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CHEM. RES. CHINESE U. Available online at www.sciencedirect.

com
2OO7, 23 ( 4 ) , 3 9 9 4 0 3
Article ID 1005-9040(2007) -04-39945 ScienceDirect

Determination of Nickel and Palladium in Environmental Samples by Low


Temperature ETV-ICP-OES Coupled with Liquid-liquid Extraction
with Dimethylglyoxime as Both Extractant and Chemical Modifier *
PAN Liang, QIN Yong-chao * , HU Bin and JIANG Zu-cheng
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, P. R. China

Received June 7 , 2006

A novel method for the determination of nickel and palladium in environmental samples by low temperature ETV-
ICP-OES with dimethylglyoxime( DMG) as both the extractant and chemical modifier has been developed. In this
study, it was found that nickel and palladium can form complexes with dimethylglyoxime(0.05% , mass fraction) at
pH 6.0 and can be extracted into chloroform quantitatively. The complexes can be evaporated into plasma at a suita-
ble temperature( 1400 'I:) for ICP-OES detection. Under the optimized conditions, the detection limits of nickel and
palladium are 0. 48 and 0.40 ng/mL, respectively, while the RSD values are separately 5.0% and 3. 1% ( p = 50
ng/mL, n = 7 ) . The proposed method was applied to the determination of the target analytes in environmental sam-
ples with satisfactory results.
Keywords Low temperature electrothermal vaporization ; ICP-OES ; Dimethylglyoxime; Chemical modifier ; Nickel
and palladium

Introduction lower the vaporization temperature of these refractory


ICP-OES is an important analytical technique for elements, increase the sampling efficiency, and de-
elemental analyses and is widely used in geological, press the memory effect. As a result, better sensitivity
environmental, and biological analyses['-31 . In ICP- and analytical performance can be obtained. Peng
et al, [14,'51 used PMBP as a chemical modifier to deter-
OES, sample introduction is a crucial factor that influ-
ences its analytical performance. Ever since Nixon mine rare earth elements of La, Y and Eu; Wu
et al. t16.171 advanced to used acetyl acetone as a che-
et aZ. [31 first described the use of tantalum filament de-
vice as vaporizer for sample introduction in ICP-OES in mical modifier; Tao et al. ['*I reported the determina-
1974, electrothermal vaporization ( ETV ) has been tion of refractory elements such as B, Nb and V by
widely studied and . When compared with ETV-ICP-OES with 8-hydroxyquinoline as the chemical
normal pneumatic nebulization, ETV is a more efficient modifier. Furthermore, DDTC ( diethyldithiocarbamate)
method for sample introduction. It consumes less and BZA ( benzylacetylactone) were successfully used
amounts of sample and affords higher sensitivity. Fur- as chemical modifier^"^'^] in the ETV-ICP-OES deter-
thermore, it meets the requirement of solid sample de- mination of refractory elements.
termination as well as liquid sample determination. Dimethyglyoxime is a commonly used analytical
However, when it is applied to the analysis of some re- reagent and has been widely used in the spectrophoto-
fractory elements, the sensitivity of determination ob- metric determination of nickel and palladiumt2']. The
viously decreases and severe memory effect cannot be complexes of nickel and palladium with dimethylg-
avoided. Thus, the application of ETV-ICP-OES is li- lyoxime are thermally stable and ~ o l a t i l e [ ~These
~,~~~.
mited. can be sublimed completely at a temperature above
To resolve these problems, analysts have used di- 100 "c under vacuum(< 267 Pa). This implies that
fferent chemical modifiers to improve the analytical per- dimethylglyoxime has the potential to be used as the
formance of ETV-ICP-OES[8-'31. Some organic chela- chemical modifier for the ETV-ICP-OES determination
ting reagents were found to form thermally stable and of Ni and Pd. In our study, a novel method for the de-
volatile complexes with metal ions. These metal com- termination of nickel and palladium in environmental
plexes can vaporize and transport into ICP at a lower samples by ETV-ICP-OES coupled with liquid-liquid
temperature for their determination. The application of extraction using dimethylglyoxime as both the extractant
this low temperature vaporization method can effectively and chemical modifier is described. The factors that af-

* Supported by the National Natural Science Foundation of China( No. 20575048).


* * To whom correspondence should be addressed. E-mail: ycqin@ whu. edu. cn
400 CHEM. RES. CHINESE U. Vol. 23

fect the formation and extraction of the complexes and 1.0% (mass fraction) dimethylglyoxime were added in-
the chemical modification of dimethylglyoxime were to a centrifugal flask and diluted to 10 mL. The mixture
studied. The method developed was applied to the de- was allowed to react for 10 min at mom temperature,
termination of environmental samples and satisfactory which was followed by the addition of 2 mL of chloro-
results were obtained. form. The mixture was sonicated for 10 min and centri-
Experimental fuged at a speed of 3500 r/s for 3 min after which the
1 Apparatus water phase was discarded. The organic phase of 10 pL
The pieces of apparatus used included: a high fre- of the solution was injected into the graphite furnace af-
*
quency ICP source [ 2 kW, ( 27 3 ) MHz, Beijing ter the ignition and stabilization of ICP. Under the
Broadcast Instrument Factory, China ] , a WDG-500- heating cycle, the analyte was evaporated into the plas-
1A type monochromator ( Beijing Second Optics, Chi- ma to determine the height of the signal peak.
na) , a WF-1C type heated device with a WF4C type Results and Discussion
graphite furnace ( Beijing Rayleigh Analytical Instru- 1 Vaporization Behavior of Ni And Pdz*
ment Corp. , China), a WR456 type photomultiplier The complexes of NiZ and Pd2+ with dimethylg-
tube ( Hamamatsu, Japan) , and a U-135C recorder lyoxime are thermally stable and volatile, which can
( Shimadzu , Kyoto, Japan ) . A WX-3000 microwave completely sublime under vacuum at a temperature
accelerated reaction system was also used( Shanghai EU higher than 100 T,These characteristics of both com-
Chemical Instruments Co. , Ltd. , China). The opera- plexes are utilized to vaporize and transport the ele-
tional parameters are shown in Table 1. ments of interest into ICP for determination. Fig. 1
Table 1 Operational parameters of ETV-ICP-OES shows the signal profiles of nickel and palladium deter-
Wavelength/nm Pd 340.3, Ni 341.4 mined by ETV-ICP-OES. It can be observed that in the
Power/kW 2.0
presence of dimethylglyoxime, nickel and palladium
Canier gas flow rate/(L * min-I) 0.6
can be completely evaporated at 1400 T [ Fig. 1 ( A ) 3
Coolant gas flow rate/( L * min-l ) 16
Plasma gas flow rate/( L min )- 0.8 and a sharp signal peak can be obtained. No obvious
Observation heighvmm 12 memory signal is observed in the cleaning step at
Drying temperature/% SO( ramp 15 s, hold 30 s) 2600 c [ Fig. 1 ( B) 1. On the contrary, weaker and
Vaporization temperature/C 1m(ramp 0 s, hold 5 s) wider signal peaks are observed in the absence of dime-
Cleaning temperatudC 2500(rampO hold4 a )
8,
thylglyoxime[ Fig. 1 ( C ) ] at 2500 r: and obvious me-
Sample volume/bL 10
mory signal can be observed at 2600 C [ Fig. 1 ( D ) ].
2 Reagents
Stock standard solutions of Ni2+( 1 mg/mL) and
Pd2+ ( 1 mg /mL) were prepared via standard me-
thods. The standard working solutions were prepared by
stepwise dilution of the stock standard solutions. Dime-
thylglyoxime( A. R. ) was purchased from Beijing Insti-
tute of Chemical Reagents and was prepared into a
1.0% ( mass fraction) solution in ethanol. The pH of
analytical solution was adjusted with a 0. 1 moVL 5s
NaOH-KH,PO, buffer solution. Other reagents used in -
11s
the experiments were of analytical reagent grade. Dou-
bly distilled water was used all through. Fig. 1 Signal profdes of nickel and palladium
( A ) Evaporated at 1800 qC ; ( C ) evaporated at 2500 9: ; ( B ) and
Artificial seawater was prepared by following the ( D ) cleaningat2600qC;p(NiZ*) a n d p ( P d z + ) : 20ng/mLfor
method reported in ref. [ 17 ] : 0.3675 g of CaC1, ( A ) and ( B ) ; 1 PdmLfor ( C ) and ( D ) .
2 H z 0 , 3.275 g of MgSO, 7H,O, and 6.975 g of The effect of temperature on the vaporization be-
NaCl.were dissolved in 250 mL doubly distilled water. havior of an analyte was optimized for further study.
Lake water sample was collected from the East Lake of The sample was injected into the graphite furnace and
Wuhan , China. dried at 100 C to remove the solvent. After that, the
3 General Procedures signal intensities were recorded at various tempera-
Solution of 2 . 0 mL of 100 ng/mL NiZ or Pd2+, +
tures. The results shown in Fig. 2 indicate that nickel
1 . 0 mL of NaOH-KH,PO, buffer, and 0.5 mL of and palladium can be evaporated at 800 r: in the pre-
No. 4 PAN Liang et al. 40 1

sence of dimethylgloxime( Fig. 2 curve u ) . With the in- be extracted with chloroform quantitatively. Therefore,
crease in vaporization temperature, the signal intensi- pH 6.0 was selected for subsequent analysis.
ties also increase gradually. When the vaporization
temperature is higher than 1400 T , the signal intensi-
ties reach the maximum and remain constant, which in-
dicates that nickel and palladium are evaporated com-
pletely. On the other hand, without dimethylglyoxime
( Fig. 2 curve b ) , the signal intensities increase gradu-
ally as the temperature is increased up to 2500 T and
no plateau can be found in the vaporization curves,
4.0 5.0 6.0 70 8.0
which indicate that nickel and palladium cannot be
PH
evaporated quantitatively at a temperature lower than
Fig.3 Effect of pH
2500 T .
p( NiZ+) =20 ng/mL; p ( Pd2+) =20 ng/mL.

3 Effect of the Mass Fraction of Dimethylglyoxime


The mass fraction of chelating reagent is an impor-
tant factor that influences the results of determination.
It is undoubtedly clear that metal ions cannot form com-

B
a
i
z
0.21
0.0 I
d a

I I I I I
plexes completely if the mass fraction of chelating rea-
gent is extremely low.
It is shown in Fig. 4 that the signal intensities of
600 1000 1400 1800 2200 2600 nickel and palladium vary along with the mass fraction
1/% of dimethylglyoxime. With increasing mass fraction of
Fig. 2 Effect of vaporization temperature on signel in- dimethylglyoxime, the signals of nickel and palladium
tensity are gradually enhanced. When the mass fraction rea-
a. With dimethylglyoxime [ p ( Ni2 ) = p ( Pd2 ) = 20
ches 0.03% , the signal intensities approach the maxi-
+ +

ng/mL] ; b. without dimethylglyoxime [ p ( NiZ+) =


p( Pd ) = 1 pg/mL].
mum. Owing to the limit of solubility, the optimal mass
fraction of dimethylglyoxime selected was 0.05 % .
The optimization of the vaporization time was also
$ 1.0
performed. It is found that with dimethylglyoxime, an d
0
.-
intact signal peak and the maximum signal intensity can 2 0.8
3
be achieved when the vaporization time is longer than .B
;a 0.6
3 ~ ( 1 4 0 0T ) . E
.9
All results obtained indicate that the use of dime-
thylglyoxime as chemical modifier has improved the va- ii 0.4
0.2
porization behavior of nickel and palladium. The vapo-
rization temperature is lowered markedly and the vapo- 0.00 0.01 0.02 0.03 0.04 0.05 0.06
rization is complete, and the shape of the signal peak is Mass fraction of dimethylglyoxime(%)
sharper and more symmetrical. In the actual analysis, Fig. 4 Effect of the mass fraction of chelating reagent
1400 T and 5 s were selected as the operational vapo- p( NiZ+) =20 ng/mL; p ( PdZ+) =20 ng/mL.

rization conditions. 4 Amount of Extraction Solvent


2 Effect of pH on Signal Intensity In liquid-liquid extraction procedures, the volume
The acidity of a medium is an important factor that ratio of water phase to organic phase has remarkable in-
influences the formation and extraction of the comple- fluence on the extraction efficiency. A higher phase ra-
xes. In this study, the variations in the signal intensi- tio usually indicates a higher concentration of analyte in
ties of nicke1 and palladium in an acidic medium pH organic phase but lower extraction efficiency. In this
4 . 0 to pH 7.5 were studied. As seen in Fig. 3, when study, chloroform was selected as the extraction solvent
the pH is between 5.5 and 7.5, the maximum signal and the signal intensities of target elements were stud-
intensity is obtained and it remains a constant. It indi- ied at various phase ratios(5: 1 , 10: 1 , 20: 1 , 50: 1,
cates that under this acidic condition, Ni2+ and Pd2+ 100: 1 ) . More intense signals can be obtained under
can form complexes with dimethylglyoxime, which can higher phase ratios. However, if the phase ratio is up
402 CHEM. RES. CHINESE U. Vol. 23

to 100, the organic phase cannot be recovered quantita- and palladium, respectively. The relative coefficients
tively because of the dissolution of chloroform in water are 0. 99676 and 0. 99673, respectively. It is noticed
and diflicult phase separation. Therefore, the volume that the calibration curves deviate from the origin espe-
ratio of water to chloroform was selected to be 50: 1. cially that of palladium. This deviation is probably
5 Effect of Coexisting Ion caused by the deposition of palladium complexes in the
In the analyses of real samples, abundant coexis- transmission procedure. The detection limits that were
ting ions will probably influence the determination of calculated to be three times the standard deviation of
concerned elements. Therefore, solutions of 50 ng/mL the reagent blank signal( n = 7 ) in accordance with IU-
Ni2' and PdZ+containing the most abundant ions in en- PAC recommendations are 0.48 ng/mL for nickel and
vironmental samples including K' , Na' , Ca2' , and 0.40 ng/mL for palladium. The relative standard devi-
M i + etc. were prepared, extracted, and determined ation is 5.0% for nickel and 3. l % for palladium
according to the aforementioned procedure. The tole- [p(NiZ') a n d p ( P d Z ' ) : 20 ng/mL, n = 5 ] .
rance limits of coexisting ions within which the coexis- Environmental Sample Analysis
ting ions do not interfere with the determinations of tar- 1 Water Sample Analysis
get elements( relative error of result is less than 10%) Water sample of 5 mL( artificial seawater and the
are given in Table 2. East Lake water) , 1.0 mL of a 0. 1 moVL buffer solu-
Table 2 Tolerance l i t s of coexisting ions tion of NaOH-KH,PO, , and 0.5 mL of a 1.0% ( mass
Tolerance limit/ Tolerance limit/ fraction) dimethylglyoxime solution were added in a 10
Coexisting ion Coexisting ion
( pg mL-l) ( pg * mL 1 mL centrifugal flask. The pH value of the mixed solu-
K+ 2oooo Fez + 10
Cu2 10
tion was adjusted to 6.0 by dropwise addition of HC1 or
Na + 2oooo +

CaZ + 2500 Zn2 + 20 NaOH solution. After dilution, the resulting solution
MgZ + 2500 Mn2 + 10 was 10 mL, to which 2 mL of chloroform was added
Fe3 + 20 ~ 1 3 + 20 and the extraction was operated according to the proce-
6 Linearity, Relative Standard Deviation, and dure described previously. The contents of nickel and
Detection Limit palladium were extremely low in the water samples to
In the concentration scale of 5 to 100 ng/mL, the be determined. Therefore, spiked water samples were
proposed method shows good linearity for the determi- analyzed so as to evaluate the reliability of the method.
nation of nickel and palladium; the regression equa- The results of determination are given in Table 3 and
tions of the calibration curves are y = 0 . 2 1 -~ 0.22 and the recoveries of the concerned elements are 91% to
y = 0.2% + 1 . 2 5 [ y: signal intensity ( a. u. ) ; x : con- 102.8%.
centration of concerned element ( ng/mL) ] for nickel
Table 3 Analytical results for water samples
- mL-' ) (means
~ ~ ~~~

Sample Element Spiked/(ng mL-l) Measured/( ng k SD, n =5 )


Artificial seawater Ni 0 -
50 51.4k3.3
100 94.8 *2.8
Pd 0 -
50 *
45.5 1. 8
100 98. 8 * 6 . 5
East Lake water Ni 0 -
50 50. 5 f 2. 3
100 101.5 k 3 . 5
Pd 0 -
50 50. I k0. 5
100 94. I k4. 5
2 Certified Reference Material ( GBW07301a ) to near dryness and 100 mL of water was added to dis-
Analysis solve the residue. The solution was transferred into a
Stream Sediment GBW07301a of 0.500 g was di- beaker, and an NaOH solution was added dropwise to
gested in a microwave digesting system ( temperature: adjust the pH value to 6.0, and the precipitate was re-
150 'T , pressure: 2.03 x lo6 Pa, power: 500 W , moved by filtration. The filtrate was diluted to 250 mL.
time: 10 min) , with 8 mL of aqua regia and 2 mL of The obtained sample solution was analyzed via the pro-
HF. After digestion, the resulting mixture was heated posed method. The result is shown in Table 4. Student
No. 4 PAN hang et d. 403

t-test was applied to evaluate the significance difference cance difference between the determined and the certi-
between the determined and the certified values. After fied values. This indicates that reliable results can be
the analysis, it was found that there was no signifi- obtained using the proposed method.
Table 4 Analytical results for certified reference material
Reference material Element - '
Certified d u e / ( pg g - ) - '
Measured/ ( p,g g - ) ( means i SD , n = 5 )
Stream sediment( GBWO7301a) Ni 56 *7 53.4 *3.5
Pd 5' 4.7i0.3
* Spiked value.
Conclusions Grotti M., Abelmoechi M. L., F . , et a l . , Anal. Bio-
anal. Chem., 2003, 375(2), 242
When compared to conventional ETV-ICP-OES
Kirkbright G. F. , Snook R. D . , Anal. C h . , 1979,
(without any chemical modifier), the usage of dime- 51(12), 1938
thylglyoxime as both extractant and chemical modifier Huang M., Jiang Z. C., Zeng Y. E . , J. Anal. Atom. Spec-
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Sun Y. C. , Hsieh C. H . , 1. Anal. Atom. Spectrom., 2002,
ted as the ratio of the slope of the calibration curves).
I 7 ( 2 ) , 94
The enhancement for nickel was 52.5 times and that Hu Bin, Jiang Zu-cheng, Zeng Yun-e, et 01. , Anal. Sci. ,
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Hang Yi-ping, Qin Yong-chao, Jiang Zu-cheng, et al. , Chem.
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