Chemosphere 220 (2019) 565e573

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Reliable quantification of mercury in natural waters using surface

modified magnetite nanoparticles

udia B. Lopes b, c, Tito Trindade b,
Daniela S. Tavares a, b, Carlos Vale c, Cla
Eduarda Pereira a, *
a
Department of Chemistry and CESAM, University of Aveiro, Campus de Santiago 3810-193 Aveiro, Portugal
b
Department of Chemistry and CICECO, University of Aveiro, Campus de Santiago 3810-193 Aveiro, Portugal
c ~es, 4450-208, Matosinhos, Portugal
CIIMAR - Interdisciplinary Centre of Marine and Environmental Research, Terminal Cruzeiros do Porto de Leixo

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Simple methodology for quantify

mercury at concentrations currently
found in waters.

Direct analysis of Hg on the Fe3O4@-
SiO2SiDTC nanoparticles using a
mercury analyser.

10 mg L1 of nanoparticles can
extract more than 90% of the total Hg
in waters.

The LOD achieved is lower than
values reported for other magnetic
materials.

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

Article history: Reliable determination of mercury (Hg) in natural waters is a major analytical challenge due to its low
Received 19 July 2018 concentration and to the risk of Hg losses or contamination during sampling, storage and pre-treatment
Received in revised form of samples. The present work proposes a simple, efficient, sensitive and easy-handling methodology for
3 December 2018
extraction, pre-concentration and quantification of total dissolved mercury in natural waters, using iron
Accepted 20 December 2018
Available online 21 December 2018
oxide nanoparticles (NPs) coated with silica shells functionalized with dithiocarbamate groups
(Fe3O4@SiO2SiDTC). Ten mg L1 of these NPs were sufficient to remove 83e97% of 500 to 10 ng L1 of Hg
Handling Editor: Petra Petra Krystek in ultra-pure water and artificial seawater, used as model Hg solutions, within 24 h. Mercury sorbed to
the NPs was then measured directly by thermal decomposition atomic absorption spectrometry with
Keywords: gold amalgamation. The detection limit of approximately 1.8 ng L1 is lower than the values reported in
Mercury quantification dispersive solid phase extraction for other magnetic sorbents. As a proof-of-concept, the proposed
Magnetite nanoparticles methodology was successfully tested in real samples of fresh and saline waters and more than 91% of Hg
Water analysis was recovered. With this methodology the extraction and pre-concentration steps may be carried out in
situ decreasing the risk of Hg losses or contamination during sampling, storage and pre-treatment of
water samples.
© 2018 Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: eduper@ua.pt (E. Pereira).

https://doi.org/10.1016/j.chemosphere.2018.12.149
0045-6535/© 2018 Elsevier Ltd. All rights reserved.
566 D.S. Tavares et al. / Chemosphere 220 (2019) 565e573
1. Introduction
Mercury (Hg) and its compounds are classified as priority haz-
ardous substances (Council, 2008). Concentrations found in the
aquatic environment are at trace levels as result of natural pro-
cesses, such as erosion and volcanism, and anthropogenic dis-
charges related mainly to industrial and mining activities (Driscoll
et al., 2013). Mercury is toxic to aquatic organisms (Mousavi et al.,
2011; Zarco-Fernandez et al., 2015), and accumulation in fishery
resources implies the transfer to humans with potential deleterious
effects (Scheulhammer et al., 2007; Driscoll et al., 2013).
Assessing mercury levels in natural waters is hence of great
relevance, as evidenced by the inclusion of this element in the list of
substances to be monitored in scope of the Water Framework
Directive and Marine Strategic Framework Directive, respectively
related to the protection of water resources and marine ecosystems
(2000/60/EC, 2000, 2008/56/EC, 2008), but also a challenge due to
its environmental concentrations. Ultra-low levels of Hg in
seawater (pg L1 to ng L1) have been reported in several studies
(Leopold et al., 2008; Lamborg et al., 2014; Huber et al., 2015).
Levels up to 10 ng L1 were found for coast waters and freshwaters
by Huber et al. (2015), while Keramat and Zare-Dorabei (2017) re-
ported values ranging from 0.2 to 100 mg L1. In contaminated
waters, such as industrial wastewaters or water bodies near gold
mines, Hg levels can reach the mg L1 range (Huber and Leopold,
2016). Inadequate analytical techniques to measure low Hg con-
centration (Gworek et al., 2016), complexity of matrix (Kramer
et al., 1998; Lamborg et al., 2012), mercury's high volatility
(Kramer et al., 1998; Donkor et al., 2006), losses or contamination of
the samples during handling (Donkor et al., 2006), storage and pre-
treatment of samples (Parker and Bloom, 2005; Hammerschmidt
et al., 2011) may generate erroneous data.
High sensitive and frequently used techniques for quantification
of Hg in aquatic environments include cold vapour atomic fluo-
rescence spectroscopy (CV-AFS) (Li and Wang, 2007; Leopold et al.,
2008), cold vapour atomic absorption spectroscopy (CV-AAS)
(Adlnasab et al., 2014; Mehdinia et al., 2016), inductively coupled
plasma-mass spectrometry (ICP-MS) (dos Santos et al., 2009) and
inductively coupled plasma-optical emission spectrometry (ICP-
OES) (Gao et al., 2009; Keramat and Zare-Dorabei, 2017). In recent
years, other techniques using NPs in Hg quantification have also
been explored. For instance, recently, Amorim et al. (2018) reported
an ultra-sensitive method (limit of detection of about 10 fg L 1) to
quantify Hg by dithiocarbamate functionalized magnetic NPs using
radioactive tracker spectroscopy, while Li et al. (2018) and Vasquez
et al. (2018) reported new sensors for Hg detection and quantifi-
cation. However, these optical or electrochemical sensors for detect
the presence of Hg in aqueous solution require the use of a specific
and expensive group of NPs with optical properties, as gold or sil-
ver, quantum dots and up conversion nanoparticles. Colorimetric
and fluorescence methods, according to the interaction between
gold nanostructures and Hg, have also been established for the
determination of Hg2þ in the water samples (Tao et al., 2014). Vahid
et al. (2016) reported a method based on the inhibited effect of gold
NPs on rhodamine Beferricyanide (Fe(CN)3 6 ) chemiluminescence
for the determination of Hg2þ. Colorimetric detection and quanti-
fication of Hg based on analyte-induced enhancement of the pho-
tocatalytic activity of TiO2eAu nanospheres toward degradation of
methylene blue was reported by Ravindranath et al. (2018). Finally,
surface enhanced Raman spectroscopy (SERS) is an ultra-sensitive
analytical method that can be used for Hg detection. Recently,
Sarfo et al. (2017) reported the application of a thiolated crown
ether derivative functionalized gold nanosensor for SERS quantifi-
cation of Hg(II) in aqueous solution. Although, these new technol-
ogies are emerging due to the development of nanotechnology,
some of them may be considered too exotic due to the use of
complex, specific and rugged instrumentation. However, on
everyday analyses these equipments or techniques are not the first
choice of laboratories or companies, and techniques like CV-AFS,
CV-AAS, ICP-MS or ICP-OES are desirable. Still, direct analysis of
Hg at ultra-trace levels in water cannot be easily conducted
specially due to the high matrix effects (Gao et al., 2012) and
insufficient detection power of instrumentation. Sample pre-
treatment procedures to eliminate interferences and enhance
sensitivity are often indispensable. Therefore, separation and pre-
concentration procedures are usually employed before Hg quanti-
fication. Cold vapour generation, amalgamation and solid-phase
extraction (SPE) are among the most common used techniques
for separation and pre-concentration procedures. Among these
procedures, several authors have highlighted SPE as a good pro-
cedure for separation and pre-concentration of Hg species, due to
its efficiency and simplicity (Zhai et al., 2010; Soleimani et al., 2011;
Panichev et al., 2014). A variety of sorbents, such as nanomaterials
like silver and gold NPs (Panichev et al., 2014; Huber et al., 2015;
Huber and Leopold, 2016), carbon-nanotubes (Herrero-Latorre
et al., 2015), mesoporous materials (Chai et al., 2010), or magnetic
NPs have been employed in SPE (Cui et al., 2015; Ma et al., 2016; Wu
et al., 2016).
The advancement of nanotechnology has allowed the design of
new materials, with specific properties due to the possibility of
controlling the morphological characteristics and the ability of
surface modification, making them selective and high efficient
sorbents, to enhance the extraction efficiency and reducing the
extraction time (Deng et al., 2008; Qu et al., 2013; Abolhasani et al.,
2015; Wu et al., 2016). In conventional SPE, sorbents need to be
packed into cartridges, disks, columns or dipsticks (Huber and
Leopold, 2016), increasing sample preparation time and the
complexity of the extraction procedure. Dispersive SPE is an
attractive configuration of this technique due to its simplicity,
fastness and low-cost, by direct dispersion of the sorbents in the
solution containing the target analyte (Khezeli and Daneshfar,
2017). After extracting the analyte, the sorbent is separated from
the solution, usually by filtration or centrifugation, and then the
target analyte is desorbed by an eluent for further determination.
Dispersive SPE techniques based on the use of magnetic sorbents
have received increasing attention because of the solid-liquid
separation facility after extraction, by the application of an
external magnetic field (Ambashta and Sillanpaa, 2010; Kim et al.,
2011). After sorption, the sorbents can be analysed for the direct
quantification of the analyte. This process does not require the use
of extraction reagents, the time-consuming column filtration step
typical of conventional SPE and reduces analyte losses or contam-
ination as well as matrix interferences. In this context, the main
objective of this study was to develop an efficient, sensitive, easy-
handling, and reagent-free procedure, based on dispersive SPE, to
extract, pre-concentrate and directly quantify trace levels of Hg in
natural waters, from rivers to the sea. Iron oxide NPs coated with
silica and functionalized with dithiocarbamate groups were
selected as extraction sorbent since this material combines high Hg
affinity with magnetic properties.
2. Material and methods
2.1. Chemicals
Ferrous sulphate heptahydrate (FeSO4$7H2O, >99%) and carbon
disulphide (CS2, 99%), ethanol (CH3CH2OH, >99%) were obtained
from Panreac (Spain); potassium nitrate (KNO3, >99%), tetraethyl
orthosilicate (Si(OC2H5)4, >99%) (TEOS) and 3-
aminopropyltriethoxysilane (H2N(CH2)3Si(OC2H5)3, >99%) were
 D.S. Tavares et al. / Chemosphere 220 (2019) 565e573
purchased from SigmaeAldrich (Sintra, Portugal); sodium hy-
droxide (NaOH, >98%) from VWR Prolabo (Carnaxide, Portugal);
ammonium solution (NH3, 25%) from Riedel-de-Ha €en; acid nitric
(HNO3, 65%), sodium hydrogen carbonate (NaHCO3, >99,5%) and
the certified standard solution of mercury nitrate (Hg(NO3)2)
(1000 ± 2 mg L1 from Merck (Carnaxide, Portugal). Silox-
ydithiocarbamate precursor (SiDTC) was synthesized following the
procedure reported by Tavares et al. (2013). The chemicals obtained
from commercial chemical suppliers were used without further
purification. Ultra-pure water (UPW) used in the experiments has
high purity (18 MU cm) and was obtained from Millipore Integral
10 system.
2.2. Synthesis and characterization of Fe3O4@SiO2SiDTC
nanoparticles
Fe3O4@SiO2SiDTC NPs were prepared according with the pro-
cedure described in a previous work (Tavares et al., 2013). Briefly,
for the preparation of the magnetic core (Fe3O4), 20 g of FeS-
O4$7H2O were dissolved into 40 mL of deionized water, then heated
at 90  C, under N2 and mechanically stirred. After total dissolution,
60 mL of H2O containing 1.62 g of KNO3 and 11.23 g of KOH were
added dropwise for 5 min to the Fe(II) solution. The black powder
obtained was stirred during 1 h at 90  C, left overnight and then
washed with water and separated magnetically. For functionaliza-
tion of magnetite NPs, 200 mg of Fe3O4 were dispersed into 150 mL
of ethanol in an ice bath and over 15 min under sonication. Then,
12 mL of ammonia solution, 148 mg of SiDTC and 332 mL of TEOS
were added and the mixture was left in an ice bath for 2 h under
sonication. After, the obtained NPs were washed with ethanol and
collected using a magnet. The morphology and the particle size of
the Fe3O4@SiO2SiDTC NPs were confirmed by transmission electron
microscopy (TEM) using a Hitachi H-9000 microscope operating at
300 kV. The chemical composition of NPs was confirmed by Fourier
Transform Infrared (FT-IR) spectroscopy, using a spectrometer
Mattson 7000 with 256 scans and 4 cm1 resolution and a hori-
zontal attenuated total reflectance (ATR) cell.
2.3. Extraction and quantification of Hg in model solutions
The efficiency of Fe3O4@SiO2SiDTC NPs to remove Hg from water
was tested in previous studies (Tavares et al., 2016) for different
operational conditions, such as mass to volume ratio, pH, Hg con-
centrations, and type of natural waters. It was found that approx-
imately 10 mg L1 of Fe3O4@SiO2SiDTC removed >99.9% of the
50 mg L1 of Hg(II) initially added to UPW, estuarine water and
seawater, and the sorbent efficiency was independent of pH (99.9%
for pH range from 2 to 8). Based on these findings we selected to
use 10 mg L1 of sorbent in the extraction experiments.
2.3.1. Extraction time determination
The present work explores the possibility of quantifying Hg at
very low concentrations, corresponding to values reported for
natural waters. Kinetic extraction experiments were designed to
calculate the time corresponding to a full Hg extraction. The
extraction essays were carried out by contacting the magnetic NPs
to 1 L of model Hg solutions (Hg-spiked UPW and Hg-spiked syn-
thetic seawater), using isothermal (21 ± 1  C) batch procedures.
Model solutions were spiked with 10, 20, 50 and 500 ng L1 of Hg
and acidified with 1 mL of HNO3 (65%) to prevent reduction or loss
of target analyte in solution. Synthetic seawater was prepared ac-
cording to the procedure described by Pearsons et al. (1984), by
completely dissolving 31 g L1 of NaCl, 10 g L1 of MgSO4$7H2O and
0.05 mg L1 of NaHCO3$H2O in UPW. Immediately after adding the
sorbent, suspensions were placed in an ultrasonic bath for 5e10 s,
567
for NPs dispersion. This time was considered the starting point of
the extraction experiments. The experiments were carried out
under mechanical stirring using a glass rod and aliquots of water
were sampled at increasing extraction times (5, 15 and 30 min, 1, 2,
4, 6, 8 and 24 h) and the concentration of total dissolved Hg (which,
depending of the type of matrix, may include Hg2þ ions, dissolved
gaseous mercury (Hg0), and Hg bound to inorganic and organic
complexes, such as Cl in seawater or organic matter in real water
samples) was determined by the reference method (CV-AFS), after
magnetic separation of the Fe3O4@SiO2SiDTC NPs using an external
magnetic field.
2.3.2. Extraction and pre-concentration steps
Dispersive SPE essays were performed as previously described,
for the same experimental conditions during 24 h. Afterwards,
magnetic NPs were separate from solution using an external
magnetic field, then washed with UPW, completed dried at room
temperature and weighted. Each dispersive SPE experiment was
replicated five times. All the glassware used in experiments was
washed prior to use with distillate water, HNO3 65% for a least 24 h
and then with UPW.
2.3.3. Quantification of mercury in nanoparticles
Total Hg concentration in the NPs, which corresponds to the
total dissolved Hg in the model solutions, was measured directly by
thermal decomposition atomic absorption spectrometry with gold
amalgamation, using a LECO 254 Advanced Mercury Analyser
(LECO-AMA254). A certain amount of the sorbent used in the SPE
essay was accurately weighed into a cleaned cuvette. Thermal
decomposition of the sample occurs in a quartz catalytic tube, at an
initial stage, the samples are dried at 120  C (10 s) and then com-
busted at 680e700  C (150 s) under oxygen atmosphere. Total Hg
vapour is transported to a gold amalgamator, which is subsequently
heated to 900  C. The released Hg vapour is transported to a heated
cell at 120  C, where the metal is quantified by atomic absorption
spectroscopy.
Mercury was quantified through an internal calibration curve
(0.1e30 ng mg1). Quality of the results was assessed by using the
Certified Reference Material CRM021-100 (Sandy Loam
3e4.7 ng mg1 of total Hg). CRM021-100 was analysed daily, and
percentages of recovery for total Hg were within the range of
80e110%. All samples were analysed in triplicate and relative
standard deviation among replicates was <10%. Percentage of the
extracted Hg was calculated by the difference between the quantity
of Hg added to the solution (Q) and quantity of Hg found in the
sorbent (Qs), divided by Q. Direct Hg analysers take advantage of
the high volatility of Hg, allowing the quantification of Hg in both
liquid and solid samples of organic or inorganic composition, and
without requiring time-consuming sample preparation or diges-
tion methods (Reis et al., 2015).
2.3.4. Quantification of total dissolved mercury in model solutions
Cold vapour atomic fluorescence spectroscopy (CV-AFS) was
used as a reference method to quantify total dissolved Hg con-
centrations in water samples, before and after its extraction by the
NPs. The CV-AFS equipment uses a PSA cold vapour generator,
model 10.003, associated with a Merlin PSA detector, model 10.023.
In this method, Hg present in the sample solution as Hg2þ is
reduced to Hg0, and the Hg vapour is then purged from the solution
with an argon stream, into the optical path of the instrument. Tin
chloride (SnCl2) is used as the reducing agent (2% m/v in HCl 10% v/
v), and Hg is quantified through a calibration curve (r2  0.999) of
five standards (0.0e100 ng L1) prepared in a HNO3 solution (2% v/
v), by dilution from the certified standard stock solution of mercury
nitrate (998 ± 2 mg L1). The detection limit of the CV-AFS is
568 D.S. Tavares et al. / Chemosphere 220 (2019) 565e573
2.5 ng L1, and the precision and accuracy, expressed respectively,
as relative standard deviation and relative error, are <5%. All water
samples were analysed in triplicate.
2.4. Stability of Hg-NPs material over time
To assess the stability of the Hg-NPs material, the total Hg
concentration in the NPs used in the dispersive SPE essays was
evaluated over time. First, dispersive SPE essays were carried out as
previously described, using UPW and synthetic seawater model
solutions with 50 ng L1 of Hg (II). After 24 h, the NPs used in the
essays were isolated using an external magnetic field, washed with
UPW, dried and storage in a glass vial with a plastic cap at room
temperature. At different periods of time (0, 7 and 30 days), total Hg
concentration was measured, as described in 2.3.3, in a portion of
the NPs stored. The total Hg concentration measured at 0 days
corresponds to the analysis of the sample immediately after dry. All
experiments were replicated 3 times.
2.5. Extraction and quantification of Hg in real water samples
To evaluate the applicability of this methodology to real sam-
ples, Hg was determined in freshwater and saline water collected in
the region of Aveiro, Portugal.
Freshwater was sampled in a well (40 45‘59.900 N 8 340 58.700 W)
and the saline water in the Aveiro coastal lagoon (40 430 28.100 N
8 370 56.400 W). Waters were sampled from a depth of 30 cm using
acid-washed polyethylene bottles that were rinsed with surface
water before filled with the sample. Samples were filtered through
a 0.45 mm pore size Millipore cellulose acetate membrane, and the
filtrates were acidified with HNO3 (63%) by adding 1 mL per litre of
sample. The water samples were characterized in terms of pH,
temperature, salinity and Hg concentration (reactive and total).
Reactive Hg is quantified by direct water analysis by CV-AFS, and
total Hg is quantified by CV-AFS after chemical/UV digestion of the
water sample. Briefly, 500 mL of a saturated solution of potassium
persulfate are added to 50 mL of filtered water, followed by UV
irradiation (1000 W) for 30 min. After, the excess of oxidant was
reduced with 40 mL of hydroxylamine solution 12% (w/v) (Mucci
et al., 1995).
Dispersive SPE essays were performed, as previously described,
using non-spiked and spiked (20 ng L1) fresh and saline real water
samples (the last ones, to overcome the possibility of values lower
than detection limit of the quantification method). After 24 h,
a)
40
Frequency
30
20
10
0
100
120
140
160
180
200
60
80
size, nm
100 nm
Fig. 1. Transmission electron microscopy (TEM) image and particle size distribution of Fe3O4@SiO2SiDTC nanoparticles (a) and ATR FT-IR spectra (b).
magnetic NPs were separate from solution using an external
magnetic field, then washed with UPW, completed dried at room
temperature and weighted. The total Hg extracted by the NPs was
quantified directly by thermal decomposition, as previous
described. The total Hg concentration in the NPs corresponds to
total dissolved Hg in the water samples or to the Hg spike plus the
total dissolved Hg originally in the water samples. These essays
allowed to evaluate matrix interferences.
3. Results
3.1. Characteristics of Fe3O4@SiO2SiDTC nanoparticles
Nanoparticles used in the present study were composed of
ferromagnetic magnetite with cubic morphology and a medium
size of 117 ± 30 nm (Fig. 1a). Morphology observed by TEM images
is in accordance with the full characterization previously described
by Tavares et al. (2013). Fig. 1b shows FT-IR spectra of Fe3O4@SiO2/
SiDTC nanoparticles. The strongest absorption band was at
559 cm1, which corresponds to the stretching vibration FeeO
related to magnetite (Fe3O4). Absorption band at 1040 cm1 reflects
the symmetric SieOeSi stretching vibration, confirming the graft-
ing of a silica network onto the Fe3O4 nanoparticles. Finally, very
weak absorption bands at 678 cm1 and 1490 cm1 correspond to
stretching of CeS and NeCS2 groups, respectively, and indicate the
presence of dithiocarbamate groups on the surface of nano-
particles. High adsorption capability of these nanosorbents has
been associated with the presence of dithiocarbamate groups at the
surface, whose chemical affinity for mercury is well-known
(Girginova et al., 2010; Tavares et al., 2013). In brief, these func-
tionalized NPs revealed an exceptional sorption behaviour for
mercury dissolved in natural waters (Tavares et al., 2016).
3.2. Performance of the method
Fig. 2 shows the performance of Fe3O4@SiO2SiDTC NPs to extract
total dissolved Hg at concentrations of 10, 20, 50 and 500 ng L1 in
model Hg solutions. The abrupt decrease of Hg concentration in
solution in the first minutes points to its fast sorption onto the NPs.
Within the first 5 min, 10 mg L1 of the NPs were sufficient to
extract more than 80% of the Hg added to UPW or to synthetic
seawater, and after 24 h it exceeded 91%. Table 1 shows the per-
centage of Hg sorbed to Fe3O4@SiO2/SiDTC after 24 h of exposure in
UPW and synthetic seawater spiked with 10, 20, 50 and 500 ng L1.
b)
T ra n s m ita n c e , a .u
1490
678
1040
559
3000 2500 2000 1500 1000 500
-1
W a v e n u m b e r, c m
 D.S. Tavares et al. / Chemosphere 220 (2019) 565e573 569

A) B)

100 100
i. i.

10 ng L-1 10 ng L-1
CHg (ng L-1)

CHg (ng L-1)

-1
20 ng L 20 ng L-1
10 10

1 1

0 4 8 12 16 20 24 0 4 8 12 16 20 24
time (h) time (h)

1000 1000
ii. ii.

50 ng L-1 50 ng L-1
100 100

CHg (ng L-1)

CHg (ng L-1)

500 ng L-1 500 ng L-1

10 10

1 1

0 4 8 12 16 20 24 0 4 8 12 16 20 24
time (h) time (h)

Fig. 2. Mercury concentrations (ng L1) in ultra-pure water (A) and synthetic seawater (B) spiked with 10, 20 (i.) 50 and 500 ng L1 (ii.) after adding 10 mg of Fe3O4@SiO2SiDTC
nanoparticles.

Table 1 60
Mercury added to ultra-pure water and synthetic seawater (Q, ng L-1), measured in
Fe3O4@SiO2SiDTC nanoparticles (Qs, expressed in ng L-1) and recovery (R, %) of Hg
from nanoparticles calculated as (Qs:Q)*100; mean ± SD, n ¼ 5.
C Hg (ng L )

40
-1

Sample Q (ng L1) Qs (ng L1) R (%)

Ultra-Pure water
Ultra-pure water 0 n.d. --- 20 Synthetic seawater
10 10 ± 3 97 ± 26
20 22 ± 3 107 ± 16
50 47 ± 3 93 ± 7
0
500 416 ± 59 83 ± 12
Synthetic seawater 0 n.d. --- 0 7 30 0 7 30
10 10 ± 2 95 ± 14
20 26 ± 7 110 ± 7 Days
50 51 ± 3 103 ± 6
500 478 ± 40 95 ± 9 Fig. 3. Estimated Hg concentration (ng L1) in ultra-pure water and synthetic seawater
n.d. - not detectable spiked with 50 ng L1, obtained by direct analysis of Hg in NPs over time (error bars
represent the standard deviation, n ¼ 3).

Recovery was 83e107% for UPW and 95e110% for synthetic
seawater. Variability among the five replicates exceeded 20% for
samples with the lowest Hg concentration (10 ng L1) and below
10% for samples with the highest concentration (500 ng L1).
Possible interfering ions in seawater had a low effect on the
extraction and pre-concentration steps. The stability of Hg con-
centrations retained in the Fe3O4@SiO2/SiDTC along time (Fig. 3)
indicated that losses or contamination over 30 days were negli-
gible, when these NPs are used to extract and pre-concentrate Hg.
The limit of detection (LOD) and the limit of quantification (LOQ)
were calculated from quantifying the amount of Hg on magnetic
NPs mixed with ten blank samples of UPW. The limits were
determined using the equations LOD ¼ mþ3s and LOQ ¼ mþ10s,
respectively, where m is the mean of the ten blanks and s is the
standard deviation of the blank. Values of LOD and LOQ obtained
were 1.8 ng L1 and 3.6 ng L1, respectively.
3.3. Application to real samples
The natural freshwater had a pH of 7.34 at 21  C and salinity of
zero, while saline water had a pH of 7.88 at 21  C and salinity 27.
Table 2 shows the Hg total concentrations quantified in freshwater
and saline water by CV-AFS, the Hg added to the corresponding
water samples, the concentration of Hg measured on the NPs after
extraction and the recovery percentage. This methodology was
applied to a spiked (20 ng L1) and non-spiked saline water, the
570 D.S. Tavares et al. / Chemosphere 220 (2019) 565e573

Table 2
Mercury concentrations in real freshwater and saline water (Q0, ng L1), Hg added to
aliquots (Q, ng L1), total Hg measured in Fe3O4@SiO2SiDTC NPs (Qs, expressed in ng
L1) and recovery (R, %) total Hg in NPs calculated as (QS: (Q0þQ))*100; mean ± SD,
n ¼ 3.
Sample Q0 (ng L1) Q (ng L1) QS (ng L1)
Fresh water 67 0 61
67 20 81
Saline water n.d 0 n.d.
n.d 20 21
n.d. - not detectable
latter with a total Hg dissolved concentration below the detection
limit, as well as to a spiked (20 ng L1) and non-spiked freshwater
sample, the latter containing 61 ng L1 of total dissolved Hg. More
than 91% of total Hg was recovery for both real freshwater and
saline water and from the corresponding spiked samples.
4. Discussion
This study describes a reliable methodology for measuring low
to moderate total dissolved Hg concentrations currently found in
saline and freshwaters. By using 10 mg L1 of Fe3O4@SiO2SiDTC NPs
as sorbents it was possible to extract and quantify as low as
10 ng L1 of Hg in water samples. One of the advantages of
extracting and pre-concentrating total dissolved Hg in water sam-
ples during the sampling campaigns is to minimize the risk of
contamination and analyte loss through stabilization, transport and
storage of water samples. Conventional methodologies require
sorbents filtration (Konshina et al., 2016a, 2016b), centrifugation
(Mohajer et al., 2017) or decantation (Krawczyk and Stanisz, 2016)
after extraction to separate the sorbents from aqueous solutions.
These time-consuming steps and source of contamination are
avoided in the proposed methodology. The ferromagnetic behav-
iour of the sorbent used in the present methodology facilitates its
separation by applying an external magnetic field (Luo et al., 2011;
Tavares et al., 2013; Ma et al., 2016). Most common analytical
techniques for Hg analysis after Hg pre-concentration process in
sorbents require further steps such as elution, digestion or
desorption of Hg species adsorbed on the sorbents in order to
obtain the analyte in aqueous solution (dos Santos et al., 2009; Gao
et al., 2009; Adlnasab et al., 2014; Mehdinia et al., 2016; Keramat
and Zare-Dorabei, 2017). These steps and the use of other chem-
icals increase the risk of contamination and analyte loss.
The direct analysis of Hg on the magnetic sorbent by thermal
decomposition does not allow the reuse of the sorbent since it is
R (%)
partly destroyed during the process. Nevertheless, in our opinion
91 ± 3 that fact it is not necessary a disadvantage due to the very low
93 ± 0
quantity of NPs which are used in each essay. In other configura-
---
103 ± 11 tions, when eluation could be used to regenerate the sorbents, re-
agents are spent, time consumption is required, and wastes are
generated. So, all these aspects should be kept in mind when
evaluating the benefits and costs of the regeneration processes.
Kinetics and stability studies indicate an irreversible, fast and
efficient sorption of Hg onto NPs probably due to the formation of
stable complexes of Hg species involving dithiocarbamate func-
tional groups at the surface of Fe3O4@SiO2SiDTC NPs, as predicted
by the stability constants reported for Hg-dithiocarbamate complex
(Venkatesan et al., 2002). Strong affinity of Hg to the functional
dithiocarbamate groups on the surface of nanoparticles explains
the high recovery experimented in both, ultra-pure water and
synthetic seawater, suggesting that complexity of the matrix does
not affect the adsorption behaviour of Fe3O4@SiO2SiDTC NPs.
Although rapid sorption was achieved with in the first minutes, it is
recommended to prolong the sorption for 24 h because it provides
a good practicability for the fixation of total Hg, either on board of
oceanographic campaigns, or on smaller vessels to sample river and
estuarine waters. If necessary, shorter periods may be adopted with
a slight increase of NPs quantity. Shorter times for total Hg
extraction from solutions have been reported, but in the most of
cases the experimental conditions require the application of high
amounts of sorbents. For example, Zhai et al. (2010) developed a
methodology for solid-phase extraction and pre-concentration of
Hg using 2 g L1 of nanoparticles as sorbent and the maximum
adsorption was achieved within 5 min; (Adlnasab et al., 2014)
applied 8 g L1 of sorbent and 5 min for adsorption time; (Cui et al.,
2015) used 1 g L1 of sorbent and the adsorption was within
15 min; Ziaei et al. (2014) used 240 mg L1 of sorbent for 10 min of
contact with solutions containing Hg. Another advantage of the
proposed methodology is the much smaller quantity of sorbent
used. Fe3O4@SiO2SiDTC NPs showed high efficiency to complex
with Hg, remaining stable after complexation and no losses of Hg

Table 3
Limit of detection (LOD, ng L1) obtained for Hg determination in this work and in published work using different configurations of solid phase extraction techniques and
different types of nanomaterials.

Configuration mode for SPE Type of sorbent Sorbent LOD (ng L1) Reference

Dispersive Magnetic MWCNTs-Fe3O4 15 Es'haghi et al. (2016)

DT-Fe3O4 50 Adlnasab et al. (2014)
Fe3O4@SiO2@AMPTs 17 Cui et al. (2015)
Fe3O4@polythionine 8 Mehdinia et al. (2016)
Fe3O4@graphene oxide/2-pyridinethiosemicarbazone 7.9 Keramat and Zare-Dorabei (2017)
Fe3O4@SiO2/SiDTC 1.8 This work
Non magnetic SiO2-APTM 4.5  102 Kaur (2016)
SiO2e 2-(2-Oxoethyl)hydrazine carbothioamide 1.0  102 Chai et al. (2010)
TiO2 4 Krawczyk and Stanisz (2016)
Ag 5 Krawczyk and Stanisz (2015)
CeO2 10 Mohajer et al. (2017)
SiO2-2,6-PDCA 90 Zhang et al. (2010)
Silica gel/DETA-TU 23 Jiang et al. (2012)
Disks/membranes Non magnetic Ag or Au 0.4 Panichev et al. (2014)
Dithizone nanofiber 1.0  104 Takahashi et al. (2009)
Columns Non magnetic Gold-Coated SiO2 0.2 Leopold et al. (2009)
oxidised carbon nanotubes-ox-CNTs 1.9 Parodi et al. (2014)
Chitosan-modified ordered mesoporous silica 9.3  102 Chen et al. (2009)
g-MPTS-modified nanometre-size Al2O3 0.5 Pu et al. (2004)
Dipsticks/Fibers Non magnetic SiO2eN,N0 -bis(3-(2-thenylidenimino) propyl)piperazine 50 Afkhami et al. (2013)
Nano cellulosic fibers 97  103 Rajawat et al. (2013)
 D.S. Tavares et al. / Chemosphere 220 (2019) 565e573
was observed over time. The detection limit of 1.8 ng L1 of the
methodology here described is compared with the LOD values of
other SPE methodologies, reported in literature, for extraction and
quantification of Hg (Table 3). Among SPE procedures, dispersive
configuration is the most common and several works using mag-
netic and non-magnetic NPs have been reported recently. As pre-
viously described, the procedure is simple and rapid, by direct
application of NPs to the water for Hg extraction. Magnetic NPs
have an additional advantage over non-magnetic NPs due to its
easy separation from aqueous solutions by application of an
external magnetic field, while non-magnetic NPs require other type
of solid-liquid separation processes, that implies additional sample
manipulation. Among dispersive SPE configuration, the LOD of the
proposed methodology is by far the lowest amongst magnetic NPs e
and it is slightly lower that the LOD reported by Krawczyk et al.
(2015, 2016) that used Ag and TiO2 NPs. In a small number, other
type of SPE configurations have also been reported for Hg extrac-
tion and pre-concentration, including the application of NPs in
columns, fibers, membranes/disks or dipsticks. The reduced num-
ber of works using these configurations maybe due to the
complexity of the procedures that are needed to pack the NPs in the
columns, membranes or fibres, increasing the sample preparation
time. Nevertheless, the lowest LOD reported (0.5 ng L1) were
found for this type of SPE configuration, using Ag, Au or MPTS-
modified with nanometre size Al2O3 (Panichev et al., 2014;
Leopold et al., 2009; Pu et al., 2004). However, comparation of
SPE methodologies is often misleading due to use of different
procedures and experimental conditions, analytical techniques or
sorbents.
Fe3O4@SiO2SiDTC NPs tested in the quantification of total dis-
solved Hg in real water samples allowed to achieve recoveries
higher than 91%, meaning that the proposal methodology can be
easily applied with adequate precision and accuracy. Furthermore,
it is demonstrated that Hg extracted by these NPs exceeded largely
the value of the Hg reactive fraction, confirming that the NPs are
able to capture not only the reactive species but also other Hg
reactive fraction, confirming that the NPs are able to capture not
only the reactive species but also other Hg species present. In this
work, we did not study the effect of natural organic matter (NOM)
contents but, knowing that Hg has high affinity for NOM we believe
that different content can have influence the proposed methodol-
ogy. We do not expect that the Hg extraction process is inhibited by
high levels of NOM but the extraction rate may differ. In a previous
work Tavares et al. (2016) found that the degree of efficiency of the
removal process using Fe3O4@SiO2SiDTC is related to differences in
water composition with competition between NPs and water
constituents for Hg(II) species, in river water where the levels of
NOM were higher. In the current study, around 90% of the Hg was
recovered from freshwater, while a value of 100% was obtained in
saline water. This difference, although small, may be attributed to
difference NOM content.
5. Conclusions
A two-step (extraction/pre-concentration þ quantification)
method was developed for a reliable determination of total dis-
solved Hg in natural waters. The method is robust and sensitive. In
the first step, Fe3O4@SiO2SiDTC NPs act as an effective sorbent,
extracting Hg from water, while in the second one, the extracted Hg
is quantified by directly analysing the NPs in a simple and low-cost
commercial mercury analyser.
As a proof-of-concept, the proposed methodology was suc-
cessfully applied to quantify Hg in real fresh and saline water, with
relative error ranging from 5 to 8.9%. As main advantages of this
methodology we may highlight, the high efficiency, sensitivity and
571
reproducibility, need of small quantities of Fe3O4@SiO2SiDTC NPs
per volume of water, possibility of extraction in situ, good stability
of the NPs after Hg extraction over time, simplicity and low-cost.
Overall, we believe that all these characteristics point to one
methodology with very good performance for Hg detection and
quantification in natural waters.
Acknowledgments
This work was supported by the National Funding for Science
and Technology (FCT) through doctoral and postdoctoral grants to
D.S. Tavares [SFRH/BD//103828/2014] and to C.B. Lopes [SFRH/BPD/
99453/2014]; and the University of Aveiro, FCT/MEC for the finan-
cial support to CESAM, CICECO and CIIMAR [UID/AMB/50017/2013;
UID/CTM/50011/2013; UID/Multi/04423/2013], through national
funds and, where applicable, co-financed by the FEDER, within the
PT2020 Partnership Agreement. The work is connected objectives
of the project CORAL - Sustainable ocean exploitation: tools and
sensors (NORTE-01-0145-FEDER-000036).
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