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Liquid–liquid extraction of mercury(II) from aqueous solution using

furosemide in benzyl alcohol

Article in Journal of Radioanalytical and Nuclear Chemistry · January 2019

DOI: 10.1007/s10967-018-6400-5

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Journal of Radioanalytical and Nuclear Chemistry
https://doi.org/10.1007/s10967-018-6400-5

Liquid–liquid extraction of mercury(II) from aqueous solution using

furosemide in benzyl alcohol
Y. A. Abbasi1,2 · S. Shahida3 · A. Ali2,4 · M. H. Khan4

Received: 9 October 2018

© Akadémiai Kiadó, Budapest, Hungary 2019

Abstract
A simple, efficient and economical liquid–liquid extraction method has been developed for quantitative extraction of
mercury(II) from aqueous buffer solution using furosemide in benzyl alcohol. The effect of various parameters and of vari-
ous anions and cations on the extraction of mercury(II) was investigated. The separation factor of mercury was quite high
in the presence of a number of transition and rare earth metals at pH 3.5. Among strippants, sodium thiosulphate was found
most suitable, and the recovery of mercury was noted to be 98%. The stoichiometric composition of the extracted species
was found to be [Hg(FS)2].

Keywords Liquid–liquid extraction · Hg(II) · Furosemide · Benzyl alcohol

Introduction environmental interest [4]. In this regard, several techniques

Mercury (Hg) is one of the most toxic heavy metals com-
monly found in the global environment. Mercury and its
compounds are considered one among the priority hazard-
ous contaminants in the environment which are harmful to
human health and natural ecosystems [1–3]. Its toxicity is
related to the capacity of its compounds to bio concentrate
in organisms and to bio magnified through food chain. The
main target of mercury and its compounds such as methyl
mercury is the human brain where it disrupts the blood brain
barrier and thereby upset the metabolism of nervous sys-
tem. Soluble mercury species are transformed by the action
of microorganisms to alkyl mercury compounds in aerobic
conditions which are extremely toxic. It also form amal-
gams with many metals and therefore its separation from
them and from waste streams is a matter of analytical and
* S. Shahida
Shabnamshahida01@gmail.com
1
Department of Chemistry, University of Azad Jammu &
Kashmir, Muzaffarabad, AJK, Pakistan
2
Chemistry Division, Pakistan Institute of Nuclear Science &
Technology, P.O. Nilore, Islamabad, Pakistan
3
The University of Poonch, Rawalakot, Azad Jammu & Kashmir,
Pakistan
4
Women University of Azad Jammu & Kashmir Bagh, Bagh,
Pakistan
have been developed so far for the removal of Hg(II) from
aqueous solutions such as reduction process [5], chemical
precipitation [6], membrane separation [7], ion-exchange
[8], coagulation [9], adsorption [10] and magnetic ferrites
treatment [11]. Most of these techniques are not suitable for
the removal of mercury from complex matrix.
Solvent extraction is commonly employed technique for
the extraction/separation of metals from the impurities which
require a selective organic reagent that can form complex
with the metal ion in aqueous medium and extract it in water
immiscible organic solvent [12]. Commonly used organic rea-
gents for mercury are cyanex 923 [13], tri-n-butyl phosphate
[14], N-octyl methane sulfonamide [15], dimethylarsinic acid
[16], n-benzoyl-N′,N′-diheptadecylthiourea [17], o-carboxy-
phenyldiazoamino-p-azobenzene [18] and 1-(2-pyridylazo)-
2-naphthol [19]. However, these organic reagents are either
very expensive or they required advance organic synthetic
laboratories. Therefore it is essential to explore more eco-
nomical and easily available metal extracting agents.
The application of active ingredient of drugs as metal
extracting agents has been very little studied so far. They
are cheap and easily available in the market and they can be
used potential metal extractants. Therefore, instead of syn-
thesizing costly extractant it is better to investigate active
ingredients of drugs as metals extractant. Active ingredient
of only a few drugs have been studied so far like piroxicam
for the spectrophotometric determination of U(IV), Fe(III)

13
Vol.:(0123456789)

and Cu(II) [20, 21], tetracycline for the solvent extraction
of rare earth metal ions [22] and some transition metal ions
[23]. In our previous studies, we have studied nalidixic acid
in dichloromethane for the solvent extraction of Nd(III),
Eu(III) [24] and Sc(III) [25] and also for the online pre-
concentration of U(IV) [26], Sc(III) [27] and Eu(III) [28].
Some other drugs like dibenzoylmethane was studied for
the online preconcentration of U(IV) [29] and oxytetracy-
cline for the online preconentration of thorium [30].
Furosemide (5-aminosulfonyl 4-chloro-2-[(2-furanyl-
methyl) amino]-5-sulfamoyl benzoic acid) is a diuretic
drug commonly administered for cardiac chronic renal
failure [31] hypertension and congestive heart failure [32].
The pKa value of furosemide is 3.8 and 7.5 [33]. It has
been found from literature that this reagent forms the che-
late complexes with metals such as Ag(I) [34] and Zn(II)
where furosemide is bonded through its carboxylate and
amino functional groups [35]. Its complexes with iron (III)
and copper (II) are also reported [36, 37] where these com-
plexes are used for the spectrophotometric determination
of the drug. However the use of this reagent for the solvent
extraction of metals is not reported in the literature so far.
In this paper we reported the extraction of Hg(II) with
furosemide (HFS) in benzyl alcohol. The purpose of the
present study was to explore the potentiality of active
ingredient of drugs as metal extractants. Extraction behav-
ior of HFS for the extraction of Hg(II) as representative of
heavy metals has been studied. In this communication opti-
mum conditions for the extraction of Hg(II) with HFS, its
mechanism of extraction, the effect of various cations and
anions on the extraction of Hg(II) is presented. The struc-
tural formula of furosemide is shown in Scheme 1 [38].
Experimental
Reagents and instrumentation
Furosemide was purified from Lasix tablets obtained from a
local pharmaceutical company. Benzyl alcohol was procured
O of Nuclear Science & Technology, Islamabad, Pakistan at a
C OH
O diation process. Concentrated nitric acid (5 mL) was used
H2NSO2 NHCH2
Cl
Scheme 1  Structural formulae of furosemide
13
Journal of Radioanalytical and Nuclear Chemistry
from Riedel-de-Hane, Germany, and used as such. All other
reagents used in the present study were of analar grade.
Buffer solutions of different pH, ranging from 1 to 3 were
prepared by mixing required quantities of 0.1 mol dm−3
solutions of ­NaClO4 and ­HClO4 and from pH 4 to 6 were
prepared by mixing required quantities of 0.1 mol dm−3
solutions of sodium acetate and acetic acid. The pH of buffer
solutions was checked by a pH meter, model 605, from
METROHOM Ltd, Switzerland whenever required. For the
shaking of organic and aqueous phases a wrist action electri-
cal shaker (Georg and Griffin, UK) was used. Radiometric
assays of metal ions were carried out by a well type NaI
(Tl) scintillation detector coupled with a counting assembly
(Tennelec Inc., USA).
Purification of furosemide (HFS)
HFS was purified from the Lasix tablets (50 mg) contain-
ing HFS as the active ingredient. Fine powder of the tab-
lets was obtained by grinding tablets in a mortar with a
pestle and a known weight of this powder was dissolved
in 500 mL of an aqueous solution of 0.1 mol dm−3 NaOH.
The insoluble impurities were separated by filtration. The
filtrate which contains the sodium salt of HFS was mixed
with 0.1 mol dm−3 HCl solution to get un-dissociated HFS,
which is insoluble in water and was separated by filtration.
It was washed with de-ionized water to remove traces of
HCl and then dried in an oven (60 °C). The whole purifica-
tion process is shown in Scheme 2. It was re-crystallized
from acetone and the purity of the HFS was checked by
HPLC, melting point and IR techniques and it was found
to be > 99%.
Preparation of radiotracers
Known amounts of spec-pure metals or metal oxides such
as, Hg(II), Eu(III), Nd(III), Sc(III), Y(III), Co(II), Mn(II),
Cu(II), Zn(II) and Cr(III) of Johnson Mathew Chemical
Ltd., England were subjected to thermal neutron irradia-
tion in the research reactor PARR-1 of Pakiatan Institute
thermal neutron flux of 5 × 1013 n cm−2 s−1 for a proper time
depending upon the half-life of the required radionuclide.
Irradiated material was given enough cooling time to get rid
of short lived radioisotopes formed (if any) during the irra-
to dissolve the irradiated material. The content was heated
to near dryness, and the solution of each radiotracer was
prepared separately by adding known volume of deionized
water. The irradiation was not 100% efficient. The isotopic
purity of the radiotracer was checked by a 25 cm3 Ge (Li)
Journal of Radioanalytical and Nuclear Chemistry

Scheme 2  Purification of COOH

furosemide COONa
NHCH2 O
NaOH NHCH2 O
H2NSO2 0.1 mol dm -3
H2NSO2
Cl
Cl
Insoluble in water Soluble in water

0.1 mol dm-3 HCl

COOH

NHCH2 O

H2NSO2
Cl

Insoluble in water

Table 1  Radio isotopes Isotopes Half life vigorous shaking for 10 min with the help of wrist action
prepared with their half lives electrical shaker. The phases were separated by centrifuga-
154
Eu 8.8 years tion and 1 mL from each phase was taken by pipette into the
147
Nd 10.9 days glass counting vials. Both phases were assayed radiometri-
60
Co 5.27 years cally to find the metal concentration in each phase. The count
64
Cu 12.7 h rate of the radiotracer was measured with the help of a well
69
Zn 13.8 h type NaI (Tl) gamma scintillation detector (Tennelec, Inc.,
203
Hg 46.6 days USA) coupled with counting assembly. In order to evaluate
51
Cr 27.7 days the extraction equilibrium, the distribution coefficient D is
46
Sc 84 days determined by the ratio of metal content in the organic phase
to that of in the aqueous phase at equilibrium. The back-
ground activity was measured by measuring the count rate
detector coupled with a 4 K series 85 Canberra multichannel of the blank solution in triplicate without adding mercury
analyzer. The count rate of the radiotracer was adjusted by radiotracer. The distribution ratio (D) and the percent extrac-
proper dilution with the help of a well type NaI (Tl) gamma tion were estimated by using the following relationship [39].
scintillation detector coupled with counting assembly (Ten-
nelec, Inc., USA). In order to maintain a constant concentra- Distribution ratio (D)
tion of metal ion, when 50 μL of each radio tracer is added Activity of organic phase − Background activity
=
in 2 mL of aqueous phase, non-radioactive solution of metal Activity of aqueous phase − Background activity
ions was added as carrier. The radiotracers produced from
pure metal/oxides with their half-lives are given in Table 1. D × 100
Extraction (%) =
D + (Vaq ∕Vorg )
Extraction procedure
where Vaq and Vorg is the volume of aqueous and organic
All the experiments were carried out at room temperature phase taken for radiometric determination.
(25 °C) in triplicate. HFS solution of desired concentration
was prepared by dissolving it in benzyl alcohol by slight
warming. An aqueous phase (2 mL) of desired pH contain- Results and discussion
ing ~ 4.9 × 10−5 mol dm−3 radiotracer of Hg(II) solution and
an equal volume of benzyl alcohol as organic phase contain- To investigate the extraction behavior of HFS towards mer-
ing known concentration of HFS were equilibrated in Pyrex cury (II) with different pH of the aqueous phase, extrac-
glass culture vials (16 mm ×120 mm) with screw cap by tion of Hg(II) (4.9 × 10−5 mol dm−3) was carried out from

13
 Journal of Radioanalytical and Nuclear Chemistry

aqueous buffer solutions of pH 1 to 6 with 0.05 mol dm−3

HFS in benzyl alcohol as shown in Fig. 1. Phase separation
was efficient and there were no appearance of third phase
formation in the pH range studied. Extraction percentage
of Hg(II) increased with pH, it was around 2% at pH 1
and 99% at pH 3.5. Further increase of pH up to pH 6 has
shown slight decrease in the extraction so high pH did
not favor the extraction of Hg(II). At pH 3.5 of aqueous
phase, Hg(II) ion replaced the hydrogen ion of HFS to
form an organometallic complex with the extracting rea-
gent (HFS) making it insoluble in aqueous phase so that it
could be extracted into the organic phase (HFS in benzyl
alcohol). From this data it was found that the optimum pH
for the extraction of Hg(II) should be 3.5. This pH (3.5)
was selected as optimum pH of the aqueous phase for the
extraction of Hg(II) for further studies.
In order to find out the effect of equilibration time on Fig. 2  Extraction of Hg(II) with HFS (0.05 mol dm−3) in benzyl alco-
the extractability of Hg(II) with HFS (0.05 mol dm−3) in hol as function of time
benzyl alcohol, extraction was carried out for different
time intervals ranging from 1 to 15 min and the results are
shown in Fig. 2. It was observed that quantitative extrac- Hg(II) (~ 4.9 × 10−5 mol dm−3) was carried out from buffer
tion of Hg(II) was possible with in first five minutes of solutions of pH 2 to 3 using 0.01 mol dm−3 HFS in benzyl
shaking time however the optimum time chosen for all alcohol. Figure 3 shows the plot of log of the distribution
other studies was 10 min. This is because the equilibration versus the pH of the aqueous phase for Hg(II). The plot is
between metal ion and extractant is attained in 5–10 min linear with a slope of 2.1 with correlation co-efficient of
only. Further increase of shaking time did not affect the 0.996. This slope value of 2 indicates that in the extracted
extraction of Hg(II) [40]. adduct 2 molecules of HFS are present as dissociated mol-
The composition of the extracted organometallic complex ecule ­(FS−) to neutralize the divalent Hg(II).
was investigated by slope analysis method. Two kinds of The effect of variation in the amount of HFS on the distribu-
experiments were conducted for this study. Effect of varia- tion ratio of Hg(II) (~ 4.9 × 10−5 mol dm−3) at constant pH of
tion in the pH of the aqueous phase was studied to find out 3.5 was studied to find out the total number of HFS attached to
the number of HFS participating as anion (FS) to satisfy the
primary valency of Hg(II). For this purpose, extraction of

Fig. 1  Extraction of Hg(II) with 0.05 mol dm−3 HFS in benzyl alco- Fig. 3  Plot of log D versus pH of Hg(II) with 0.01 mol dm−3 HFS in
hol as a function of pH benzyl alcohol

13
Journal of Radioanalytical and Nuclear Chemistry
the central metal atom. This was investigated by changing the
amount of HFS from 0.0004 to 0.004 mol dm−3 and the Fig. 4
shows the results of this experiment. It shows that the slope
value of the plot of log D versus log of concentration of HFS is
1.9 ± 0.03 (correlation co-efficient of 0.995). This slope value
of 1.93 indicates that two molecules of HFS are involved in the
formation of organometallic complex with Hg(II).
The data from these experiments can be utilized to derive
the extraction mechanism of Hg(II) with HFS as, using this
equation the extraction constant (Kex) can be calculated as;
Kex
Hg+2 + 2HFS(O) ⟷ Hg(FS)2(o) + 2H+
From above reaction the value of Kex is given by
] [ ]2 [
Kex = M(FS)2 (o) H+ ∕ M+2 [HFS]2 (o)
[ ]
Since, D = [M(FS)2](o)/[M2+]
+ 2
So, Kex = D ­[H ] /[HFS] . 2 benzyl alcohol is quite good without any degradation.
Here, organic phase is represented by the subscript
(o). The log Kex values for Hg(II) were calculated to be
− 5.9 ± 0.05.
Loading capacity of the extractant (0.05 mol dm−3 in ben-
zyl alcohol) for Hg(II) from aqueous buffer solution of pH
3.5 was studied by varying the concentration of Hg(II) from
10 to 300 µg mL−1. Results are shown in Fig. 5. It appears
from the results that extraction of Hg(II) by this extraction
system is quantitative up to 250 µg mL−1 and then decreases
at 300 µg mL−1 concentration of Hg(II). This decrease in
extraction at high concentration of metal ions may be due
to the change in the activity coefficient of metal ions [41].
This indicates that extraction of Hg(II) can be improved by
increasing the concentration of extractant in the organic
Fig. 4  Log–log plot of D versus log [HFS] in benzyl alcohol at pH
3.5 of aqueous phase
100
98
Extraction (%)
96
94
92
90
0 50 100 150 200 250 300
Hg(II) conc. (µg mL-1)
Fig. 5  Effect of Hg(II) concentration on extraction with
0.05 mol dm−3 HFS in benzyl alcohol at pH 3.5
phase. It was found that extraction efficiency of the HFS in
The effect of various anions and cations on the extraction
of Hg(II) was checked by adding their higher concentration
in Hg(II) solution (4.9 × 10−5 mol dm−3) maintained at pH
3.5. First, the % extraction of Hg(II) was determined without
adding cations and anions. Then, the cations were added as
their sodium or potassium salts while anions were added
as their sodium or potassium salts. The cations and anions
were added one by one into Hg(II) solution. The results are
presented in Tables 2 and 3 respectively. The results have
shown that out of the investigated metal ions, none of the
them has any significant interference on the extractability
of Hg(II) under the conditions optimized for this extraction
system (0.05 mol dm−3 HFS in benzyl alcohol, shaking time
10 min and pH 3.5).
The results for the extraction behavior of Hg(II) from
aqueous phase containing added anions has indicated that
cyanide and thiosulfate has significant interference. Both
these anions have lowered the extraction of mercury to 43%
and 4.35% respectively. However the extractability of Hg(II)
was not effected by the presence of other added anions and
remain quantitative. Stable complexes of Hg(II) with thio-
sulfate have been reported therefore the interference in the
presence of cyanide and thiosulphate could be due to the
formation of their stable complexes with Hg(II) [42].
The separation efficiency of Hg(II) from various metal
ion i.e. Sc(III), Co(II), Cu(II), Zn(II), Mn(II), Cd(II), Cr(III),
Fe(III), Pb(II), ­UO2(VI) and rare earth elements Ce(III),
Nd(III) and Eu(III) was investigated by carrying out extrac-
tion of these metals from aqueous buffer solution of pH 3.5
under the conditions optimized for the extraction of Hg(II).
Separation factor of Hg(II) from above mentioned metal
ions were calculated by using the relation (DHg/DM2 where
DHg = distribution ratio of Hg and DM2 = distribution ratio
of the metal tested) and the results are given in Table 4. The
13
 Journal of Radioanalytical and Nuclear Chemistry

Table 2  Effect of various cations on the extractability of Hg(II) with Table 4  Separation factor (SF) for Hg(II) from various metal ion at
0.05 mol dm−3 HFS in benzoyl alcohol from aqueous solution of pH pH 3
3.5
Metal Concentration DM SF = DHg/DM
Cations Concentration Hg(II) extraction ± Deviation (mol dm−3) DHg = 107
(mol dm−3) (%), n = 3 from normal
value Cd(II) 1.0 × 10−4 0.011 9.7 × 103
Pb(II) 6.0 × 10−4 0.01 1.0 × 104
Hg(II) 4.9 × 10−5 99.0 ± 0.2 –
Cr(III) 4.1 × 10−5 0.02 5.3 × 103
Zn(II) 1.5 × 10−3 99.3 ± 0.2 + 0.3
Cu(II) 3.9 × 10−4 0.01 1.0 × 104
K(I) 1.4 × 10−2 96.5 ± 2.8 − 2.5
Fe(III) 2.6 × 10−4 0.04 2.6 × 103
Na(I) 1.0 × 10−1 99.2 ± 0.2 + 0.2
Sc(III) 3.3 × 10−5 0.003 5.6 × 103
Mn(II) 1.8 × 10−3 93.7 ± 5.2 + 5.3
Co(II) 1.3 × 10−5 0.004 2.6 × 104
Pb(II) 4.8 × 10−3 98.6 ± 1.1 − 0.4
Ce(III) 1. 8 × 10−5 0.003 3.5 × 104
Fe(III) 1.78 × 10−3 96.7 ± 2.1 − 2.3
Zn(II) 7.6 × 10−5 0.04 2.6 × 103
Fe(II) 1.78 × 10−3 94.0 ± 4.8 − 5.0
Eu(III 1.5 × 10−5 0.007 1.5 × 104
Ba(II) 7.2 × 10−3 99.3 ± 0.2 + 0.3
Nd(III) 2.0 × 10−5 0.006 1.7 × 104
Ni(II) 1.6 × 10−3 98.8 ± 0.4 − 0.2
U(VI) 2.0 × 10−4 12.5 8.56
Cu(II) 1.5 × 10−3 93. 6 ± 5.1 − 5.4
Y(III) 1.1 × 10−3 98.6 ± 0.5 − 0.4
Cr(III) 1.9 × 10−3 96.5 ± 2.4 − 2.5
Table 5  Determination of Hg(II) in spiked sea water
Samples Hg(II) added % Recovery, n = 3 ± Deviation (%)
Table 3  Effect of various anions on the extractability of Hg(II) with (mg L−1)
0.01 mol dm−3 HFS in benzyl alcohol (pH 3.5)
Sea water 25 99.1 ± 0.5 − 0.9
Anion Concentration Hg(II) extrac- ± Deviation from
(mol dm−3) tion (%), n = 3 normal value (%) 15 98.5 ± 1.1 − 1.5

Hg(II) 4.9 × 10−5 99.0 ± 0.2 –

Fluoride 2.6 × 10−2 98.5 ± 0.6 − 0.5
chloride, hydrochloric acid and distilled water. It was found
Chloride 1.4 × 10−2 93.3 ± 3.2 − 5.7
that 0.1 mol dm−3 of ­Na2S2O3 was enough for the 98%
Cyanide 1.9 × 10−3 43.3 ± 4.4 − 55.7
stripping of Hg(II) to the aqueous phase. At this concentra-
Dichromate 2.3 × 10−3 99.4 ± 0.1 + 0.4
tion of ­Na2S2O3, S2 O−2 ion replaced the extracting reagent
Citrate 1.7 × 10−3 99.4 ± 0.2 + 0.4 3
to form the extracted metal complex in the organic phase
Carbonate 8.3 × 10−3 97.8 ± 1.1 − 1.2
which was insoluble in the organic phase and was stripped
Phosphate 5.2 × 10−3 99.4 ± 0.1 + 0.4
into the aqueous medium. This is due to the fact that Hg(II)
Thiosulphate 4.4 × 10−3 4.4 ± 5.2 − 94.6
form more stable complexes with thiosulfate log K = 29.86
Nitrate 8.1 × 10−3 97.8 ± 1.1 − 1.2
[42] than HFS log K = −5.89 ± 0.05. Back extraction with
Oxalate 3.0 × 10−3 98.1 ± 0.8 − 0.9
(0.1 mol dm−3) ­NH4Cl and HCl was around 92%, while dis-
Thiocyanide 8.6 × 10−3 94.8 ± 3.8 − 4.2
tilled water was not able to back extract Hg(II) from loaded
Sulfate 5.1 × 10−3 97.9 ± 1.1 − 1.1
organic phase to fresh aqueous phase.
Chlorate 1.0 × 10−1 99.2 ± 0.1 + 0.2
In order to assess the applicability of the method on real
samples, the proposed method was applied to the spiked
mocked sea water for the determination of Hg(II) with the
data revealed that only U(VI) could be co-extracted whereas proposed procedure and the results are presented in Table 5.
the extraction of other metals is negligible using this extrac- The mocked sea water was prepared according to the compo-
tion system. High separation factor for other metals ­(103 sition given in the literature [43]. The results showed that a
to ­104) given in Table 4 indicates that clean separation of good recovery of Hg(II) from spiked samples was obtained.
Hg(II) from tested transition metals and rare earth metal ions
is possible with this extraction.
In order to find out the optimum conditions for the back Conclusions
extraction of Hg(II) from loaded organic phase into fresh
aqueous phase, shaking of the loaded organic phase was car- The liquid–liquid extraction system comprising furosem-
ried out with different molar concentrations (0.01 mol dm−3 ide in benzyl alcohol has been found to be efficient extrac-
to 1.0 mol dm −3) of sodium thiosulphate, ammonium tion systems for the quantitative extraction of Hg(II) from

13
Journal of Radioanalytical and Nuclear Chemistry
aqueous buffer of pH 3.5. Various parameters that effect
the extraction of Hg(II) like shaking time and metal con-
centration were optimized. The composition of extracted
complex was studied by slope analysis method and found
to be [Hg(FS)2]. This extracting system is quite stable and
can be recycled without any degradation. Furosemide in
benzyl alcohol showed high loading capacity for Hg(II).
The extracted Hg(II) can be stripped back in ­Na2S2O3 as
stripping agent and the recovery of mercury was noted
to be 98%. High separation factor of Hg(II) from Cd(II),
Pb(II), Cu(II), Co(II), Zn(II), Cr(III) and Fe(III) was
observed. The developed extraction system has good selec-
tivity for Hg(II) and most of the cations and anions have
no significant interference on the extraction of Hg(II). In
order to access the applicability of the method on real
samples, it was applied on spiked mock sea water and good
recovery of Hg(II) was found. Price of furosemide drug is
very low as compared to the commonly used extractants
for Hg(II). This was the continuation of our study to check
the potential of active ingredients of pharmaceutical drugs
for the extraction of metals.
Acknowledgements We are grateful to the Reactor Operation Group
(ROG) of PINSTECH Islamabad, Pakistan for irradiating the target
samples in the research reactor for the production of radionuclides used
in this study. We are also grateful to Higher Education Commission,
Pakistan for providing financial support to complete this study.
References
1. Clifton JC (2007) Mercury exposure and public health. Pediatr
Clin North Am 54(2):237–269
2. Clarkson TW, Magos L (2006) The toxicology of mercury and its
chemical compounds. Crit Rev Toxicol 36(8):609–662
3. Hylander LD, Goodsite ME (2006) Environmental costs of mer-
cury pollution. Sci Total Environ 368(1):352–370
4. Ospar T (2008) Directive 2008/105/EC of the European Parlia-
ment and of the council of the European Union. OJEC 348:84–97
5. Matlock MM, Howerton BS, Atwood DA (2001) Irreversible pre-
cipitation of mercury and lead. J Hazard Mater 84:73–82
6. Barron-Zambrano J, Laborie S, Viers P, Rakib M, Durand G
(2004) Mercury removal and recovery from aqueous solutions by
coupled complexation-ultrafiltration and electrolysis. J Membr Sci
229:179–186
7. Anirudhan TS, Divya L, Ramachandran M (2008) Mercury (II)
removal from aqueous solutions and wastewaters using a novel
cation exchanger derived from coconut coir pith and its recovery.
J Hazard Mater 157:620–627
8. Li Z, Wei Q, Yuan R, Zhou X, Liu H, Shan H, Song Q (2007)
A new room temperature ionic liquid 1-butyl-3-trimethylsilylim-
idazolium hexafluorophosphate as a solvent for extraction and
preconcentration of mercury with determination by cold vapor
atomic absorption spectrometry. Talanta 71:68–72
9. Basha S, Murthy ZVP, Jha B (2009) Sorption of Hg(II) onto
Carica papaya: experimental studies and design of batch sorber.
Chem Eng J 147:226–234
10. Rae IB, Gibb SW, Lu S (2009) Biosorption of Hg from aqueous
solutions by crab carapace. J Hazard Mater 164:1601–1604
11. Prashant DZ, Dattatray MD (2007) Retrieval of mercury from
wastewater as stable mercury ferrite. Water Qual Res J Canada
42:311–318
12. Marcus Y, Kertes AS (1969) Ion exchange and solvent extraction
of metal complexes. Wiley, London
13. Meera R, Francis T, Reddy MLP (2001) Studies on the liquid–liq-
uid extraction of mercury (II) from acidic chloride solutions using
Cyanex 923. Hydrometallurgy 61(2):97–103
14. Sato T, Enokida T, Noguchi Y (2002) Liquid–liquid extraction of
mercury (II) from hydrochloric acid solutions by tributyl phos-
phate. Solvent Extr Res Dept Jpn 9:1–11
15. Bicak N, Sungur S, Gazi M, Tan N (2003) Selective liquid–liquid
extraction of mercuric ions by octyl methane sulfonamide. Sci
Technol. 38(1):201–217
16. Wahlen R, Catterick T (2004) Simultaneous co-extraction of
organometallic species of different elements by accelerated sol-
vent extraction and analysis by inductively coupled plasma mass
spectrometry coupled to liquid and gas chromatography. Rapid
Commun Mass Spectrom 18(2):211–217
17. Fontas C, Hidalgo M, Salvado V, Antico E (2005) Selective
recovery and preconcentration of mercury with a benzoylthio-
urea-solid supported liquid membrane system. Anal Chim Acta
547(2):255–261
18. Zaijun L, Qin W, Rui Y, Xia Z, Huizhen L, Haixia S, Qijun S
(2007) A new room temperature ionic liquid 1-butyl-3-trimethyl-
silylimidazolium hexafluorophosphate as a solvent for extraction
and preconcentration of mercury with determination by cold vapor
atomic absorption spectrometry. Talanta 71(1):68–72
19. Zhefeng F, Xuejuan L (2008) Determination of methyl mercury
and phenyl mercury in water samples by liquid–liquid–liquid
microextraction coupled with capillary electrophoresis. J Chro-
matogr A 1180(1–2):187–192
20. Sadeghi S, Mohammadzadeh D, Yamini Y (2003) Solid-phase
extraction and spectrophotometric determination of uranium (VI)
in natural waters. Anal Bioanal Chem 375:698–702
21. Sadeghi S, Mohammadzadeh D, Imampur JS (2005) Selective
transport of copper (II) ions across a liquid membrane mediated
by Piroxicam. Anal Bioanal Chem 383:261–267
22. Nastasi MJC, Lima FW (1977) Solvent extraction of the lantha-
nide elements, scandium, uranium and thorium using tetracycline
as complexing agent. J Radioanal Chem 35:289–301
23. Saiki M, Lima FW (1978) Solvent extraction studies using tet-
racycline as complexing agent. Radiochem Radioanal Lett
35(1–2):63–66
24. Ali A, Yasar AA, Khan MH, Saeed MM (2010) Liquid–liquid
extraction of Nd(III) and Eu(III) using nalidixic acid in dichlo-
romethane. Radiochim Acta 98(8):513–517
25. Yasar AA, Ali A, Khan MH, Saeed MM, Naeem K (2012) Liq-
uid–liquid extraction of scandium with nalidixic acid in dichlo-
romethane. J Radional Nucl Chem 292(1):277–283
26. Shahida S, Ali A, Khan MH, Saeed MM (2013) Flow injection
online spectrophotometric determination of uranium after pre-
concentration on XAD-4 resin impregnated with nalidixic acid.
Environ Monit Assess 185(2):1613–1626
27. Shahida S, Ali A, Khan MH (2013) On-line spectrophotometric
determination of scandium after preconcentration on XAD-4 resin
impregnated with nalidixic acid. J Iran Chem Soc 10(3):461–470
28. Shahida S, Ali A (2014) Determination of europium (III) in envi-
ronmental samples using a flow injection analysis system with
on-line preconcentration and spectrophotometric detection. J
Radioanal Nucl Chem 300(1):423–429
29. Shahida S, Ali A, Khan MH, Saeed MM (2011) Flow injection on-
line determination of uranium after preconcentration on XAD-4
resin impregnated with dibenzoylmethane. J Radioanal Nucl
Chem 289(3):929–938
13

30. Shahida S, Ali A, Khan MH (2014) Flow injection on-line spectro-
photometric determination of thorium (IV) after preconcentration
on XAD-4 resin impregnated with oxytetracycline. J Iran Chem
Soc 11(1):1–8
31. Wright JM, Lee CH, Camber EK (1999) Systematic review of
anti-hypertensive therapies: Does the evidence assist in choosing
a first-line drug? Can Med Assoc J 161:25–32
32. Goodman LS, Gilman A (2011) the pharmacological basis of
therapeutic, 10th edn. McGraw-Hill, New York
33. Yoshimasa O, Akio A, Yoshihiro T, Abe H (1976) A metal com-
plexing property of furosemide and bumetanide. Determination
of pka and stability constants. Arznein-forsch 26:11–13
34. Lustri WR, Lazarini SM, Lustri BR, Corbi PP, Silva MAC,
Aquino R, Amaral AC, Filho OT, Massabni AC, Barud HS (2017)
Spectroscopic characterization and biological studies in vitro of
a new silver complex with furosemide: prospective of application
as an antimicrobial agent. J Mol Struct 1134:386–394
35. Uwe H, Heinrich VZ, Naturforsch B (1994) Zinc complex of sul-
fonamide. Chem Sci 49:1725–1730
36. Ljiljana Z, Snezana A, Dusanka R (1990) Spectrophotometric
determination of furosemide as its Fe(III) complex in pharma-
ceutical preparations. Mikrochim Acta 1:49–54
37. Khade BC, Deore PM, Arbad BR (2007) Potentiometric studies
on the stability constants of some drugs with Cu(II), Cr(III) and
13
View publication stats
Journal of Radioanalytical and Nuclear Chemistry
Ca(II) in 80% v/v ethanol-water medium. Acta Ciencia Indica
Chem 33:105–108
38. Golcu A (2006) Spectrophotometric determination of furosemide
in pharmaceutical dosage forms using complex formation with
Cu(II). J Anal Chem 61:748–754
39. Khan MH, Shahida S, Ali A (2008) Liquid–liquid extraction of
uranium from nitric acid solution using di-n-butylsulfoxide in
petroleum ether as extractant. Radiochim Acta 96:35–40
40. Fabrega FM, Guimaraes AS, Resende GPS, Mansur MB (2016)
Solvent extraction of mercury (II) from aqueous chloride solu-
tions using Cyanex 302. Miner Proc Extrac Metall IMM Trans
126(4):1–6
41. Nyman CJ, Salazar T (1961) Complex ion formation of mercury
(II) and thiosulfate ion. Anal Chem 33(11):1467–1469
42. Chen J, Wang Y, Wei X, Xu P, Xu W, Ni R, Meng J (2018) Mag-
netic solid-phase extraction for the removal of mercury from water
with ternary hydro sulphonyl-based deep eutectic solvent modified
magnetic graphene oxide. Talanta 188(1):454–462
43. Lyman J, Fleming RH (1940) Composition of sea water. J Mar
Res 3:134–146
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