Talanta 170 (2017) 451–456

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Talanta
journal homepage: www.elsevier.com/locate/talanta

Recycling polymer residues to synthesize magnetic nanocomposites for MARK

dispersive micro-solid phase extraction
Hoda Ghambaria, Emilia M. Reyes-Gallardob, Rafael Lucenab, Mohammad Sarajia,
⁎
Soledad Cárdenasb,
a
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran
b
Departamento de Química Analítica, Instituto Universitario de Investigación en Química Fina y Nanoquímica IUIQFN, Universidad de Córdoba, Campus
de Rabanales, Edificio Marie Curie, E-14071 Córdoba, Spain

A R T I C L E I N F O A BS T RAC T

Keywords: The ubiquitous presence of plastics, an obvious consequence of their usefulness and low price, has turned them
Dispersive micro-solid phase extraction into a problem of environmental and safety concern. The new plastic economy, an initiative recently launched
Magnetic polystyrene nanocomposite by the World Economic Forum and Ellen MacArthur Foundation, with analytical support from McKinsey &
Polymer recycling Company, promotes a change in the use of plastic worldwide around three main pillars: redesign, reusing and
Sustainable chemistry
recycling. Recycled plastics, with the aim of extending their life spam, can be used to synthesize materials for
Parabens
LC–MS/MS
analytical purposes. In this article polystyrene (PS) trays, previously used for food packaging, are proposed as
polymeric source for the synthesis of magnetic nanocomposites. The synthesis plays with the solubility of PS in
different solvents in such a way that PS is gelated in the presence of cobalt ferrite nanoparticles which are finally
embedded in the polymeric network. The extraction capability of the magnetic PS nanocomposite was evaluated
using the determination of four parabens (methylparaben, ethylparaben, propylparaben and butylparaben) in
water using liquid chromatography-tandem mass spectrometry as model analytical problem. Under the
optimum conditions, limits of detection and quantification were in the range of 0.05–0.15 and 0.15–0.5 ng/
mL, respectively. The precisions, expressed as relative standard deviation (RSD), varied between 4.4% and 8.5%
and the relative recoveries for analysis of the water samples were in the interval 81.2–104.5%.

1. Introduction complemented by a new document [9] where specific actions, hinged

around three main pillars (namely: redesign, reusing and recycling),
The overall production of plastics worldwide reached 311 millions are recommended. Analytical Chemistry may play a double role in this
of tons in 2014 [1], the European Community contribution represent- complex scenario. As it is obvious, the development of methods able to
ing the 20% of this amount. The undoubted usefulness and low price of determine all these compounds in samples of different nature is
plastics, that build the world we live in, make these materials essential to control these situations indicating the necessity of further
ubiquitous. Owing to that, plastics have become a current problem of actions (e.g. remediation). Complementarily, plastics can be recycled to
environmental and safety concern. The pollution of environmental fabricate new materials with analytical applications.
waters with bulk materials (e.g single use plastic bags) [2], fibers [3], Polymers are extensively used in analytical laboratories for different
plastic residues [4,5] and even plastic additives [6] is periodically purposes including passive (containers, flasks, tubing and filters) and
reported, having a dramatic effect on the ecosystems. This is also a active ones. Among the latters, their potential as sorptive phases in
safety problem for humans whose exposure is further aggravated by the solid phase extraction [10] and solid phase microextraction [11–14] is
extensive use of plastic containers for food packaging [7]. In the light of beyond any doubt. Polymers are versatile thanks to their availability in
the data exposed above, policy-makers have identified this situation as different compositions and formats (beads, coatings, membranes).
a critical and priority issue. The World Economic Forum and Ellen Apart from the high commercial availability, some polymer can be
MacArthur Foundation, with analytical support from McKinsey & ad-hoc synthesized in the lab [15,16] according to the analytical
Company, promoted the so-called "The new plastics economy" [8] in problem under study.
2016 to face this global challenge. This initiative has been recently The combination of nanoparticles (NPs) and polymers, forming the

⁎
Corresponding author.
E-mail address: [email protected] (S. Cárdenas).

http://dx.doi.org/10.1016/j.talanta.2017.04.026
Received 2 March 2017; Received in revised form 3 April 2017; Accepted 11 April 2017
Available online 12 April 2017
0039-9140/ © 2017 Elsevier B.V. All rights reserved.
H. Ghambari et al. Talanta 170 (2017) 451–456

so-called polymeric nanocomposites, expands even more the applica- tion. The polymer (150 mg) was dissolved in chloroform (5 mL) and
tion scope [17]. Nanocomposites, which merge the properties of both 200 mg of MNPs were dispersed into solution aided by ultrasounds
materials, can be synthesized in different ways. On the one hand, the (5 min). The dispersion was added over acetone (50 mL) by a glass
polymer can be attached by electrostatic [18] or covalent [19] interac- dropper. The solvent changeover, from chloroform to acetone, reduces
tions to the NPs surface, the resulting composite maintaining the dramatically the solubility of PS inducing its gelation around MNPs.
nanometric size. On the other hand, the NPs can be embedded in the The final magnetic PS nanocomposite was washed and dried in a oven
micrometric polymeric network [20] modifying the porosity of the before being used.
structure. Among all the combinations, magnetic nanocomposites are
the preferred option in dispersive micro-solid phase extraction thanks 2.3. Characterization of the magnetic polystyrene nanocomposite
to their easy dispersion and retrieval applying an external magnetic
field [21,22]. The magnetic PS nanocomposite was characterized using several
In 2016, Psillakis et al. demonstrated the potential of industrial instrumental techniques aimed at knowing its chemical composition
plastic pellets as sorptive phases towards polycyclic aromatic hydro- (infrared spectroscopy and elemental analysis) and morphology (mi-
carbons opening a door to use plastic overstock in a different way [23]. croscopy and superficial area measurements).
The present article delves into this idea proposing the recycling of Fourier transform infrared (FT-IR) spectra were recorded with a
polystyrene (PS) into nanocomposite to extend the usable life of the Bruker Tensor 37 FT-IR spectrometer, equipped with a diamond ATR
plastic. PS, which is widely employed for food packaging among other cell with a circular surface of 3 mm diameter and three internal
uses, presents a very slow degradation rates in the environment [24]. reflections. The spectrometer has a Deuterated Triglycine Sulfate
Its expandable form, as that use in this work, causes outsized troubles (DTGS) detector for spectra acquisition. The measurements were
when they leak into marine environments and contaminate water [25]. performed in the range of 600–4000 cm−1 at a 4 cm−1 resolution with
The synthesis of the magnetic nanocomposite is based on the different 64 coadded scans. Data collection was carried out using OPUS software
solubility of the polymer in two solvents following a workflow that has (Bruker, Ettligen, Germany). Carbon content of the synthesized
been successfully used by our group on the synthesis of polyamides- composites was measured by a EuroVector Elemental Analyzer
based nanocomposites [26,27]. In short, the polymer is dissolved in an EA3000 (EuroVector SpA, Milan, Italy).
appropriate solvent and a defined amount of magnetic NPs (MNPs) are Scanning electron microscopy (SEM) images of the synthesized
dispersed into this solution. The dispersion is finally injected in a composite were obtained using a JEOL JSM 6300 scanning electron
different medium which induces the precipitation of PS around the microscope while the superficial area of the materials was measured in
MNPs. The synthesized nanocomposite has been completely character- a Quantachrome® ASiQwinTM-Automated Gas Sorption Data analyzer.
ized and practically evaluated for the extraction of selected parabens The measurements were based on the nitrogen adsorption/desorption
from water samples. at −196 °C and BET (Brunauer–Emmett–Teller) equation was used for
calculation of the specific surface area values.
2. Experimental section Both the micrographs and elemental analysis were developed in the
Central Service for Research Support (SCAI) of the University of
2.1. Reagents Cordoba. Gas sorption measurements were played out in the Institute
of Fine Chemistry and Nanochemistry at the University of Cordoba.
All the reagents were of analytical grade or better. Unless otherwise
specified, they were purchased from Sigma-Aldrich (Madrid, Spain). 2.4. Extraction procedure
Stock standards solutions of the analytes (methylparaben, ethylpar-
aben, propylparaben and butylparaben) were prepared in acetonitrile The dispersive micro-solid phase extraction involves several and
at a concentration of 1000 µg/mL. These solutions were stored at 4 °C well defined steps. First of all, 40 mg of the magnetic PS nanocompo-
in the dark until being used. Working solutions were prepared daily by site is placed in a 25 mL glass vial and 1 mL of methanol is added for
rigorous dilution of the stocks in methanol or Milli-Q water (Millipore sorbent conditioning. After that, Milli-Q water at pH 3 is added for
Corp., Madrid, Spain) as required. sorbent equilibration followed by the addition of 20 mL of aqueous
Iron(III) nitrate nonahydrate, cobalt(II) nitrate hexahydrate, so- standard or sample adjusted at pH 3. The vial, containing both the
dium hydroxide and hydrogen peroxide (33% v/v) were employed for sorbent and the sample, is agitated in a vortex for 15 min to enhance
the synthesis of the magnetic nanoparticles (Fe2CoO4). Commercial PS the transference of the analytes from the bulk solution to the
trays, previously used for food packaging, were used as polymer source. nanocomposite. The use of multiport vortex allows the simultaneous
Chloroform and acetone were selected as solvents to induce the extraction of several samples. After the extraction, the nanocomposite
solubilization/precipitation of PS which is essential in the synthesis is washed with 5 mL of Milli-Q water, dried and eluted with 500 µL of
of the magnetic nanocomposite. methanol. The final eluate is evaporated to dryness in a multiport
vacuum concentrator and the residue is dissolved in 50 µL of methanol
2.2. Synthesis of the magnetic polystyrene nanocomposite for further instrumental analysis. The above described procedure takes
advantage of the magnetic nature of sorbent in such a way that the
MNPs were synthesized using iron(III) nitrate nonahydrate (20.2 g) nanocomposite is easily recovered from the working solution (solvent,
and cobalt(II) nitrate hexahydrate (7.3 g) as precursors. These com- standard or sample) by an external magnet (549.4 N of maximum
pounds were firstly dissolved in 50 mL of Milli-Q water, the solution magnetic force, Supermagnete, Gottmadingen, Germany).
being heated at 80 °C. After that, 250 mL of a sodium hydroxide
solution (1.2 M) was added dropwise, maintaining the reaction mixture 2.5. LC-MS/MS analysis
under vigorous stirring for 2 h at the same temperature. Finally,
250 mL of hydrogen peroxide (33% v/v) was gradually added, the Liquid chromatographic analyses were carried out by an Agilent
resulting dispersion being in continuous stirring for 2 h. As a result of 1260 Infinity HPLC system (Agilent, Palo Alto, CA, USA) equipped with
this process, Fe2CoO4 MNPs were obtained. These MNPs were isolated an autosampler and a binary high-pressure pump for mobile phase
by using an external magnet, rinsed with Milli-Q water and acetonitrile, delivery. Separation was performed on a Poroshell 120 SB-C18 column
and finally dried in an oven at 80 °C. (2.7 µm, 2.1 mm×75 mm) from Agilent, under a gradient elution
Commercial PS trays were manually ground to favor the prelimin- program using water (solvent A) and acetonitrile (solvent B) as mobile
ary washing of the polymer (water and acetone) and its final dissolu- phase components. The gradient elution program was as follows: 30%

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H. Ghambari et al. Talanta 170 (2017) 451–456

solvent B for 6 min then, linearly increased to 60% within 1 min, kept
60% for 8 min and returned to 30% within 0.1 min. The flow rate was
maintained at 0.2 mL/min and injection volume was 20 µL.
An Agilent 6420 Triple Quadrupole mass spectrometer equipped
with electrospray ionization (ESI) source was used for analytes detec-
tion. Data analysis was carried out by Agilent MassHunter Software
(Version B.06.00). The tandem mass spectrometer was operated in the
multiple reactions monitoring (MRM) mode and ESI was performed in
the negative ion mode. The temperature and flow of the drying gas (N2)
were 350 °C and 5 L/min respectively. The nebulizer pressure was set
at 20 psi, and the capillary voltage was 6000 V. Optimized parameters
for each compound are mentioned in Supplementary material Table 1.

3. Results and discussion

The synthesis of the PS magnetic nanocomposite plays with the

solubility of the polymer in different solvents. Among the usual lab
solvents, only chloroform is able to dissolve PS easily. On the other
hand, PS is not soluble in many solvents like water, acetone or
methanol. The nanocomposite synthesis requires a fast solvent change-
over to allow the gelation of PS around the MNPs. Water was avoided
as gelation solvent due to immiscibility with chloroform. Therefore,
other solvents were evaluated, acetone being finally selected because its
low price and toxicity.
We have to admit that the use of organic solvents (chloroform and
acetone) hinders the environmental friendship of the proposal, even
when it involves the recycling of a polymer residue. However, it should Fig. 2. Scanning electron microscopy (SEM) images of the magnetic-polystyrene
also be considered that the volume (55 mL) is comparable or even nanocomposite at ×500 and ×2000 magnifications.
lower than that commonly used in organic synthesis. The separation of
the solvents after the synthesis is also an option. Classical distillation,
the first option coming to mind, is not possible since the solvents form C-H deformation). On the other hand, the MNPs shows an intense
an azeotrope. However, extractive distillation and pressure-swing absorption band around 600 cm−1 which matches with it characteristic
distillation can be applied (usually on a large scale) for that purpose bending vibration. In addition, the presence of remaining water over
[28] opening a door to solvents recycling. the MNP surface can be observed in the spectrum background. The IR
spectrum of the nanocomposite combines the bands of PS and MNPs
3.1. Characterization and preliminary evaluation of the synthesized which corroborates its efficient synthesis. Fig. 2 shows the SEM images
magnetic PS nanocomposite of a nanocomposite at two different magnifications. SEM images were
pretty similar in all the nanocomposites showing a rough surface due to
The success on the synthesis of the magnetic PS nanocomposite can the NPs. These MNPs interfere in the normal stacking of the polymer
be proven by FTIR spectroscopy. Fig. 1 shows the IR spectra for PS, chains inducing a porosity enhancement as it will be further discussed.
MNPs and resulting nanocomposite. As it can be observed, PS presents Attending to the literature [29], the proportion of polymer and NPs
different and characteristics absorption regions, namely: 3080– usually has a dramatic effect on the nanocomposite properties. For this
3030 cm−1 (aromatic C-H stretching), 3000–2800 cm−1 (aliphatic C- reason, several nanocomposites with a different starting amount of PS
H stretching), 1625–1475 cm−1 (aromatic C-C stretching), 1250– (50, 100, 150 and 200 mg) were synthesized following the procedure
900 cm−1 (aromatic C-H deformation) and 900–650 cm−1 (aromatic described in Section 2.2. The extraction ability of the resulting
nanocomposites as well as their carbon content and porosity were
evaluated. Fig. 3 shows the analytical signal obtained for all the
analytes after the extraction (30 min) of an aqueous standard
(10 mL, 500 ng/mL in each analyte) with a given nanocomposite
(20 mg, final elution with 500 µL of methanol). As it can be observed,
the analytical signal increases up to 150 mg of PS being lower at
200 mg. In addition, the precision got worse at the higher PS amount.
The carbon content and the superficial area of the solids were
further studied in order to clarify the results. The obtained data were
different, in some cases, than those expected. The carbon content
should increase with the increasing of the starting PS amount.
Although this tendency was observed for the first three solids (%C
average values: 16, 23 and 27 respectively), it broke for the last one
(22% of C). On the other hand, the superficial area should be reduced
with the PS amount as it covers the MNPs surface. Once again, the first
three solids followed the expected trend (average surface values: 110.3,
82.9 and 52.4 m2/g) but the last one failed (75 m2/g). The results
indicate that PS is not easily incorporated to the nanocomposite in the
latter conditions. In fact, the heterogeneity of the material was obvious
Fig. 1. Infrared spectra of polystyrene, the MNPs and the magnetic-polystyrene during the synthesis, weak magnetic material and PS blocks being
nanocomposite. observable apart from the normal nanocomposite.

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H. Ghambari et al. Talanta 170 (2017) 451–456

Fig. 3. Effect of the polystyrene amount on the extraction capability of the nanocompo-
site. The percentage of C and the superficial area of each solid are also shown. Analytes:
methylparaben (MP), ethylparaben (EP), propylparaben (PP) and butylparaben (BP).
Fig. 4. Effect of the sample volume on the extraction of the analytes. Analytes:
In summary, the third nanocomposite provided the best surface and methylparaben (MP), ethylparaben (EP), propylparaben (PP) and butylparaben (BP).
carbon values to enhance the extraction and therefore it was selected as
the optimum sorbent.

3.2. Optimization of D-μSPE

Once the optimum composition of the nanocomposite was evalu-

ated, the dispersive micro-solid phase extraction was characterized in
depth considering several variables. For brevity, only those with an
interesting effect will be discussed although the complete list of
variables and their optimum values are included in Table S2.
Sorbent amount, which defines the maximum extraction capacity,
was studied in the interval from 5 to 50 mg for the extraction of 10 mL
of an aqueous standard (500 ng/mL, pH 3). The results, data not
shown, demonstrated an increase of the analytical signal for all the
analytes up to 20 mg but a signal decreases for larger amounts. The
latter decline can be ascribed to a worse dispersion of the sorbent in
such conditions. In the light of the results, 2 mg of sorbent per mL of
solution was selected as the optimum dispersion conditions.
Sample volume was studied in the interval from 5 to 50 mL. In
order to work under the optimum dispersion conditions, the sorbent/
volume ratio was maintained at the above mentioned value. The
signals, as it can be observed in Fig. 4, increases with the sample
volume up to 20 mL remaining almost constant for larger volumes.
Therefore, 20 mL was selected as the optimum value to minimize the Fig. 5. Effect of the extraction time on the extraction of analytes. Analytes: methylpar-
sorbent and sample requirements. aben (MP), ethylparaben (EP), propylparaben (PP) and butylparaben (BP).
Extraction time, studied the range from 5 to 60 min, shows (Fig. 5)
a rapid kinetic. Although 5 min is enough to achieve a high extraction
rate, 15 min was selected as it provided better precision.
Among all the solvents tested (methanol, ethanol, acetone, n- Table 1
hexane and toluene), methanol provided the best elution rates. In Analytical figures of merit of the proposed method for the selected analytes.
order to improve the preconcentration of the analytes, an evaporation/
redisolution of the final eluates was selected. Analyte Linear Coefficient of LODa LOQb EFc RSD%
range determination (R2) (n=6)d
(ng/mL) (ng/mL) (ng/mL)
3.3. Analytical figures of merit and sample analysis
MP 0.5–50 0.997 0.15 0.50 11.7 8.5
EP 0.5–50 0.998 0.13 0.42 14.8 6.5
The method was analytically characterized in terms of linearity PP 0.5–50 0.998 0.07 0.23 42.3 6.3
(linear range and correlation coefficient), sensitivity (limits of detection BP 0.5–20 0.997 0.05 0.15 35.3 4.4
and of quantification), precision (repeatability and reproducibility) and
extraction efficiency (enrichment factor and extraction recovery). The Analytes: methylparaben (MP), ethylparaben (EP), propylparaben (PP) and butylparaben
results, which are summarized in Table 1, showed a good linearity for (BP).
a
Limit of detection.
all the analytes (R2≥0.997). Limits of detection (LODs) and quantifica- b
Limit of quantification.
tion (LOQs) were calculated for a signal to noise ratio of 3 and 10 c
Enrichment factor.
d
respectively. LODs range from 0.05 to 0.15 ng/mL while LOQs were in Relative standard deviation.

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H. Ghambari et al. Talanta 170 (2017) 451–456

Table 2 at the 2 ng/mL to evaluate the accuracy of the proposal. The relative
Analysis of water samples spiked with the target analytes at 2 ng/mL level. recoveries, summarized in Table 2, were in the range of 81.2–104.5%
and fulfill the criteria for environmental analysis. Fig. 6 shows the
Analyte River Creek Tap
(R ± SD)a (R ± SD) (R ± SD) obtained chromatograms obtained for a creek sample analyzed before
and after its spiking at 2 ng/mL.
MP 90 ± 4 104 ± 4 89 ± 4 The proposed was also compared with other counterparts reported
EP 90 ± 4 104 ± 5 93 ± 2
in the literature [30–37] for the resolution of the same analytical
PP 93 ± 1 98 ± 1 95 ± 6
BP 81 ± 7 94 ± 2 87 ± 6 problem. The comparison, which is summarized in Table 3, indicates
that our proposal provides the best sensitivity compared with the LC or
Analytes: methylparaben (MP), ethylparaben (EP), propylparaben (PP) and butylparaben CE-based methods. Only a GC-MS method resulted to be more
(BP). sensitive but it requires the derivatization of the analytes. The precision
a
Relative recovery ± standard deviation (n=3) expressed as percentage.
levels and relative recoveries are better or comparable with other
methodologies. The most important advantage of the technique in
the interval from 0.15 to 0.5 ng/mL. The repeatability of the method, comparison to the other methods is the simplicity of the composite
expressed as intra-day relative standard deviation (RSD %), was synthesis and the uses of cheap/recycled materials as precursors.
evaluated at 1 ng/mL in sextuplicate (n=6) providing results in the
interval 4.4–8.5%. Inter-day RSD was determined by performing three 4. Conclusions
replicate extractions in three subsequent days (n=9) at the same
concentration level resulting in values in the range from 7.1% to In the present study, a new composite based on the combination of
11.2%. Inter-day RSD also involves the synthesis reproducibility. MNPs and polystyrene was synthesized and evaluated for the disper-
Enrichment factor (EF) values were in the range from 11.7 to 42.3 sive micro-solid phase extraction of four parabens from water samples.
and absolute extraction recoveries in the range of 2.9–10.6%. The nanocomposite combines in a synergic way the favorable features
Several environmental water samples were analyzed by the pro- of both polymeric network and MNPs: extraction capabilities of PS and
posed method. As no analytes were detected, the samples were spiked the magnetic behavior of the MNPs which allows the recovery of the

Fig. 6. Total ion current chromatogram of (a) creek water sample and (b) creek water sample spiked with 2 ng/mL of the analytes after D-μSPE under optimum conditions. Peak
identification: (1) MP, (2) EP, (3) PP, (4) BP.

Table 3
Comparison of the present method with other reported methods for determination of the selected parabens.

Sample treatment Instrumental technique LOD (ng/mL) LOQ (ng/mL) RSD% Extraction time (min) Relative recovery (%) Ref.

In-tube SPME UHPLC-MS/MS – 3–10 1–14.8 – – [30]

On-line SPE HPLC-MS/MS 0.1–0.2 – 5.0–11.5 5 82–108 [31]
Magnetic D-µ-SPE HPLC-DAD 10–25 25–100 3.18–6.11 6 91.46–108.08 [32]
VA-D-μ-SPE HPLC-DAD 0.1–0.6 0.3–2 1.7–16 28 61.3–101 [33]
SPE CE-DAD 1.8–2.3 6.2–7.7 2.9–5.4 – 93.7–110.6 [34]
Derivatization-SPME GC-MS/MS 7.5–260 25–890 0.1–10 – 69.8–126 [35]
Derivatization-HS-SPME GC-MS/MS 0.004–0.017 – 4–10 20 – [36]
MIP-SPME GC-FID 0.22–0.30 0.72–0.99 2.88–3.92 25 92.17–97.86 [37]
Magnetic D-µ-SPE HPLC-MS/MS 0.05–0.15 0.15–0.50 4.4–8.5 15 81.2–104.5 Proposed method

SPME, solid phase microextraction; SPE, solid phase extraction; VA-D-μ-SPE, vortex-assisted dispersive micro-solid phase extraction; HS, headspace; MIP, molecularly imprinted
polymer; DAD, diode array detection; CE, capillary electrophoresis; FID, flame ionization detector.

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