Biol Trace Elem Res (2011) 144:1381–1393

DOI 10.1007/s12011-011-9078-x

Development of Dispersive Liquid–Liquid

Microextraction Based on Solidification of Floating
Organic Drop for the Determination of Trace Nickel

Yukun Wang & Jingwen Zhang & Bin Zhao & Xin Du &
Jingjun Ma & Jingci Li

Received: 15 November 2010 / Accepted: 9 May 2011 /

Published online: 20 May 2011
# Springer Science+Business Media, LLC 2011

Abstract A liquid-phase microextraction technique was developed using dispersive liquid–

liquid microextraction based on solidification of floating organic drop combined with flame
atomic absorption spectrometry, for the extraction and determination of trace amounts of
nickel in water samples. Microextraction efficiency factors, such as the type and volume of
extraction and dispersive solvents, pH, extraction time, the chelating agent amount, and
ionic strength, were investigated and optimized. Under optimum conditions, the calibration
graph was linear in the range of 4.23–250 μg L−1 with a detection limit of 1.27 μg L−1. The
relative standard deviation for ten replicate measurements of 10 and 100 μg L−1 of nickel
were 3.21% and 2.55%, respectively. The proposed method was assessed through the
analysis of certified reference water or recovery experiments.

Keywords Dispersive liquid–liquid microextraction . Solidification of floating organic

drop . Flame atomic absorption spectrometry . Preconcentration . Nickel

Introduction

Nickel is a naturally occurring element found in rocks, soil, water, biological cycles,
and atmospheric fallout. It is the metal component of the enzyme urease and as such
considered to be essential to plants and some domestic animals. Compared with other
transition metals, Ni is a moderately toxic element. However, it is known that excess
inhalation of nickel and its compounds can lead to serious problems, including
respiratory system cancer, malignant tumors, and dermatological problems [1–4]. With
the development of industry, more and more nickel enters waters from industrial
processes and waste disposal. According to the international regulation on water quality,
the approved content of nickel in drinking water is 20.0 μg L−1 [3]. It is clear that

Y. Wang : J. Zhang : B. Zhao : X. Du : J. Ma (*) : J. Li (*)

Hebei Key Laboratory of Bioinorganic Chemistry, College of Science,
Agricultural University of Hebei, Baoding 071001 Hebei, People’s Republic of China
e-mail: majingjun@hebau.edu.cn
e-mail: jingcili63@yahoo.com.cn
1382 Wang et al.

determination of nickel, at trace level, in water and environmental samples is of great

significance from the public health and environmental point of view [5]. Therefore,
highly sensitive determination methods of trace Ni in environmental samples need to be
established.
Modern instrumental methods including spectrometry, inductively coupled plasma mass
spectrometry, inductively coupled plasma atomic emission spectrometry, and atomic
absorption spectrometry, etc. [6–8] have been used for determining traces of metal ions
in various media. Flame atomic absorption spectrometry (FAAS) is especially the most
widely used in this group due to its low cost, friendly operation, high sample throughput,
and good selectivity. However, difficulties still lie in the direct determination of Ni at very
low concentrations because of their low abundance levels in the samples, insufficient
sensitivity of this technique as well as the high complexity of the sample matrices [9].
Under these circumstances, in order to determine trace levels of Ni, a preceding separation
and enrichment step prior to the determinations may be beneficial. Several methods have
been proposed for separation and preconcentration of trace Ni, including liquid–liquid
extraction (LLE) [10–12], coprecipitation [13], ion exchange [14], solid-phase extraction
(SPE) [15–17], and cloud point extraction [18–20]. Although satisfactory results can be
obtained with the above mentioned separation/preconcentration techniques, they have some
drawbacks such as large consumption of reagent, low enrichment factor, multistage
operation, and lengthy separation.
Modern trends in analytical chemistry now lean toward the simplification and
miniaturization of sample preparation, as well as the minimization of the organic solvent
used. So solid-phase microextraction and liquid-phase microextractions (LPME), the
miniaturizing of traditional SPE and LLE, have emerged as new attractive alternatives for
sample preparations, which can save time, labor, and solvent consumption and therefore can
improve the analytical performance of the procedure. Recently, several different types of
LPME have been developed, including single drop microextraction [21, 22], hollow fiber
LPME [23, 24], and homogeneous liquid–liquid extraction [25, 26]. Microextraction
techniques are fast, simple, inexpensive, environmentally friendly, and compatible with
many analytical instruments. Nevertheless, some drawbacks, such as instability of the
droplet and relatively low precision, are often reported [27]. Subsequently, Rezaee and
co-workers developed a novel microextraction technique, termed dispersive liquid–liquid
microextraction (DLLME) [28]. This technique is based on the formation of tiny droplets
of the extractant in the sample solution using a water-immiscible organic solvent
(extractant) dissolved in a water-miscible organic dispersive solvent [29]. The advantages
of the DLLME method are speed, low cost, and high enrichment factors. However, the
extract solvent is limited by the solvents used; these solvents, such as chlorobenzene,
chloroform, and tetrachloromethane, have a higher density than water and are toxic and
environment unfriendly.
In 2007, Khalili Zanjani et al. [30] developed a novel mode of liquid-phase
microextraction based on solidification of floating organic droplet (LPME-SFO), in which
small volume of the extractant with low density, low toxicity, and proper melting point near
room temperature (in the range of 10–30°C) was used. At low temperatures, the extractant
is readily solidified and floated on the surface of aqueous solution. Thus, it can be collected
easily. Since it was reported, LPME-SFO has been applied in the preconcentration of
organic compounds and metal ions [31–33] that in water samples. It is simple, accurate,
high precision, low cost, and environmentally friendly and high enrichment factor.
However, the extraction time in LPME-SFO is usually prolonged and often needs about
30 min, which cannot meet the needs of rapidity analysis.
Development of Dispersive Liquid–Liquid Microextraction 1383

To overcome the above problem, Leong et al. combined DLLME and LPME-SFO,
developing a new microextraction technique termed dispersive liquid–liquid micro-
extraction based on solidification of floating organic droplet (DLLME-SFO) [34]. In
DLLME-SFO, the appropriate extraction solvent (low density, low toxicity, and proper
melting point near room temperature) dissolved in a water-miscible dispersive solvent was
rapidly injected into aqueous sample by syringe. A cloudy solution containing fine droplets
of extraction solvent dispersed entirely in the aqueous phase was formed. After
centrifugation, the extractant droplet floated on the top of the test tube was easily solidified
in an ice bath and then carried out from the aqueous sample to a new test tube where it
melted immediately. The melted organic solvent is used for analytes determination. In this
method, the analysis time can be as fast as DLLME and is much shorter than LPME-SFO
[35], and the extractant is of lower density rather than water and lower toxic but higher
extraction efficiency for heavy metal ions in contrast to DLLME [36].
In this study, the possibility of enrichment by DLLME-SFO was considered.
Ammonium pyrrolidine dithiocarbamate (APDC) was selected as the chelating reagent,
and a new microextraction method combined with FAAS was developed for separation,
enrichment, and determination of nickel in aqueous samples. In order to obtain a high
extraction efficiency, the effect of different parameters affecting the complex formation and
extraction conditions (such as the type and volume of extraction and dispersive solvents,
pH, extraction time, the chelating agent amount, and ionic strength) were investigated and
optimized.

Experimental

Reagents and Solutions

A stock standard solution of nickel at a concentration of 1,000 μg mL−1 was purchased

from the National Institute of Standards (Beijing, China). Working standard solutions were
prepared by serial dilutions of the stock solution with deionized water immediately prior to
analysis. The chelating agent, 0.2 gL−1 APDC, was prepared by dissolving the appropriate
amount of APDC (Beijing Chemistry Reagent Company, Beijing, China) in deionized
water. 1-Dodecanol, n-hexadecane, and 1-bromohexadecane, as extraction solvents, were
obtained from Beijing Chemical Reagents Company (Beijing, China). Sodium chloride
(NaCl), acetone, acetonitrile, tetrahydrofuran (THF), ethanol, and methanol were from
Tianjin Fuchen Chemical Reagent Factory (Tianjin, China).
Nitric acid (0.1 mol L−1) was used to adjust the pH 2–3, and ammonium acetate buffers
(0.2 mol L−1) were prepared by adding an appropriate amount of acetic acid to ammonium
acetate solutions resulting in solutions of pH 4–6. For pH 7–8, a phosphate (0.2 mol L−1)
buffer solution was prepared by adding an appropriate amount of disodium hydrogen
phosphate to sodium dihydrogen phosphate. Ammonium chloride buffer solutions
(0.2 mol L−1) were prepared by adding an appropriate amount of ammonia to ammonium
chloride solutions, resulting in solutions of pH 9–10.
All reagents used were of analytical reagent grade. Deionized water was used in the
preparation of all solutions. The laboratory glassware was kept in 10% nitric acid for at
least 24 h and subsequently washed four times with deionized water.
Tap, sea, and river water samples used for development of the method were collected in
polytetrafluoroethylene containers from Hebei province, filtered using a 0.45-μm pore-size
membrane filter to remove suspended particulate matter, and stored in a refrigerator in the dark.
1384 Wang et al.

Apparatus

The experiments were performed with a Hitachi Z-5000 atomic absorption spectrometer
(Japan) equipped with Zeeman background correction. A nickel hollow cathode lamp
operating at 232.0 nm was utilized as the radiation source. The instrumental parameters
were adjusted according to the manufacturer’s recommendations. All pH measurements
were carried out using a pH3-3C digital pH meter equipped with a combined glass-calomel
electrode (Hangzhou Dongxing Instrument Factory, Hangzhou, China). A Model LD5-2A
centrifuge (Beijing Jingli Instrument Factory, Beijing, China) was used to accelerate the
phase separation.

DLLME-SFO Procedure

A 10.0-mL sample of standard solution containing 250 μg L−1 of nickel was poured into a
screw cap glass test tube; 1.0 mL acetate buffer and 1.8 mL APDC (0.2 gL−1) solution were
added. Then, 0.75 mL of ethanol (as disperser solvent) containing 80 μL of 1-dodecanol (as
extraction solvent) was injected rapidly into the sample solution by using 1.0 mL syringe. A
cloudy solution that consists of very fine droplets of 1-dodecanol dispersed into aqueous
sample was formed, and the analytes were extracted into the fine droplets in a few seconds.
Emulsions were then disrupted by centrifugation at 3,000 rpm for 2 min, which resulted in
the organic phase floating on the surface of the solution. After this process, the test tube
was transferred into an ice bath and the organic solvent solidified after 1 min. The solidified
solvent was then transferred into a conical vial where it melted immediately at room
temperature. Finally, the extract was diluted to 500 μL with ethanol and manually injected
into the flame atomic absorption spectrometer.

Results and Discussion

Selection of Extracting and Dispersive Solvent

The extraction solvent in DLLME-SFO should fulfill the following requirements: This
solvent must be immiscible with water and dissolve the analyte better than water to promote
the extraction of the analytes. What is more, it should have low volatility, low toxicity,
lower density than water, and a low melting point around room temperature (in the range
from 10°C to 30°C). Accordingly, three extraction solvents, i.e., 1-bromohexadecane
(melting point 17.3°C), n-hexadecane (melting point 18°C), and 1-dodecanol (melting point
24°C), were examined in the extraction of nickel. On the other hand, selection of the
dispersive solvent is also a key step. It should be miscible with both water and the
extraction solvents and could form a cloudy state when injected with the extractant into
aqueous samples. Thus, acetone, methanol, THF, acetonitrile, and ethanol were selected for
the study. Due to the limited number of the organic extractants, all combinations of using 1-
dodecanol, n-hexadecane, and 1-bromohexadecane as extractant with acetone, methanol,
ethanol, acetonitrile, and THF as dispersive solvent were investigated. The experiments
showed that n-hexadecane and 1-bromohexadecane cannot be dissolved in all the five
dispersive solvents possibly due to their strong hydrophobicity; the best extraction efficiency
for the target analyte was obtained when 1-dodecanol was used as extraction solvent and
ethanol as dispersive solvent. Based on the above results, 1-dodecanol and ethanol were
selected as the extraction and dispersive solvents in subsequent studies.
Development of Dispersive Liquid–Liquid Microextraction 1385

Effect of the Disperser Solvent Volume

As mentioned in the previous section, ethanol was chosen as disperser. In order to optimize
its volume, different volumes of ethanol (0 to 1.75 mL with 0.25 mL intervals) along with
120 μL 1-dodecanol as the extraction solvent were investigated. The results in Fig. 1
showed that the absorbance increased by increasing the volume of ethanol to 0.75 mL.
Slightly reduction in the absorbance was observed after the volume of ethanol exceeded
1.00 mL. At low volume, the extractant could not disperse well in the sample solution, and
cloudy solution was not formed completely. Reversely, at high volume, the solubility of
complex in water increased by the increase of the volume of ethanol. Finally, 0.75 mL
ethanol was chosen as the optimum volume.

Effect of Extraction Solvent Volume

To evaluate the effect of the extraction solvent volume, different volumes of 1-

dodecanol in the range of 30–120 μL (at 10 μL intervals) were examined in the
preconcentration procedure. The results illustrated in Fig. 2 show that, by increasing the
volume of 1-dodecanol, the analytical signal increases, reaching a maximum value at
80 μL and then remaining constant. Therefore, in the subsequent studies, 80 μL was used
as the optimum volume of the extraction solvent. After the preconcentration procedure,
the obtained volume of 1-dodecanol was 78±2 μL.

Influence of pH

The separation of metal ions by DLLME-SFO involves prior formation of a complex with
sufficient hydrophobicity that allows it to be extracted into the small volume of the floated
phase, where the desired preconcentration is obtained. The pH plays a unique role in metal
chelate formation and subsequent extraction. The effect of pH on the complex formation
and extraction of Ni from water samples was studied in the range of 2.0–10.0 by using
nitric acid, ammonium acetate, phosphate, and ammonium chloride. The results
demonstrated in Fig. 3 reveal that the analytical signal is nearly constant in the pH range
of 5.0–6.0. The progressive decrease in extraction of nickel at low pH is due to competition

Fig. 1 Effect of the volume of 0.40

dispersive solvent on the extrac-
tion of nickel by the DLLME- 0.35
SFO method. Extraction condi-
tions: sample volume, 10.0 mL; 0.30
extraction solvent, 120 μL 1-
dodecanol; dispersive solvent, 0.25
Absorbance

ethanol; pH, 5–6; APDC amount,

0.36 mg 0.20

0.15

0.10

0.05

0.00
0.00 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00
Volume of dispersive solvent/mL
1386 Wang et al.

Fig. 2 Effect of the volume of 0.40

extraction solvent on the extrac-
tion of nickel by the DLLME- 0.35
SFO method. Extraction condi-
tions: sample volume, 10.0 mL; 0.30
extraction solvent, 1-dodecanol;
dispersive solvent, 0.75 mL etha- 0.25

Absorbance
nol; pH, 5–6; APDC amount,
0.36 mg 0.20

0.15

0.10

0.05

0.00
20 30 40 50 60 70 80 90 100 110 120 130
Volume of extraction sovent/µL

of the hydrogen ion with the analyte for reaction with APDC. At higher pH values, the
hydrolysis of cations occurs. Thus, the value of pH 5.0 was selected for the following
experiments.

Influence of the Amount of APDC

The effect of the amount of APDC on the absorption was studied, and the results are shown
in Fig. 4. The amount of APDC was increased until the total extraction of Ni was obtained.
The absorbance was stable when the APDC volume was higher than 1.5 mL, indicating
complete complexation. When the volume of APDC is greater than 1.8 mL, the analytical
signal decreases. This effect is probably caused by competition between complexing agent
molecules, which are in excess in the solution, and Ni complex molecules for extraction
solvent interaction. Therefore, a APDC volume of 1.8 mL was chosen as the optimum
amount for the nickel determination.

Fig. 3 Effect of pH value on the 0.40

extraction of nickel by the
DLLME-SFO method. Extraction 0.35
conditions: sample volume,
10.0 mL; extraction solvent,
0.30
80 μL 1-dodecanol; dispersive
solvent, 0.75 mL ethanol; APDC
Absorbance

amount, 0.36 mg 0.25

0.20

0.15

0.10

0.05
1 2 3 4 5 6 7 8 9 10 11
pH
Development of Dispersive Liquid–Liquid Microextraction 1387

Fig. 4 Effect of the amount of 0.40

APDC on the extraction of nickel
by the DLLME-SFO method.
Extraction conditions: sample 0.35
volume, 10.0 mL; extraction sol-
vent, 80 μL 1-dodecanol; disper- 0.30
sive solvent, 0.75 mL ethanol;

Absorbance
pH, 5; concentration of APDC,
0.2 gL−1 0.25

0.20

0.15

0.10
0.0 0.3 0.6 0.9 1.2 1.5 1.8 2.1 2.4 2.7 3.0
APDC volume/mL

Effect of the Extraction Time

Extraction time is an important factor influencing the extraction efficiency. In DLLME-

SFO, extraction time is defined as the time interval between injection the mixture of
disperser solvent and extraction solvent and the time starting to centrifuge. The effect of
extraction time was examined in the range 0–60 min with constant experimental conditions.
As a result, extraction time has no impact on extraction efficiency. It may be the large
contact surface area between extraction solvent and aqueous phase. Thereby, transition of
analytes from aqueous phase to extraction solvent is fast. In this method, extraction time is
very short and the most time-consuming step is the centrifugation.

Effect of Salt

To investigate the influence of ionic strength on performance of DLLME-SFO, various

experiments were performed by adding varying NaCl amount from 0% to 5% (w/v). Other
experimental conditions were kept constant. By increasing the NaCl from 0% to 5%, the
volume of the floated phase increases slightly from 78 to 82 μL. The results showed that
salt addition has no significant effect on the enrichment factor, perhaps because of the two
opposite effects of salt addition DLLME-SFO of nickel: One involves increasing the
volume of the floated phase, which decreases the enrichment factor, and the other is the
salting out effect that increases the enrichment factor [37, 38]. Therefore, the enrichment
factor is nearly constant by increasing the amount of sodium chloride, and the extraction
experiments were carried out without adding salt.

Effect of Coexisting Ions

The effects of coexisting ions on the recovery of Ni in real water samples were studied. In
these experiments, 10.0 mL solutions containing 250 μg L−1 of nickel and various amounts
of interfering ions were treated according to the recommended procedure. If the resulting
FAAS signal showed a ±5% variation, the foreign ion was considered to interfere in Ni
determination. The results obtained are given in Table 1.
1388 Wang et al.

Table 1 Effect of interfering ions on the recovery of 250 μg L−1 Ni in water samples using DLLME-SFO-
FAAS

Interferent Concentration (μg L−1) Interferent/Ni2+ ratio Recovery (%)

Na+ 25,000,000 100,000 96.4

K+ 25,000,000 100,000 95.8
Ba2+ 25,000 100 95.5
Mn2+ 25,000 100 96.8
Ca2+ 25,000 100 95.3
Mg2+ 25,000 100 96.7
Hg2+ 25,000 100 97.2
Ag+ 20,000 80 96.1
Cd2+ 20,000 80 97.6
Bi3+ 12,500 50 98.4
Co2+ 12,500 50 96.5
Cu2+ 12,500 50 95.2
Pb2+ 12,500 50 96.2
Al3+ 12,500 50 97.0
Fe3+ 12,500 50 96.4
As5+ 12,500 50 96.0
Zn2+ 10,000 40 95.9
Sn4+ 10,000 40 97.5
Fe2+ 10,000 40 99.1
Cr3+ 10,000 40 98.8
As3+ 7,500 30 95.5
Cl− 25,000,000 100,000 100.2
NO3− 25,000,000 100,000 97.2
CH3COO− 250,000 1,000 97.4
PO43− 250,000 1,000 96.8
SO42− 25,000 100 97.4
Cr2O72− 25,000 100 97.5

Analytical Figures of Merit

The analytical characteristics of the proposed method, such as linear range, limit of detection,
reproducibility, correlation coefficient, and enrichment factor, obtained by processing standard
solutions of Ni under the optimum conditions described are summarized in Table 2. The
calibration graph was linear in the range of 4.23–250 μg L−1 of nickel. The equation of the
calibration curve after the preconcentration procedure was given as A ¼ 1:72  103 C þ
0:0021 with a correlation coefficient of 0.9991 (n=10), where A is the atomic absorbance for
nickel in the rich phase at 232.0 nm and C is the concentration of Ni2+ in the sample solution
in micrograms per liter. The limit of detection and quantification defined as 3SB/m and 10SB/m
(where SB is standard deviation of the blank and m is the slope of the calibration graph) were
1.27 and 4.23 μg L−1, respectively. The relative standard deviation (RSD) for ten replicate
measurements of 10 and 100 μg L−1 of nickel were 3.21% and 2.55%. Phase volume ratio,
calculated as the ratio between the volume of the aqueous phase (13.55 mL) and the final
injection volume (0.5 mL ethanol containing the analyte), was 27.1 times.
Development of Dispersive Liquid–Liquid Microextraction 1389

Table 2 Analytical characteristics of DLLME-SFO-FAAS for determination of Ni

Analytical parameters Analytical feature

Linear range (μg L−1) 4.23–250

Slope 1.72×10−3
Correlation coefficient 0.9991
Detection limit (μg L−1) 1.27
Quantification limit (μg L−1) 4.23
Relative standard deviation (RSD, %; n=10, 10 μg L−1) 3.21
Relative standard deviation (RSD, %; n=10, 100 μg L−1) 2.55
Enrichment factora 158
Enrichment factorb 24.6
a
The preconcentration factor is the ratios of the nickel concentration in the solidified floating organic drop
(78 μL) to that initially in the bulk phase
b
The preconcentration factor is the ratios of the nickel concentration in 0.5 mL ethanol to that initially in the
bulk phase

The enrichment factor [39, 40] is defined as the ratios of the nickel concentration in the
organic-rich phase to that in the bulk phase, initially. Equation 1 was used for calculation of
the enrichment factor. In this equation, Cs is the nickel concentration (micrograms per liter)

Table 3 Analytical results of nickel determination (dissolved fraction) in certified reference materials and
spiked natural water samples with the DLLME-SFO-FAAS method (n=3)

Sample Certified Added Founde Recovery (%)

GSBZ 50009-88 (μg L−1) 9.97±0.48 – 9.55±0.45 95.8

19.94±0.96 – 19.64±0.86 98.5
GSB 07-1186-2000 (μg L−1) 6.99±0.25 – 6.65±0.30 95.1
13.98±0.5 – 13.46±0.48 96.3
Tap watera (μg L−1) 0.0 <LOD –
5.0 4.75±0.21 95.0
10.0 9.63±0.38 96.3
Seawaterb (μg L−1) 0.0 10.53±0.37 –
10.0 20.41±0.78 98.8
15.0 25.61±0.92 100.5
River waterc (μg L−1) 0.0 6.36±0.25 –
5.0 11.17±0.40 96.2
10.0 16.31±0.56 99.5
River waterd (μg L−1) 0.0 5.40±0.22 –
5.0 10.22±0.34 96.4
10.0 15.13±0.50 97.3
a
From drinking water system of Baoding, China
b
Beidaihe seawater, Qinhuangdao, China
c
Yongding river water, Baoding, China
d
Tang river water, Baoding, China
e
Mean of three experiments ± standard deviation
1390 Wang et al.

Table 4 Characteristic performance data obtained by using DLLME-SFO-FAAS and other techniques in
determination of nickel

Method LODa RSDb Enrichment Sample Calibration Extraction References

(μg L−1) (%) factor consumption range (μg L−1) time (min)
(mL)

DLLME- 0.033 8.2 200 6 – 2 [5]

GFAAS
CPE-FAAS 1.2 2.3 39c 10 4–180 10 [41]
HF-LPME- 0.03 4.2 60c 3 0.08–2.0 12 [42]
ETAAS
IL/MVBE- 12.5 3.1 40.2c 25 50–500 15 [43]
FI-FAAS
SFODME- 0.0004 3.6 497d 10 0.005–0.05 30 [44]
GFAAS
DLLME- 1.27 2.55 158d 10 4.23–250 A few seconds Represented
SFO-FAAS method

DLLME-GFAAS dispersive liquid–liquid microextraction–graphite furnace atomic absorption spectrometry,

CPE-FAAS cloud point extraction–flame atomic absorption spectrometry, HF-LPME-ETAAS hollow fiber-
based liquid-phase microextraction–electrothermal atomic absorption spectrometry, IL/MVBE-FI-FAAS ionic
liquid/microvolume back extraction procedure–flame atomic absorption spectrometry, SFODME-GFAAS
solidification of floating organic drop microextraction–graphite furnace atomic absorption spectrometry
a
Limit of detection
b
Relative standard deviation
c
The enhancement factor is the slope ratio of calibration graph after and before extraction
d
Enrichment factor defined as the ratio of the concentration of analyte after preconcentration to that without
preconcentration giving the same analytical response

in the floating organic drop after phase separation (78±2 μL organic-rich phase), and C0 is
the initial concentration of nickel (micrograms per liter). The enrichment factor was
determined to be 158 (n=3).
Cs
EF ¼ ð1Þ
C0

As for the determination of the absorbance for nickel in the floating organic drop, the
extraction solvent (78±2 μL) was diluted with ethanol to a volume of to 0.5 mL; the
enrichment factor for the proposed method is 24.6.

Analysis of Natural Waters

The proposed method was applied to the determination of nickel in several water samples.
The results, along with the recovery (for spiked samples), are given in Table 3. The
recoveries for the addition of different Ni concentrations to water samples were in the range
95.0–100.5%. To verify the accuracy of the proposed procedure, the method was used for
the determination of Ni in a sample of National Standard Reference Material for
Environmental Water (GSBZ 50009-88 and GSB 07-1186-2000) after appropriate dilution.
The results of this test are presented in Table 3. Good agreement between the determined
and certified values was obtained.
Development of Dispersive Liquid–Liquid Microextraction 1391

Comparison to Other Methods

A comparison of the represented method with other reported preconcentration methods

[5, 41–44] is given in Table 4. Generally, the enrichment factor and the detection limit
obtained from the present method are comparable to or better than those reported
methods. A lower enrichment factor and higher LOD than SFODME–graphite furnace
atomic absorption spectrometry (GFAAS) and DLLME-GFAAS could be the result of the
determination system. However, DLLME-SFO requires much shorter extraction time than
those for most of the other methods, which is better able to meet the needs of rapidity
analysis. Furthermore, DLLME-SFO is easy to operate without any special instrument
(such as the hollow fiber), and the extractant droplet can be readily collected and carried
out than DLLME, which are of key interest for routine laboratories in trace metal ion
analysis.

Conclusions

DLLME-SFO, combined with FAAS, was evaluated for the preconcentration and the
determination of the trace nickel (at micrograms per liter level) from various water samples.
It has the advantages of both DLLME and LPME-SFO. The analysis time can be as fast as
DLLME and is much shorter than LPME-SFO. DLLME-SFO employs 1-dodecanol as
extraction solvents which are less toxic and dense than the solvents used in DLLME. Due
to the melting point and density of the extracting solvent, extractant droplet can be easily
collected after solidified on the surface of the sample at low temperatures. Furthermore, the
solidified phase can be easily separated from the aqueous phase. The developed method has
been successfully applied to the preconcentration and determination of trace nickel in river,
sea, and tap water samples, and the precision and accuracy of the method are satisfactory.
Although the results obtained in this research were related to the nickel determination, the
system could be readily applied to the determination of other metals with the help of
various chelating agents and other organic solvents.

Acknowledgments This project was sponsored both by the Development Foundation of the Department of
Education of Hebei Province, People’s Republic of China (2007121) and the Research Development
Foundation of the Agricultural University of Hebei.

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