Microchemical Journal 104 (2012) 33–37

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Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Ultrasensitive determination of cobalt and nickel by atomic fluorescence

spectrometry using APDC enhanced chemical vapor generation
Chujie Zeng a, Yunzhen Jia a, Yong-Ill Lee c, Xiandeng Hou a, b,⁎, Li Wu b,⁎⁎
a
College of Chemistry, Sichuan University, Chengdu, Sichuan 610064, China
b
Analytical & Testing Center, Sichuan University, Chengdu, Sichuan 610064, China
c
Department of Chemistry, Changwon National University, Changwon 641–773, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Ammonium pyrrolidine dithiocarbamate (APDC) was used to enhance the chemical vapor generation (CVG)
Received 3 April 2012 efficiency of nickel and cobalt. Volatile nickel and cobalt species were effectively generated through reduction
Accepted 5 April 2012 of acidified analyte solution with 2% potassium tetrahydroborate (KBH4) solution in the presence of
Available online 15 April 2012
0.02% (m/v) APDC. Thus, a new CVG-atomic fluorescence spectrometric (AFS) method was developed for
determination of ultratrace nickel and cobalt. Influencing parameters were evaluated in detail, including
Keywords:
Nickel
the complexing reagents, the concentrations of APDC, nitric acid and KBH4, flow rates of carrier gas and shield
Cobalt gas, lengths of the reaction tube and the transfer tube, as well as interferences. Under the optimized condi-
Chemical vapor generation tions, the limits of detection (LOD) were 1 ng mL − 1 and 6 ng mL − 1 for nickel and cobalt, respectively. The
Atomic fluorescence spectrometry calibration curves were linear in the range of 10 to 300 ng mL− 1 and 50 to 1200 ng mL− 1 for nickel and
Ammonium pyrrolidine dithiocarbamate cobalt, respectively. The potential application of this method was validated by the accurate determination
of nickel in three certified reference materials. It was also applied to determination of cobalt in water samples
and Vitamin B12 with good recoveries of spiked samples.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction and reliable analytical methods to determine ultratrace nickel and

Chemical vapor generation (CVG) has been widely used in analyt-
ical atomic spectrometry because of its obvious advantages of efficient
matrix separation, enhanced analyte transport efficiency, efficient
analyte atomization, and potential speciation analysis over conven-
tional pneumatic nebulization [1–3]. There are several chemical
vapor generation schemes that can be used to convert different ana-
lytes into gaseous forms, allowing them to be determined with good
sensitivity and selectivity [1,3]. Hydride generation (HG) is the most
widely used CVG techniques [4], but the number of elements that
can generate hydrides upon derivatization with tetrahydroborate
(III) is still limited, which stimulates the development of new CVG sys-
tems for more detectable elements. In recent years, CVG has been
expanded its scope to transition and noble metals following reaction
with tetrahydroborate (III), such as Cu, Fe, Co, Zn, Mn, Au, Ag, Pt, and
Pd [5–11]. Recent advances in the CVG of transition and noble metals
can be found in some recent comprehensive reviews [12–14].
Trace nickel and cobalt have been the subject of many investiga-
tions since they are essential for living organism but toxic when
excessive. Therefore, it is important to develop sensitive, rapid, simple
⁎ Correspondence to : X. D. Hou, College of Chemistry, Sichuan University, Chengdu,
Sichuan 610064, China. Tel.: +86 28 8547 0818; fax; +86 28 8541 5695.
⁎⁎ Corresponding author.
E-mail addresses: houxiandeng@yahoo.com.cn (X.D. Hou), scuwl@163.com (L. Wu).
cobalt in varied kinds of samples. Conventional nickel CVG procedures
involve the reaction of the analyte with carbon monoxide to generate
volatile nickel carbonyl species [15–21]. However, the extremely toxic
nature of both carbon monoxide and nickel carbonyl largely restricts
its wide applications. Volatile nickel and cobalt species were firstly
detected by merging acidified sample solution with sodium tetrahy-
droborate aqueous solution by Wickstrom and co-workers [22]. Very
recently, Pohl et al. [23] detected nickel and cobalt volatile species
from a HG process although at a very low efficiency. The method
was also used to determine nickel in varied samples by chemical
vapor generation-inductively coupled plasma optical emission spec-
trometry (CVG-ICP-OES) [24–26].
As the CVG efficiency of transition and noble metals is much lower
compared with conventional hydride-forming elements, great efforts
have been made to increase the CVG efficiency of transition and noble
metals in recent years. Trace amount of complexing reagents were
found to be helpful with improving the CVG efficiency of transition
and noble metals, such as sodium diethyl-dithiocarbamate (DDTC)
for Au [27–29], 1,10-phenanthroline for Cu [30], Cd and Zn [31], 8-
hydroxyquinoline (8-HQ) for Zn and Cd [31]. In this work, we found
APDC could remarkably improve the CVG efficiency of nickel and
cobalt. An intermittent-flow injection CVG-AFS instrument was used
for nickel and cobalt determination due to its low sample and reagent
consumption, high sampling frequency, good precision, automated
operation, high sensitivity, selectivity and accuracy, and low cost.

0026-265X/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.microc.2012.04.003
34 C. Zeng et al. / Microchemical Journal 104 (2012) 33–37

Fig. 1. Schematic diagram of experimental setting. GLS: gas/liquid separator.

This method has been successfully applied to the determination of

ultratrace amount of nickel and cobalt in certified reference materials
and water samples, respectively.
Fig. 2. Effect of chelating reagents on the atomic fluorescence intensity of 100 ng mL− 1
nickel, with concentration of respective chelating reagent of 0.05% (m/v); and “without”
2. Experimental means no chelating reagent and 1 mg L− 1 of Ni.

2.1. Instrumentation
(human hair) and GBW (E) 08608 (simulated water sample) were pur-
chased from National Research Center for CRM (Beijing, China). Tap
A Model AFS2202 double-channel non-dispersive atomic fluores-
water was collected in our laboratory, and pond water and river water
cence spectrometer coupled with a programmable intermittent-flow
were obtained from Hehua pond on our campus and Funan River
vapor generation apparatus (Beijing Kechuang Haiguang Instrument
(Chengdu, China), respectively. All samples were stored at 4 °C in a re-
Co., Beijing, China) was used in this work. High intensity nickel and
frigerator before analysis.
cobalt hollow cathode lamps (Hebei Ninqiang Instrument Co., Hebei,
China) specially designed for AFS were employed as the excitation
2.3. Procedure of CVG
source, respectively. The schematic diagram of the intermittent-flow
vapor generation apparatus was shown in Fig. 1. The flow rate of argon
As shown in Table 1, in step 1, two sample delivering tubes were
carrier was controlled by a flowmeter in order to operate at low flow
put into the sample solution and KBH4 solution, respectively; in step
rate. A teflon tube was used as a transfer tube and a reaction tube. The
2, acidified sample solution and KBH4 solution were sucked for 10 s
operation program of peristaltic pump (Table 1) was controlled by a
and sample solution was stored in a sample storage coil; then in
manufacturer AFS software. A microwave oven (Galanz Co., Guangdong,
step 3, the delivering tube for sample solution was changed to the
China) was used to digest the certified reference materials.
carrier solution; and in the last step (step 4), sample solution was
pushed by the carrier into the reaction coil to mix with the KBH4
2.2. Reagents and materials
solution for the CVG reaction. The generated nickel or cobalt volatile
species were separated in the gas–liquid separator and swept into
The stock standard solutions of Ni and Co (1 mg mL− 1) were pur-
the AFS atomizer with the aid of the carrier gas. The AFS atomizer
chased from the National Center for Reference Materials (Beijing,
was described in detail in a previous work [32]. Because enough H2
China). Working solutions were freshly prepared daily by appropriate
could be produced by the reaction of the acidified sample solution
dilution of the stock solutions with distilled deionized water (DDW).
and KBH4 solution, no auxiliary H2 was needed to maintain the Ar/H2
The complexing reagent, 0.02% (m/v) ammonium pyrrolidine dithiocar-
flame. When step 4 is accomplished, the next measurement cycle can
bamate (APDC, Alfa) solution, was obtained by dissolving appropriate
be started.
amount of APDC with DDW. Other complexing reagents, including
ascorbic acid, 8-hydroxyquinoline, dithizone, 5-sulfosalicylic acid, thio-
2.4. Sample preparation
urea, 1, 10-phenanthroline, ethylene diamine tetraacetic acid (EDTA)
and diethyldithiocarbamate (DDTC), were purchased from Chengdu
Certified reference materials of 0.2047 g tea (GBW 07605) and
Kelong Chemical Reagents Co. (Chengdu, China). A solution of 2.0%
0.2326 g human hair (GBW 09101b) were accurately weighed and
(m/v) KBH4 was daily prepared by dissolving appropriate amounts of
KBH4 (Chengdu Kelong Chemical Reagents Co., Chengdu, China) in
0.5% (m/v) potassium hydroxide solution. Nitric acid, hydrochloric
acid, sulfuric acid, potassium hydroxide and hydrogen peroxide were
purchased from Chengdu Kelong Chemical Reagents Co. (Chengdu,
China). Vitamin B12 injection and tablets were purchased from local
market. Certified reference materials, GBW 07605 (tea), GBW 09101b

Table 1
Working program for the intermittent-flow reactor.

Step Flow rate (mL min− 1) Time Function

(s)
Sample/carrier KBH4

1 0 0 6 Put the sampling tube into

sample solution
2 5 5 10 Sampling
3 0 0 6 Change over the sampling
tube into carrier solution
Fig. 3. Effect of APDC concentration on the atomic fluorescence intensity of 100 ng mL− 1
4 8 8 16 Readout and clean up
nickel and 500 ng mL− 1 cobalt, respectively.
 C. Zeng et al. / Microchemical Journal 104 (2012) 33–37
Fig. 4. Effect of HNO3 concentration on the atomic fluorescence intensity of
100 ng mL− 1 nickel and 500 ng mL− 1 cobalt, respectively.
separately dissolved in 8 mL mixture of nitric acids and hydrogen
peroxide (VHNO3:VH2O2 = 6:2) in closed teflon digestion vessel, and
subsequently the samples were digested in a microwave oven with
a digestion procedure from a reference method [33], then the diges-
tion solutions were heated near dryness on a hot plate. After cooling,
the residue was diluted with 1.5% (m/v) HNO3 and 0.02% (m/v) APDC
for the measurement by CVG-AFS. The digestion of Vitamin B12 injec-
tion and tablets were also carried out by the same procedure.
3. Results and discussion
3.1. Selection of complexing reagents
Complexing reagents have been used for improving the CVG effi-
ciency of transition and noble metals upon reaction with tetrahydrobo-
rate. Xu et al. [30] firstly found that phenanthroline could greatly
improve the CVG efficiency of copper. Later, a number of conventionally
used complexing reagents were explored as enhancing reagents for the
CVG of transition and noble metals [11,27–29,31]. Sun et al. [34] found
phenanthroline was able to improve the CVG efficiency of nickel. In this
work, we found that APDC gave better performance for nickel CVG than
that of phenanthroline. As can be seen from Fig. 2, the nickel CVG
efficiency in the presence of APDC was almost twice as that in the pres-
ence of phenanthroline. Several other common complexing reagents,
including ascorbic acid, EDTA, thiourea and DDTC, were also studied.
Generally, the enhancing effects by ascorbic acid and EDTA were
minimal; thiourea, DDTC, phenanthroline and APDC could improve
the nickel CVG efficiency, and APDC gave the best performance. Thus,
APDC was selected for the following investigations and optimal concen-
tration of APDC was found to be 0.02% (m/v), as shown in Fig. 3.
Fig. 5. Effect of potassium tetrahydroborate concentration (in 0.5% KOH) on the atomic
fluorescence intensity of 100 ng mL− 1 nickel and 500 ng mL− 1 cobalt, respectively.
35
Fig. 6. Effect of the carrier gas flow rate on the atomic fluorescence intensity of
100 ng mL− 1 nickel and 500 ng mL− 1 cobalt, respectively.
For the cobalt CVG, many complexing reagents such as 8-
hydroxyquinoline, dithizone, 5-sulfosalicylic acid, phenanthroline,
EDTA, DDTC or APDC were used as an enhancing reagent to improve
the CVG efficiency of cobalt. It was found that APDC had optimal
signal intensity than other complexing reagents. Therefore, APDC
was selected for enhancing reagent for the cobalt CVG. The influence
of APDC concentration on the fluorescence intensity of 500 ng mL − 1
cobalt was studied, with results shown in Fig. 3. Also, the APDC con-
centration of 0.02% (m/v) was selected for use in this work.
3.2. CVG variables
The CVG generation efficiency highly depended on the reaction
acidity and acid types. Preliminary experiments with HCl, HNO3 and
H2SO4 showed that HNO3 was the best medium for the CVG. The con-
centration of HNO3 was studied in the range of 0.5% to 3.0% (v/v) and
1.0% to 4.0% (v/v) for nickel and cobalt, respectively. As can be seen
from Fig. 4, the atomic fluorescence intensity of nickel and cobalt
were all optimal at the HNO3 concentration of 1.5% (v/v). Meanwhile,
the amount of the generated H2 was also enough to maintain the
micro Ar/H2 flame. Therefore, 1.5% (v/v) HNO3 was selected for use.
Nickel CVG with tetrahydroborate derivatization eliminates the
use of toxic carbon monoxide that is needed in conventional nickel
carbonyl generation. A series of KBH4 concentrations in the range of
1.0% to 4.0% (m/v) were studied. As can be seen from Fig. 5, when
KBH4 concentration was 2.0% (m/v), the atomic fluorescence intensity
of nickel and cobalt were optimal. Excessive amount of hydrogen was
produced when KBH4 concentration was higher than 2.0% (m/v),
resulting in dramatic dilution and short residence time of volatile
Fig. 7. Effect of the length of reaction tube on the atomic fluorescence intensity of
100 ng mL− 1 nickel and 500 ng mL− 1 cobalt, respectively.
36 C. Zeng et al. / Microchemical Journal 104 (2012) 33–37

Table 3
Analytical results for Ni in reference materials.

Sample Matrix Found (μg g− 1)* Certified (μg g− 1)

GBW 07605 Tea 4.3 ± 0.5 4.6 ± 0.5

GBW (E) 08608 Water 57 ± 4 60 ± 3
GBW 09101b Human hair 5.32 ± 0.5 5.77 ± 0.4

*Average ± standard deviation (n = 3), and same for Tables 4 and 5.

to 21 cm for nickel and cobalt, respectively (Fig. 7), and 12 cm for

nickel and 15 cm for cobalt was found to be optimal. The length of
the transferring tube between the gas–liquid separator and the AFS
torch was also carefully studied. Guo et al. [24] pointed out that nickel
volatile species may be decomposed during transportation and the
resultant Ni atoms might be adsorbed on the active sites of inner
Fig. 8. Effect of the length of transfer tube on the atmic fluorescence intensity of wall surface of the transferring tube, thus the length of the transfer-
100 ng mL− 1 nickel and 500 ng mL− 1 cobalt, respectively. ring tube should be kept as short as possible. However, in this work,
we found that if the transferring tube was too short, the Ar/H2
analyte species in the atomizer. Therefore, 2.0% (m/v) KBH4 was micro flame would be unstable. The length of transferring tube was
chosen for further experiments. studied in the range of 3 to 13 cm and 5 to 15 cm for nickel and cobalt,
respectively. As can be seen from Fig. 8, the fluorescence intensity of
3.3. AFS instrumental variables nickel and cobalt was found to be the optimal at 7 cm and 9 cm,
respectively.
It was reported that the nickel volatile species was highly unstable
and fast gas–liquid separation should be a prerequisite to prevent 3.4. Evaluation of interference
volatile nickel species decomposition [24]. However, at high carrier
gas flow rate, the dilution of the volatile species and short residence In this work, several metal and metalloid ions were selected for
time of volatile nickel and cobalt species in the atomizer would be dom- evaluation of the selectivity of the proposed method, namely Ca(II),
inant, resulting in the decrease of the atomic fluorescence intensity. The Mg(II), K(I), Na(I), Zn(II), Mn(II), Cu(II), Au(I), Ag(I), Cr(III), Bi(III),
effect of Ar flow rate was studied in the range of 50 to 400 mL min− 1 Pb(II), Cd(II), Ge(IV), Sn(II), Fe(III), Sb(III), As(III), Co(II), Ni(II), Se(IV)
and 100 to 400 mL min− 1 for nickel and cobalt, respectively, with re- and Te(VI). As can be seen from Table 2, macro constituents of Ca(II),
sults shown in Fig. 6. When Ar flow rate was 100 mL min− 1 and Mg(II), K(I), Na(I), Zn(II) and Mn(II) had no significant influence on
150 mL min− 1, respectively, the fluorescence intensity of nickel and nickel and cobalt determination. Some transition metal ions and tradi-
cobalt was optimal. Argon was also used as shield gas in this work in tional hydride generation elements at high concentrations may still
order to prevent extraneous air from entering the flame, alleviating affect the nickel and cobalt CVG.
the interference from the alien environment. The flow rate of the shield
gas was evaluated in the range of 500 to 1200 mL min− 1 for nickel and 3.5. Analytical figures of merit and sample analysis
cobalt. It was found that 900 mL min− 1 argon flow rate was the best.
The length of the reaction tube had a key influence on the atomic Under the optimal experimental conditions, analytical figures of
fluorescence intensity of nickel and cobalt, as it was a compromise merit of the proposed method for the determination of nickel and
between sample amount and fast gas–liquid separation. The length cobalt were established. The calibration curve was linear in the
of the reaction tube was studied in the range of 8 to 18 cm and 11 range of 10 to 300 ng mL − 1 for nickel (R 2 > 0.994) and 50 to
500 ng mL− 1 for cobalt (R2 > 0.998), respectively. The limit of detection
Table 2 (LOD) of 1 ng mL− 1 and 6 ng mL− 1 for nickel and cobalt was obtained,
Interference study of various co-existing metal and metalloid ions. respectively, on the basis of 3σ criterion for 11 measurements of a
Co-existing ions [M]/[Ni (II)]* Recovery (%) [M]/[Co(II)]* Recovery (%) blank. The LOD was equivalent to those by similar techniques [24,25].
The relative standard deviation (RSD) calculated from five measure-
Ca(II) 1000 94 1000 106
K(I) 1000 98 1000 96
ments for nickel at 100 ng mL− 1 and cobalt at 500 ng mL− 1 was 4.7%
Na(I) 1000 96 1000 93 and 4.2%, respectively.
Mg(II) 1000 97 1000 91 To validate the potential application of the proposed method, two
Zn(II) 500 93 10 91 biological certified reference samples (GBW 07605 tea and GBW
Mn(II) 500 91 100 94
09101b human hair) and one certified reference water sample
Cu(II) 200 94 50 96
Ag(I) 200 91 20 93 (GBW (E) 08608) were analyzed for nickel. The analytical results
Au(I) 200 90 20 91
Pb(II) 50 104 50 94
Cr(III) 50 95 50 105 Table 4
Ge(IV) 50 103 100 95 Analytical results for Co in real water samples.
Bi(III) 50 92 50 97
Sample Added (ng mL− 1) Found (ng mL− 1) Recovery (%)
Cd(II) 50 95 20 96
Sn(II) 50 93 50 102 River water 0 – –
Fe(III) 50 91 5 92 100 102 ± 10 102
Sb (III) 20 90 20 97 200 196 ± 12 98
Co(II) 20 90 – – Tap water 0 – –
As(III) 20 94 20 90 100 112 ± 15 112
Se(IV) 20 96 20 98 200 216 ± 20 108
Te(VI) 10 93 10 95 Pond water 0 – –
Ni(II) – – 5 94 100 93 ± 10 93
200 190 ± 18 95
*100 ng mL− 1 for Ni (II) and 500 ng mL− 1 for Co(II).
 C. Zeng et al. / Microchemical Journal 104 (2012) 33–37
Table 5
Analytical results for Co in vitamin B12.
Sample ICP-MS CVG-AFS
Vitamin B12 injection 21.6 ± 0.2 21.0 ± 0.5
(μg mL− 1)
Vitamin B12 tablet 15.03 ± 0.05 13.9 ± 0.4
(μg g− 1)
were in good agreement with the certified values (Table 3). Three
water samples were collected and subjected to cobalt analysis by
the proposed method. The analytical results were shown in Table 4.
Good spike-recoveries were in the range of 93–112%. Vitamin B12
injection and tablets were also analyzed for cobalt. The analytical
results were in good agreement with the determined values by induc-
tively coupled plasma mass spectrometry (ICP-MS) (Table 5).
4. Conclusion
It has been demonstrated that APDC can greatly improve the gen-
eration efficiency of nickel and cobalt volatile species upon tetrahy-
droborate derivatization. A new CVG-AFS method for ultratrace
nickel and cobalt determination was then developed, which offers
the advantages of high sensitivity, good accuracy, rapidity, simplicity,
ease of use and low cost. With compromised experimental conditions
for CVG of nickel and cobalt elements, their simultaneous determina-
tion can be easily realized by using this two channel AFS instrument
at minimum sacrifice of sensitivity.
Acknowledgements
The authors gratefully acknowledge the financial support for this
project from the National Natural Science Foundation of China
(20835003 and 20775051) and the Projects of International Science
and Technology Cooperation and Exchanges of Sichuan Province of
China (2010HH0032).
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