M
ref
}100 (1)
where M
obs
and M
ref
are the observed and reference val-
ues, respectively, in Table 3.
When there were two reference values, the averaged
values of them were used as M
ref
in the calculation of
the relative variance. Furthermore, the ratios of the
concentrations of the elements in sediment (observed
values; M
obs
) to those in earth crust (M
crust
) are also
given in Table 3.
Table 3 shows that the analytical values for 42 ele-
ments were obtained in the concentration range from
27.5% of Si to 0.34 g g
1
of Lu, which covered 7
orders of magnitude in concentration. The RSDs of the
observed values were within 5% except for Co, Dy, Gd,
Sm and Eu. These results indicate that the present
method was precise enough to apply to the multiele-
ment analysis of the sediment samples. The RSD for
Co (m/z=59) was poor in Table 3; this value was also
poor in the case of marine sediment, as is seen in Table
4. This may be ascribed to matrix effects due to major
constituents as well as to the large background intensi-
ties caused by ArO and ArOH because a low-resolution
ICP-MS instrument of quadrupole-type was used in the
present experiment.
Table 3 shows that the relative variances for Cr, Rb,
V, Ni, Co, Th, Hf, Sm, U, Yb, Er, Eu, Ho and Tm were
larger than 10%, while those for 28 other elements
were less than 10%. Since the certified values for river
sediment reference material (NIES No.16) have not
been issued from NIES, it is difficult to discuss the rea-
sons for disagreement between the observed and refer-
ence values for the elements whose relative variances
are larger than 10%. Even so, it may be concluded here
that the observed and reference values in Table 3 are in
fair agreement with each other.
As mentioned earlier, the river sediment reference
material used here was collected near the Taishi bridge
in the Tama River Estuary. Thus, it should be taken
into account that some influences from seawater may
be found in the river sediment sample examined. The
influences of seawater on river sediment reference
material (NIES No.16) will be discussed later.
Analytical results for marine sediment reference
material
The marine sediment reference material (NIES
No.12), which was collected in the Tokyo Bay, was
also analyzed in a similar manner to the way river sedi-
ment reference material was analyzed. The analytical
results for marine sediment reference material are sum-
marized in Table 4, together with the reference
values.
1214
In addition, the RSDs of the observed val-
ues, the relative variances defined by Eq. (1), and the
ratios of M
obs
/M
crust
, which were estimated in the same
ways as those in Table 3, are also shown in Table 4. In
Table 4, the RSDs for Cu, Ni and Co are larger than
731 ANALYTICAL SCIENCES AUGUST 1999, VOL. 15
Table 2 Analytical detection limits obtained by the ICP-AES
and ICP-MS instruments
a. I and II indicate atomic and ionic lines, respectively. The ele-
ments with these signs were determined by ICP-AES, and others
by ICP-MS.
b. The analytical detection limits were estimated as the concentra-
tions in the sediment sample per unit amount (1 g).
Element
Wavelength
a
or m/z
Analytical detection
limit
b
/g g
1
10%, while those for other elements are much smaller
than 10%. The poor precision of the observed value is
often obtained for Cu in the ICP-MS measurement,
when the sampling cone made of copper becomes dete-
riorated. In the case of Ni (m/z=60), the poor precision
might be caused by large matrix effect due to major
constituents because of their high concentrations in
marine sediment. The poor precision for Co in the
marine sediment sample may be also ascribed to a simi-
lar reason in the case of the river sediment sample.
The relative variances larger than 10% were obtained
for 21 elements (K, Cr, V, Pb, Zr, Cu, Rb, Ni, Ga, Co,
Cs, Pr, U, Dy, Gd, Sm, Hf, Yb, Eu, Tm and Lu) among
42 elements. In general, the relative variances for
marine sediment reference material are rather larger
than those for river sediment reference material. The
reference values shown in Table 4 were obtained by
various analytical methods, such as atomic absorption
spectrometry, ICP-AES and ICP-MS
1214
, and the inter-
calibrations between the different analytical methods
have not been made yet. Thus, it is strongly required to
carry out the certification work for marine sediment
reference material (NIES No.12).
It is seen from Table 4 that the ratios of M
obs
/M
crust
for
Na, S, Zn, Cr, Pb, Cu, Cs, U and W are larger than 1.
Furthermore, the significantly large value for S is clear-
732 ANALYTICAL SCIENCES AUGUST 1999, VOL. 15
Table 3 Analytical results for river sediment reference material(NIES No.16) determined by ICP-AES and ICP-MS
a. Mean valueSD (standard deviation), n=3. b. Cited from ref. 11. c. {(M
obs
M
ref
)/M
ref
}100 (%), where M
obs
and M
ref
are the
observed and reference values, respectively. The average of two values was used as M
ref
, when there were two reported values.
d. M
crust
: elemental abundance in earth crust.
Element
M
obs
/ M
crust
d
Observed value
a
M
obs
/g g
1
RSD,
%
Reference value
b
,
M
ref
/g g
1
Relative
variance
c
, %
ly characteristic of marine sediment. Such large con-
tent of S in marine sediment originates from SO
4
2
in
seawater. The high concentrations of Zn, Pb and U in
marine sediment (NIES No.12) may reflect pollution
due to human activities around urban cities.
15
Comparison of chemical compositions between river
and marine sediment reference materials
The correlation between the elemental concentrations
of river and marine sediment reference materials is
shown in Fig. 1. Figure 1 shows that the concentrations
of Na, Mg, Ca and S, which are major constituents in
seawater, are markedly higher in marine sediment than
in river sediment. Trace elements such as Mn, Zn, Cr,
V, Pb and Ni are also higher in marine sediment than in
river sediment. These elements are known to be
anthropogenic, and thus they have been possibly accu-
mulated in marine sediment of the Tokyo Bay for a
long time. Major constituents of river and marine sedi-
ment samples such as Si, Al, Fe and Ti showed fair cor-
relation, although their concentrations were slightly
lower in marine sediment. The lower concentrations of
such major elements in marine sediment may be due to
dilution by the higher contents of organic matter. In
fact, it was found that ignition loss of marine sediment
was ca. 10% of total amount, while that of river sedi-
733 ANALYTICAL SCIENCES AUGUST 1999, VOL. 15
Table 4 Analytical results for marine sediment reference material (NIES No.12) determined by ICP-AES and ICP-MS
a. Mean valueSD (standard deviation), n=3. b. The values for the elements with * and ** were cited from ref. 12 and ref. 13,
respectively. The data for P was obtained by ICP-AES (ref. 14). c. {(M
obs
M
ref
)/M
ref
}100 (%), where M
obs
and M
ref
are the ob-
served and reference values, respectively. d. M
crust
: elemental abundance in earth crust.
Element
M
obs
/ M
crust
d
Observed value
a
M
obs
/g g
1
RSD,
%
Reference value
b
,
M
ref
/g g
1
Relative
variance
c
, %
ment was ca. 8%. Akagi and Haraguchi investigated
the behavior of suspended particulates in water collect-
ed near the Tama River Estuary and in Tokyo Bay.
According to their reports
1618
, the suspended particu-
lates collected near the Tama River Estuary were rich in
weathered mineral and rock components, and most of
them sank immediately in the off-shore area of Tokyo
Bay. On the other hand, the suspended particulates col-
lected in the center of Tokyo Bay were coated with
organic matter like humic substances.
In Fig. 2, the ratios of the elemental concentrations in
river and marine sediment reference materials to the
averaged abundances of the elements in earth crust,
which are expressed as (M
obs
/M
crust
) in Tables 3 and 4,
are drawn as a bar graph. It can be considered that the
elements, whose ratios are larger than 1, are enriched in
the sediment through sedimentation processes. The
most significant characteristics of the marine sediment
is the extremely high concentration of S. It is also
noted here that S in the river sediment is also quite
high, compared to that in earth crust. These results
indicate that river sediment reference material (NIES
No.16) certainly received some influences from sea-
water because the river sediment sample was collected
at the Tama River Estuary near Tokyo Bay.
The concentration of Na was also higher in marine
sediment than in river sediment. The M
obs
/M
crust
ratio of
Na for marine sediment reference material was larger
than 1, although that for river sediment reference mate-
rial was smaller than 1. This result can be interpreted
by the fact that Na is more scavenged in the particulate
formation during marine sedimentation process. It
should be also noticed that Pb and Zn are significantly
high in both river and marine sediment reference mate-
rials. In addition, Cs, P, Cr, Cu, Zr, Hf, W, Th and U
are enriched in river and/or marine sediments. The
high concentration, especially for Pb, may indicate that
pollution due to human activities especially derived
from the automobiles is progressing around Tokyo Bay.
All lanthanoid elements, which are hereafter referred to
as rare earth elements (REEs), provided the ratios of
M
obs
/M
crust
less than 1 in both samples.
Chondrite-normalized REE patterns of sediment
samples
The concentrations of REEs in the sediment samples
were normalized by those of Leedey chondrite. This
normalized distribution pattern, which is hereafter
referred to as chondrite-normalized REE pattern
19
, is
shown in Fig. 3. In Fig. 3, the REE patterns are drawn
for river sediment reference material (NIES No.16) and
marine sediment reference material (NIES No.12) as
well as for Lake Biwa sediment reference material
(JLk-1) and Lake Baikal sediment reference material
(BIL-1), which were investigated in the previous work.
6
As is seen in Fig. 3, the general characteristics of the
REE patterns for all the sediment samples is that the
slope is down from the left (light REEs) to the right
(heavy REEs). It should be pointed out here that all the
REE patterns in Fig. 3 provided smooth curves. These
results suggest that the present analytical data for REEs
are quite reliable because such smooth curves of the
734 ANALYTICAL SCIENCES AUGUST 1999, VOL. 15
Fig. 1 Correlation between the elemental concentrations of
river (NIES No.16) and marine (NIES No.12) sediment refer-
ence materials.
Fig. 2 Comparison of elemental concentrations in sediment
samples (Mobs) to elemental abundances of earth crust (Mcrust).
Black bar: river sediment (NIES No.16); white bar: marine
sediment (NIES No.12).
Fig. 3 The chondrite-normalized REE patterns of various sed-
iment reference materials. : river sediment (NIES No.16);
: marine sediment (NIES No.12); : Lake Biwa sediment
(JLk-1); : Lake Baikal sediment (BIL-1).
REE patterns are obtained only when the data are accu-
rate and precise. It is also noted that all the samples
showed Eu-anomaly. Although the Ce-anomaly is
often observed for the REE pattern of seawater
20
, such
Ce-anomaly was not found even for the marine sedi-
ment sample examined in the present experiment.
The concentrations of REEs in Fig. 3 are higher in the
order of JLk-1, BIL-1, NIES No.16 and NIES No.12,
although light REEs in both lake sediment samples are
almost at the same concentration level. These results
indicate that the concentrations of REEs in marine sedi-
ment is the lowest among the sediment samples exam-
ined. This suggests that the supply of REEs from the
river around Tokyo Bay is rather small and they are not
accumulated in marine sediment.
The authors express our sincere thanks to Dr. Hideyuki
Sawatari in Miyagi University of Education and Dr. Akiko
Hokura in Nagoya University for their kind help and sugges-
tions in the present work. The present research was supported
by the Grant-in-Aid for the program of Future Research from
the Japan Society for Promotion of Science. One of the authors
(Rong Wei) also gives her heartful appreciation to Prof.
Shigekatsu Mori of Nagoya University, the representative of the
above research project, for his support of her research fellow-
ship.
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735 ANALYTICAL SCIENCES AUGUST 1999, VOL. 15