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Separation and Purification Technology 179 (2017) 328–334

Contents lists available at ScienceDirect

Separation and Purification Technology


journal homepage: www.elsevier.com/locate/seppur

Application of high gradient magnetic separation for oil remediation


using polymer-coated magnetic nanoparticles
Seyyedali Mirshahghassemi a, Armin D. Ebner b, Bo Cai c, Jamie R. Lead a,⇑
a
Center for Environmental Nanoscience and Risk (CENR), Department of Environmental Health Sciences, Arnold School of Public Health (PHRC 511), University of South Carolina,
921 Assembly St, Columbia, SC 29208, United States
b
Department of Chemical Engineering, 3C06 Swearingen Engineering Center, University of South Carolina, Columbia, SC 29208, United States
c
Department of Epidemiology and Biostatistics, Arnold School of Public Health, University of South Carolina, Discovery 1, Room 460, 915 Greene Street, Columbia, SC 29208,
United States

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

Article history: Oil can be released into the environment from different sources such as runoff, accidental oil spills and
Received 29 September 2016 oily wastewater discharges produced during industrial activities and can have dramatic impacts on the
Received in revised form 13 January 2017 environment. The limitations of current clean-up techniques have inspired researchers to study the
Accepted 22 January 2017
application of nanotechnology for oil remediation. Previously, we reported excellent oil-removal effi-
Available online 10 February 2017
ciency of a reference MC252 oil using polyvinylpyrrolidone (PVP)-coated magnetic nanoparticles (NPs)
from an oil-water mixture under a wide range of environmentally relevant conditions. In the current
Keywords:
report, the same type of NPs were used with a high gradient magnetic separation (HGMS) technique
Nanoparticles
Iron oxide
for the rapid removal of oil from oil-water mixtures in a continuous flow system. Using a high magnetic
Oil spill field (0.56 T) and 1 h mixing time, fluorescence and inductively coupled plasma-optical emission
Remediation spectrometer (ICP-OES) data showed approximately 85–95% oil and NP removal under all conditions.
Magnetic separation Gas chromatography–mass spectrometry (GC–MS) results show 88 and near 100% removal of alkanes
Polymer (C9-C22) for experiments in the presence or absence of stainless steel wool, respectively. Continuous
use over 7 h of operation (17 L oil-water mixture was treated) showed no reduction in oil and NP removal
capacity. Results showed that increasing the magnetic field and inserting stainless steel wool significantly
increased oil and NP removal efficiencies. This study shows that using HGMS is a promising technique for
oil remediation using PVP-coated magnetic NPs.
Published by Elsevier B.V.

1. Introduction including low removal efficiency, high operational cost and time
and environmental constraints [5,6]. Similar to the clean-up tech-
The use of oil and other hydrocarbons are a necessary and inte- niques for oil spills, different wastewater treatment techniques
gral part of our daily lives, although they also bring significant have been proposed for treatment of oily wastewater including
problems with the risk of spills and other releases to the environ- electrochemical treatment [7], microfiltration [8], sorbent materi-
ment, with concomitant economic and environmental damages als [9] and membrane bioreactor [10]. Although great progress
[1]. Crude oil and petroleum products can be released into the has been made in the application of these techniques, they have
aquatic systems from different sources such as accidental oil spills, limitations such as high operating costs, operating issues (e.g.
runoff and industrial activities such as petroleum refineries, metal membrane fouling) and slow removal rate [11].
manufacturing and automotive industries [2]. Oily discharges can In recent years, the application of nanotechnology in water and
damage aquatic systems and can also contaminate groundwater wastewater treatment has been widely investigated including for
and drinking water resources and impact population centers [3]. the removal of dyes [12,13], heavy metals [14] and crude oil
The most common clean-up techniques for removing oil in oil [15,16]. Magnetic nanoparticles (NPs) are particularly interesting
spills are skimming, in-situ burning, dispersants and sorbents [4]. due to their inherent low toxicity and magnetism allowing easy
However, there are challenges associated with these methods separation of NPs from fluids [16,17]. For example, Calcagnile
et al. functionalized polyurethane foam by means of oleic
acid-capped superparamagnetic iron oxide NPs and polytetrafluo-
⇑ Corresponding author. roethylene (PTFE) particles which showed high water-repellency
E-mail address: jlead@mailbox.sc.edu (J.R. Lead).

http://dx.doi.org/10.1016/j.seppur.2017.01.067
1383-5866/Published by Elsevier B.V.
S. Mirshahghassemi et al. / Separation and Purification Technology 179 (2017) 328–334 329

and fast oil absorption [18]. We have synthesized polyvinylpyrroli- 6.25 mL ammonium hydroxide (25–30%, BDH) was added drop-
done (PVP)-coated iron oxide NPs capable of sorbing over 150 wise with vigorous stirring and the solution was stirred for
times its own volume of crude oil [16]. We have also developed a 25 min at 90 ± 5 °C. After the mixture cooled down, the precipitates
cost-effective, efficient, low toxicity and facile hydrothermal syn- were washed once with ultrapure water and separated magneti-
thesis technique to produce PVP-coated iron oxide NPs [19]. The cally and redispersed in water by sonication. The NP suspensions
synthesized iron oxide NPs show excellent oil removal efficiency were stored for the HGMS experiment. NP characterization data
under different environmentally relevant conditions, including a are provided in the Supporting Information.
wide concentration range of natural organic macromolecules In a typical oil removal experiment, crude oil from the Deepwa-
(NOM) and different ionic compositions [19,20]. The oil removal ter Horizon spill (sample ID number: A0068H, Aecom Environ-
mechanism of PVP-coated magnetic NPs is likely based on the
hydrophobic effect forcing oil from the aqueous phase onto the
PVP layer, which is bound to the core. Magnets can then be used
to separate the nanomaterial, with associated oil, from the water
[20]. Despite the excellent oil removal performance in the previous
studies, these techniques were only tested in the laboratory scale
and their performance at a larger removal scale remains unclear.
In this study, a high gradient magnetic separation (HGMS) tech-
nique, which can be utilized to remove oil in a continuous and lar-
ger volume, was tested as a function of the operating parameters
(e.g. magnetic field strength, mixing time and stainless steel (SS)
wool content). The HGMS system has an externally applied mag-
netic field which can be energized using a fine ferromagnetic wire
matrix (e.g., SS wool) inserted into the column. This technique has
been widely used in wastewater treatment [21,22], drug delivery
[23] and other industries such as paper manufacturing and food
industry [24].

2. Experimental

The hydrothermal synthesis technique and NP characterization


have been published previously [19] and a short summary is given
here. In a typical synthesis process, 28.8 mM PVP (Mw 10 kDa,
Sigma-Aldrich) was dissolved in 6.25 mL ultrapure water (Milli-
pore) while the solution was stirred at 80 ± 5 °C. Then, 160 mM
FeCl24H2O (98%, Alfa Aesar) and 640 mM FeCl36H2O (>98%,
BDH) were added to the solution and stirred at 80 ± 5 °C. Subse-
quently, 19.2 mM PVP was added while the solution was stirred
and the temperature was kept constant at 80 ± 5 °C. Finally,

Fig. 2. Effect of magnetic field strength on the oil and NP removal efficiencies (a) oil
Fig. 1. Schematic diagram of the HGMS system: (A) stirred oil-water-NPs mixture; and NP removal for the last collected sample, (b) oil removal efficiency and (c) NP
(B) peristaltic pump; (C) magnet; (D) SS wool (if used); (E) treated solution. removal efficiency (mixing time: 1 h and mass of SS wool: 100 mg).
330 S. Mirshahghassemi et al. / Separation and Purification Technology 179 (2017) 328–334

ment) was mixed with ultrapure water in a vial via sonication In the presence of SS wool, NPs were collected either on the wall
(Branson 2800, 40 kHz, ambient conditions) for 30 min to prepare of column or were trapped in the SS wool. Each HGMS experiment
the oil-water sample. The oil concentration used was was replicated three times. Following the HGMS experiment, the
0.15 ± 0.05 g L 1 which is based on literature data [25] and is sim- column was removed from the magnetic field and collected NPs
ilar to our previous works [19,20]. The NP concentration used was were removed by rinsing with ultra-pure water. The variables
18 ppm, which had been previously optimized [19,20]. Following studied include the applied magnetic field strength, mixing time
the preparation of an oil-water mixture, the NP suspension was and SS wool content. Fig. 1 shows a schematic of HGMS system
added to the mixture and mixed for specific periods of time used in this study.
(5 min or 1 h) using a mechanical stirrer. The suspension contain- To study the performance of HGMS process, oil and NP concen-
ing the NPs was then pumped into a glass column (upflow trations before and after HGMS was measured. Oil concentration
40 mL min 1 with a velocity of 0.14 cm s 1 via a peristaltic pump; was measured by fluorescence spectroscopy and individual alkanes
300 mm length and 11.1 mm I.D.) within the magnet assembly, removal efficiencies were further quantified using gas chromatog-
with no water recirculation. The eluent was then collected in sev- raphy–mass spectrometry (GC–MS). For the fluorescence measure-
eral small sample bottles to measure oil and NP removal efficien- ments, emission spectra of oil-water mixtures were recorded over
cies. A 0.18 or 0.56 T permanent magnetic assembly consisting of the range of 350–650 nm at the excitation wavelength of 337 nm
two 2  4  0.5 inch NdFeB blocks with a minimum gap of 5/8 inch using a Horiba Jobin Yvon Fluorolog-3 spectrofluorometer. This
was used as the magnetic source. The magnetic field strength was excitation wavelength has been used to detect polycyclic aromatic
changed by adjusting the gap between the two magnets and the hydrocarbons of crude oil [27]. A calibration curve was obtained
magnetic field was measured using a Model 4048 Bell Gauss/Tesla based on samples with known oil concentration and the oil
meter. For additions of SS wool, an AISI 434 stainless steel wool removal efficiency was quantified. GC–MS analysis was performed
(average fiber width: 120 mm), packed at different packing densi- on an Agilent 6890 N gas chromatography system and an Agilent
ties (50 and 100 mg SS wool in the column) was placed in the col- 5975 mass spectrometer equipped with an autosampler (Agilent
umn and magnetically energized. The external magnetic field 7683B) to quantify the removal efficiency for individual hydrocar-
created large magnetic field gradients around the SS wool which bons. The samples were prepared via extraction in dichloro-
improved the removal efficiency [26]. In the absence of SS wool, methane (>99.8%, Sigma-Aldrich). The analytical column was an
NPs were collected by the magnetic field on the wall of column. Agilent TG-5MS (30 m  0.25 mm I.D., 0.25 mm film thickness)

Fig. 3. GC–MS results. (a and b) Chromatograms and (c and d) mass spectrometry results for the solution remaining after HGMS (mixing time: 1 h and mass of SS wool:
100 mg).
S. Mirshahghassemi et al. / Separation and Purification Technology 179 (2017) 328–334 331

coated with 5% phenylmethylsiloxane stationary phase. High pur- we could accommodate the correlation within subject (i.e. the cor-
ity helium (99.9%) at a constant flow rate of 1.5 mL min 1 was used relation among repeated measures for each effluent) and the vari-
as the carrier gas. The injection port was maintained at 250 °C in ation across different collected samples. Statistical analysis was
splitless mode and 1 ml of extracted sample was injected. Spectra performed by using R software (version 3.2.1). The statistical sig-
were obtained in the electron impact mode (70 eV) scanning from nificance was set as p < 0.05.
40 to 400 m/z. The oven temperature was operated from 40 to
300 °C rising at 10 °C/min. A full scan mode was used and alkanes 3. Results and discussion
were monitored in the initial oil-water mixture and the last col-
lected sample after HGMS. To study the effect of magnetic field strength on the oil and NP
To measure NP removal efficiency, NPs in the initial oil-water- removal efficiencies, HGMS experiments were performed using
NP mixtures and suspensions remaining after the HGMS treatment two different magnetic field strengths (0.18 and 0.56 T) which
were digested by fresh aqua regia and the total iron concentration are comparable to previous studies [28,29]. In this set of experi-
was measured, after dilution, using a Varian 710-ES inductively ments, the mixing time was 1 h and, for the experiment in the
coupled plasma-optical emission spectrometer (ICP-OES). The presence of SS wool, 100 mg of SS wool was inserted in the column.
removal efficiency of both oil and NP was measured simultane- Based on the fluorescence and ICP-OES results (Fig. 2a) in the
ously from the same collected solutions. Mean and standard errors absence of SS wool, using a magnetic field of 0.18 T and 0.56 T,
of data are provided. the oil removal percentage was 81.4% ± 2.9 and 87.3% ± 4.0, while
The comparison of operating parameters on the oil and NP the NP removal efficiency was 48.8% ± 3.8 and 84.4% ± 5.2, respec-
removal efficiencies was conducted using the one-way analysis tively. At the higher magnetic field (0.56 T), the insertion of 100 mg
of variance (ANOVA) with random effects, which is the simplest SS wool into the column changed oil and NP removal from
case of the linear mixed effects model. The typical ANOVA analysis 87.3% ± 4.0 to 89.5% ± 3.0 and from 84.4% ± 5.2 to 92.9% ± 2.6,
was not used for multiple group tests because each effluent had respectively, compared to the experiment in the absence of SS wool
repeated measures based on three repeated experiments, which (Fig. 2a). These results, showing a high oil removal and low NP
are somewhat correlated. This violated the independent assump- removal at low magnetic strength and no increase in oil removal
tion in the ANOVA. By including random effects into the ANOVA, at the higher NP removal% and higher field strength

Fig. 4. Effect of mixing time on the oil and NP removal efficiencies (a) oil and NP removal for the last collected sample, (b) oil removal efficiency, (c) NP removal efficiency and
(d) mass spectrometry results for the solutions remaining after HGMS (magnetic field strength: 0.56 T and mass of SS wool: 100 mg).
332 S. Mirshahghassemi et al. / Separation and Purification Technology 179 (2017) 328–334

(Fig. 2b and c), suggest that only a fraction of the NPs are respon- absence of SS wool, results indicate that approximately 60% of all
sible for oil sorption. Most likely this is due to the (a) heterogeneity detected alkanes (C9-C22) were removed (Fig. 3c). Adding
of oil-NP agglomerates or (b) the polydisperse nature of the PVP 100 mg of SS wool to the column, hydrocarbon removal efficiency
coating on the NPs, with a specific fraction of the (highly coated) increased by approximately 10% (Fig. 3c). Fig. 3d shows that using
NPs active in separation. The low magnetic field presumably 0.56 T magnetic field, in the presence and absence of SS wool, there
removes the larger oil-NPs agglomerates resulting high oil removal was approximately 100% and 80% removal of all detected alkanes
efficiency. At the high magnetic field, more of the individual dis- (C9-C22), respectively.
persed NPs are also removed. Moreover, results indicated that Fig. 4 shows the effect of mixing time (5 min and 1 h) on oil and
increasing the magnetic field strength and inserting SS wool in NP removal efficiencies. In this set of experiments, a magnetic field
the column provides a small but highly significant enhancement of 0.56 T in the presence of 100 mg of SS wool was used. For a
of oil and NP removal efficiencies (P-value < 0.0001). The external 5 min mixing time, 90.7% ± 1.8 and 88.6% ± 1.7 oil removal and
magnetic field creates larger magnetic field gradients around the 75.3% ± 1.6 and 62.6% ± 3.3 NP removal was achieved in the pres-
SS wool which improves the oil and NP removal [26]. Increasing ence and absence of SS wool, respectively (Fig. 4a). GC–MS results
the magnetic field increases oil and NP removal. However a nar- also showed that using a five minute mixing time, greater than 86%
rower gap between the magnets is required meaning that lower and near 80% of alkanes (C9-C22) were removed with and without
volumes of the oil-water mixture can be treated compared to the SS wool, respectively (Fig. 4d). By increasing the mixing time to 1 h,
condition using a lower magnetic field. A trade-off therefore exists there was a small but significant improvement in NP removal effi-
between volume treated and efficacy of treatment which must be ciency, 92.9% ± 3.0 and 84.4% ± 5.2 in the presence and absence of
optimized on a case by case basis. SS wool, respectively (P-value < 0.0001). Increasing the mixing
Fig. 3 shows the chromatograms for the oil-water mixtures time presumably enhanced interactions between oil and NPs
before and after HGMS and removal percentages for the individual resulting in a more strongly bound oil-NP complex. Subsequently,
hydrocarbons obtained by GC–MS. Chromatography peaks for all the NPs aggregated and removal efficiency improved. However,
suspensions after treatment were significantly reduced compared increasing the mixing time did not significantly alter the oil
to the original oil-water mixture, showing the removal of alkanes removal efficiency (P-value > 0.05). This again suggested that a
(Fig. 3a and b). Using a lower magnetic field (0.18 T) and in the fraction of NPs are responsible for oil sorption. GC–MS results show

Fig. 5. Effect of SS wool content on oil and NP removal efficiencies (a) oil and NP removal for the last collected sample, (b) oil removal efficiency, (c) NP removal efficiency and
(d) mass spectrometry results for the solutions remaining after HGMS (magnetic field: 0.18 T and mixing time: 1 h).
S. Mirshahghassemi et al. / Separation and Purification Technology 179 (2017) 328–334 333

increasing the SS wool content increased hydrocarbon removal


efficiencies (Fig. 5d). For example, in the absence of SS wool, alkane
removal efficiencies (C9-C22) were 50–72%, while using 100 mg SS
wool, C9-C22 removal efficiencies were between 73% and approx-
imately 100% (Fig. 5d). Inserting the SS wool in the column can
energize SS wool and creates larger magnetic field gradients
around the fine ferromagnetic wires, thereby improving the
removal efficiency [26]. Statistical analysis showed that increasing
the SS wool content from 0 to 100 mg significantly increased oil
and NP removal efficiencies (P-value < 0.0001). However, the
statistical analysis does not show a significant increase in oil
removal for the experiment with 50 mg SS wool compared to the
experiment with no SS wool. For the experiment in the presence
of 50 mg SS wool, it is likely that a large fraction of the SS wool
was oriented in the direction of the flow. In this situation, that part
of the SS wool has no magnetic field of its own to collect oil.
Finally, we tested the HGMS system for a longer time by run-
ning the system for 7 h (3.5 h in two consecutive days) and treating
nearly 17 L oil-water mixture (oil concentration was 0.15 g L 1). In
this set of experiments, magnetic field of 0.56 T and 1 h mixing was
used i.e., the optimum removal conditions. Fig. 6a and b shows the
oil and NP removal efficiencies for the experiment in the presence
and absence of SS wool. Removal in all cases was greater than 80%.
It is also clear that, despite fluctuations over time (probably due to
instrument drift, despite calibration, and variation due to changing
batches of sample every hour) that oil removal was slightly, but
significantly, improved in the presence of the SS wool. However,
no significant changes were observed for NP removal. The lack of
correlation indicated again that a subset of the NPs removes most
Fig. 6. Breakthrough experiment in the presence and absence of SS wool. Vertical of the oil. Our results show that even after 7 h of operation (17 L of
gridlines show when the new oil-water-NP mixture was pumped (magnetic field: oil-water mixture was treated), the oil and NP removal efficiencies
0.56 T, mixing time: 1 h and for the experiment in the presence of SS wool, 100 mg
for both separation conditions and the ability of the system to
of SS wool was used). In the absence of SS wool, the average and standard deviation
of oil and NP removal efficiencies were 81.2% ± 1.8 and 81.2% ± 1.9 and in the work were unchanged, indicating excellent removal efficiency over
presence of SS wool, the oil and NP removal efficiencies were 89.5% ± 2.9 and time (Fig. 6a and b) and the potential of the system to be used at a
82.0% ± 2.2, respectively. larger scale.
Clearly, the primary motivation in this technique is oil removal
and our preliminary data indicates there may be benefits in leaving
that using 1 h mixing, in the presence and absence of SS wool near these NPs in situ in the environment (data not shown). Certainly,
100% and greater than 88% of C9-C22 were removed, respectively oil is considerably more hazardous than these NPs. Nevertheless,
(Fig. 4d). Based on both sets of data, it appears that the aromatic given the concerns regarding NPs as an emerging contaminant
fraction is more easily removed (in the absence of full removal of [31–35], it may also be important to be able to remove the NPs
the NPs), while the aliphatic hydrocarbons are sorbed more equally and prevent them being discharged to the environment in order
over the NPs, indicating different modes of removal. to meet any pertaining regulatory requirements [36]. Additionally,
We studied the removal efficiency of the pristine NPs in the for commercial applications, an improved NP capture efficiency
absence of oil to investigate if the oil enhances their removal. A and oil removal would reduce costs and waste discharges. A
magnetic field of 0.56 T with no SS wool was used. Pumping the scaled-up version could simply use larger volumes and flow rates,
pristine NPs through the column, no color change in the suspen- or develop this system in a massively parallel format. In this case,
sion was observed and based on ICP-OES results, approximately the NPs would be added to the oil-water mixture and pumped
10% of NPs were removed (data not shown). This suggests that through a HGMS to separate the nanomaterial, with associated
the oil coating on the NP surface enhanced agglomeration of the oil, from the contaminated site. Alterations of residence time or
NPs, enhancing the NP magnetic separation resulting in increased magnet strength can be used in practice to remove greater percent-
removal. As the magnetic NPs are single-domain and magnetic ages of the NPs, in scaled-up processes.
force upon a magnetic particle is linearly proportional to its vol-
ume, magnetic separation is more effective on the aggregated
oil-NP complexes which resulted in higher NP removal efficiency 4. Conclusions
[30]. Previous use of atomic force microscopy (AFM) and dynamic
light scattering (DLS) showed that the NPs strongly aggregate upon Previously, we have shown a facile synthesis of PVP-coated
oil addition [16,19] and this appears to be the likely cause of magnetic NPs which are cheap, environmentally-friendly and reli-
increased magnetic removal in the presence of oil. able as a technique for oil removal under a wide range of environ-
The effect of SS wool content on oil and NP removal efficiencies mentally relevant conditions. This study demonstrates that these
were studied by conducting the separation experiment using a low NPs can be used in a larger scale for the removal of oil from an
magnetic field (0.18 T) and 1 h mixing, with and without SS wool. oil-water mixture (or potentially from oil contaminated soil
Based on both fluorescence and ICP-OES data, increasing the SS slurries). Using a high magnetic field (0.56 T) and 1 h mixing time,
wool content from 0 to 100 mg, the oil and NP removal efficiencies fluorescence and ICP-OES data showed approximately 85–100% oil
increased from 81.4% ± 2.0 to 86.7% ± 0.9 and from 48.8% ± 2.7 to and NP removal under most conditions, with the higher magnetic
68.1% ± 0.4, respectively (Fig. 5a). GC–MS results also reveal that field and the presence of SS wool giving significantly improved
334 S. Mirshahghassemi et al. / Separation and Purification Technology 179 (2017) 328–334

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