Fresenius J Anal Chem (1992) 343 : 600- 603
Springer-Verlag 1992
Determination of trace amounts of molybdenum in water samples
by inductively coupled plasma atomic emission spectrometry
after cobalt-dithiocarbamate coprecipitation
Jiang Zucheng* and P. Schramel
GSF Research Centre of Environment and Health, Institute of Ecological Chemistry, W-8042 Neuherberg, Federal Republic of Germany
Received November 2, 1991; revised January 17, 1992
Summary. A method for the determination of trace amounts
of molybdenum in fresh water and seawater samples by
sequential ICP-AES with microsampling technique after co-
balt-dithiocarbamate coprecipitation was developed, The
precipitate was dissolved in 100 1~1of diluted nitric acid (1 : 2),
and the solution obtained was then introduced into an ICP
via a concentric nebulizer. By use of 1.7 ml sample, a precon-
centration factor of 17 was achieved. Different factors in-
cluding integration time, sample volume, pumping rate as
well as coprecipitation conditions such as pH of the solution,
amounts of reagents, standing time for the precipitate and
matrix effects were examined and optimized in detail. Under
selected conditions the detection limit of the method for Mo
is 0.52 gg/1 using 1.7 ml sample. The procedure was applied
to the analysis of water samples (artificial water and open
ocean seawater reference material) with quantitative recov-
ery. The analytical results were in good agreement with the
certified value. The method is sensitive, simple, accurate and
effective, also in the presence of interfering salts and can be
applied to small sample volumes.
Introduction
Molybdenum is considered as an essential trace element for
man, but relatively little is known about the biochemical
functions. On the other hand, it is of increasing environmen-
tal interest. Therefore, some effort has to be made to improve
the reliability of Mo-analysis in environmental samples. Un-
fortunately, most analytical techniques do not provide suf-
ficient sensitivity to directly monitor Mo at ppb levels. In
addition, the volume of water sample is often limited. There-
fore, the development of a method is desirable for determin-
ing traces of Mo with a preconcentration procedure prior to
the final measurement by using small sample volumes.
Several preconcentration methods have been proposed
including solvent extraction [1 - 3 ] , ion exchange [4, 5], flo-
tation [6] and coprecipitation [7 - 10] combined with differ-
ent analytical techniques for the determination of Mo and
* On leave from the Department of Chemistry, Wuhan University,
Wuhan, 430072 China
Offprint requests to: P. Schramel
Fresenius' Journal of
Table 1. ICP operating parameters
RF output power 1.1 kW
Frequency 40.86 MHz
Coolant gas Ar, 14 l/rain
Shielding gas Ar, 0.1 l/rain
Carrier gas 0.4 l/rain Ar + 0.4 1/min (Ar + Hz)
Observation height 14 mm
Nebulizer Concentric type
Signal integration 2s
Wavelength Mo II 202.03 nm
other trace elements in water, seawater and biological
sample. Recently Akagi and Haraguchi [11] developed a
method for the simultaneous multielement determination of
trace metals using 10 ml of seawater by ICP-AES with gal-
lium coprecipitation and microsampling technique; a pre-
concentration factor of 200 was achieved. The tris(pyrroli-
dine dithiocarbamate)-cobalt (III) precipitate has been used
for preconcentrating trace metals in seawater by coprecipita-
tion before graphite furnace atomic absorption spectrometry
or X-ray fluorescence analysis [10, 11]. For sequential ICP-
AES a preconcentration technique for the determination of
trace Mo in water and seawater samples by means of cobalt
dithiocarbamate as a coprecipitation reagent and the
microsampling technique was developed, because of the rela-
tively poor detection limit of this method for Mo (in the
range of 5 gg/1). The method was applied to the analysis of
water and seawater samples with satisfactory results. It was
especially developed for the analysis of Mo in small sample
volumes. This is the main advantage compared with other
techniques.
Experimental
Instrumentation
A Jobin-Yvon model 38P sequential ICP spectrometer was
used with a l-m Czerny-Turner monochromator with a
special 2400 lines/mm grating (1. and 2. order). The main
operating conditions are given in Table 1. The grating was
used in second order with a real resolution of 0.005 nm. The
intensity of the analytical line was measured at the fixed
peak position with 2 s integration time.
 601
Table 2. Influence of integration time

Integration time(s) 0.5 1 2 3 4 5 6 8

Net signal 371 743 1437 2145 2785 3235 3686 4850
Background 141 281 562 844 1126 1410 1696 2272
Signal-to-background ratio 2.63 2.60 2.58 2.54 2.47 2.27 2.19 2.13

intensity intensity
2500 700 q

600 j
2000-
/ ~'--~---~
1500
400 1 S/

1000
al/
200 ~]f
500
100

I I I L ~ 0 ~ I - - I I I

0 100 200 300 400 500 600 0 20 40 60 80 100

sample volume (IJI) H N 0 3 1:10 (pl)
Fig. 1. Influence of sample volume on the signal intensity Fig. 3. Acidity effect on the coprecipitation of Mo

relative intensity recovery (%)

12

110
10-

8
90

70

I i 50 I I I I

0 0,5 1 1,5 2 2,5 3 0 1 2 3 4

time (h) time (h)
Fig. 2. Stability of the analytical signal Fig. 4. influence of standing time on Mo coprecipitation

Reagents and standards
Distilled water was used for all solutions and dilutions. Nitric
acid was of Suprapur grade (65%, Merck). Cobalt solution
(500 mg/1) was prepared by diluting the stock standard solu-
tion (1000 gg/ml) with water. A Mo solution of 1000 rag/1
was prepared by dissolving 0.2522 g of Na2MoO4 2H20
in water and diluting to 100 ml. Sodium dithiocarbamate
solution was prepared by dissolving 5 g of DDTC-Na in
water and diluting to 100 ml. This solution should be filtered
through a membrane filter with 0.45 gin pore size and kept at
4 C for longer storage. Sodium chloride, magnesium nitrate
and calcium sulphate were of analytical grade. Their con-
tents in artificial seawater were 3.5g NaC1, 0.5g
Mg(NO3)2 - 6HzO and 0.1 g CaSO4 2H20 in 100 ml water.
The calibration solutions were treated in the same way as
the samples, i.e. they have been measured after the
coprecipitation procedure.
Recommended procedure
Exactly 1.7 ml of water sample is placed into a 2 ml plastic
centrifugation tube. Then 0.1 ml of the cobalt solution
(500 rag/l) and 40 ~tl of diluted HNO3 (1:10) is added fol-
lowed by 0.2 ml of 5% (w/v) DDTC-Na solution. The
centrifugation tube is closed, the mixture shaken for several
602

intensity Table 4. Influence of the matrix

580
NaC1, mg/ml
570

560 0 10 20 30 40 50

550 Io 173
Im 182 177 153 166 159
540 Im:Io 1.05 1.02 0.88 0.96 0.92
530 Mg(NO3)2 " 6H20, mg/ml
520 - 0 2 4 6 8 10
510 I I I 7 - - 1
In 173
0 5 10 15 20 25 30 Im 196 179 185 186 179
time (s) Im: Io 1.13 1.04 1.07 1.08 1.04
Fig. 5. Background variations caused by different reagents. H20; CaSO4 2H20, mg/ml
+ HNO3 1:2; * (DDTC)3 Co + HNO3 1:2
0 0.5 1 2

Table 3. Influence of Mo concentration on the coprecipitation Io 173

efficiency Im 190 188 185
Im:Io 1.10 1.09 .07
Concentration of Mo Coprecipitation efficiency
in water samples, ng/ml % In = signal intensity of Mo without matrix
I m = signal intensity of Mo with matrix
5 100
10 98
50 79 Table 5. Precision of the method
100 73
500 46 Element Sample Concen- Concen- Amounts
tration tration of the
of Mo of Mo measurement
added, ng/ml found 4- std.
dev. ng/ml
seconds and allowed to stand for 2 h. Then it is centrifuged
at 11500 rpm/min for 10 min. A small precipitate adheres Mo Water 10 10.18 _ 0.82 10
to the bottom o f the tube. After the supernatant fluid is Mo Artificial 10 10.48 + 0.34 10
removed, 0.1 ml of diluted HNO3 (1:2) is added to dissolve seawater
the precipitate. The end of a capillary leading to the nebulizer
is directly inserted into the centrifugation tube, and the signal
of the analyte is measured by the sequential ICP system.
1.7 ml of deionized water is treated in the same way and Table 6. Reovery of the method
used as a blank.
Sample Number Added Mo Found Mo Recovery
ng/ml ng/ml %
Influence of integration time and sample volume
Water 1 10 9.5 95
The integration time was varied between 0.5 and 8 s to find 2 10 10 100
the best sensitivity for the 100 gl sample solution. The results 3 10 10 100
4 10 9.4 94
are given in Table 2. They indicate that both signal and
background are increasing with increasing integration time; Artificial 5 10 10.5 105
but their ratio is tending downwards. N o significant change seawater 6 10 10 100
was observed in the range o f 0.5 s to 3 s. A n integration time 7 10 10.5 105
8 10 10.3 103
of 2 s was chosen.
The sample volume introduced into the ICP shows a
significant influence on the net signal o f the analyte. As
shown in Fig. 1, first the intensity o f M o is increasing with
that the stability of the intensity was very sufficient within
increasing sample volume, then a plateau is reached when
a few hours (see Fig. 2).
the sample volume is more than 200 g l .

Stability of the signal
In case o f the microsampling technique the signal intensity
was measured at a fixed wavelength position. Theferore, a
wavelength shift becomes more important. The results show
Coprecipitation conditions
Optimal pHfor coprecipitation. It has been pointed out [9]
that molybdenum can quantitatively be coprecipitated with
cobalt-PDC at a p H of 4 -I- 0.5. In these experiments, diluted
nitric acid (1 : 10) was used to roughly adjust the pH. After

Table 7. Analytical results of seawater sample
Seawater Reference Material NASS-3
Element Method 1 Method 2 Certified
(l~g/1) (ixtml) (ixg/1)
Mo 11.3 4-0.9 11.1 +_0.7 11.5 +_1.9
Method 1 - Calibration curve method (number of replicates = 8)
Method 2 - Standard addition method (number of replicates = 3)
adding DDTC-Na [5%(w/v)] the pH of the sample solution
will be about 4, and the coprecipitation process takes place.
Figure 3 shows the effect of the acidity.
Amounts of precipitate reagents. The amounts of cobalt ions
and D D T C - N a were selected experimentally. 0.1 ml of
500 rag/1 of Co and 0.2 ml of D D T C - N a solution were used
for 1.7 ml of sample.
Standing time for coprecipitation. As shown in Fig. 4, 1 - 2 h
is sufficient for a complete coprecipitation of Mo.
Dependence of coprecipitation efficiency on the Mo concen-
tration. The results indicate that the coprecipitation ef-
ficiency is dependent on the Mo-concentration in the solu-
tion (Table 3). Two conclusions can be drawn: (1) The same
chemical treatment for the standard solutions is required.
(2) The method can be applied up to a Mo concentration of
100 Ixg/1 with a satisfactory recovery. But it should not be
measured outside the calibration range. The method can
sufficiently be used for practical samples because of the
normally low "natural" concentrations of Mo in water and
seawater samples of < 20 Ixg/1 (including all the relatively
unknown environmental influences from the so-called "dif-
fuse sources" !).
Interfering effects
Figure 5 shows the interference effect of some reagents on
the background intensity. In order to improve the accuracy
of the method, the background intensity caused by the re-
agents must be substracted from the whole intensity.
603
Interferences by major ions such as Na, Mg and Ca were
studied and the results were listed in Table 4. No significant
interference had been observed.
Detection limit, accuracy, precision
The detection limit for Mo was calculated to be 0.5 Ixg/1(3e~).
A preconcentration factor of 17 was found. The precision of
the method was examined by using a fresh water and an
artificial seawater sample spiked with 10 Ixg/1 Mo. The re-
sults are given in Table 5. The precision obtained was better
than ___10% for 10 Ixg/1Mo in water samples. The recovery
for Mo-spiked samples was satisfactory (Table 6).
Molybdenum was determined by the proposed method
in an open ocean seawater reference material (NAAS-3). The
results were compared with calibration curve and standard
addition method. They are shown in Table 7. A very good
agreement with the certified values is obvious.
Conclusion
The procedure described here can be applied to the analysis
of Mo in water samples with satisfactory accuracy and pre-
cision. The detection limit is sufficient, especially for
seawater samples. The use of a C R M (NAAS-3) shows a
good agreement with the certified values. The method is
simple, accurate and effective also in the presence of rela-
tively high amounts of different salts.
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