Environmental Science and Ecotechnology 6 (2021) 100097

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Environmental Science and Ecotechnology

journal homepage: www.journals.elsevier.com/environmental-science-and-
ecotechnology/

Original Research

Magnetic poly(acrylic acid)-based hydrogels for rapid ammonium

sorption and efficient sorbent separation from sewage
Heidy Cruz a, e, Miriam Yap Gabon a, Sirajus Salehin a, d, Thomas Seviour c,
Bronwyn Laycock b, Ilje Pikaar a, *
a
School of Civil Engineering, The University of Queensland, Brisbane, Queensland, 4072, Australia
b
School of Chemical Engineering, The University of Queensland, Brisbane, Queensland, 4072, Australia
c
WATEC Aarhus University Centre for Water Technology, Nørrebrogade 44, Bldg 1783, 8000, Aarhus, Denmark
d
Advanced Water Management Center, The University of Queensland, Brisbane, Queensland, 4072, Australia
e
Department of Civil and Environmental Engineering, National University of Singapore, 1 Engineering Drive 2, Singapore, 117576, Singapore

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

Article history: Ammonium sorption and recovery processes typically take place in conventional packed columns, with a
Received 27 January 2021 configuration that enables maximum sorption by the sorbents. However, batch or semi-continuous
Received in revised form operations in packed columns have associated issues such as scaling and frequent backwashing re-
10 May 2021
quirements, which are economically prohibitive. As an alternative, ammonium sorption could occur in
Accepted 11 May 2021
well-mixed continuously stirred tanks, which would allow for the ammonium sorption process to be
retrofitted in existing wastewater treatment plants, provided that efficient sorbent separation can be
Keywords:
achieved. This study demonstrates, for the first time, the preparation of magnetic poly(acrylic acid)-
Sewage
Wastewater treatment
based (PAA) ammonium sorbents through the incorporation of magnetic (Fe3O4) nanoparticles (MNP)
Resource recovery produced via scalable and cost-effective electrochemical synthesis. The MNP and PAA hydrogels were
Polymer hydrogels synthesized independently and the MNPs subsequently integrated into the PAA hydrogel network by
Ammonium recovery particle diffusion and physical entrapment. No adverse effects on swelling and ammonium sorption
Magnetic nanoparticles following immersion in either synthetic or real sewage were observed after MNPs were incorporated into
the hydrogels. Importantly, PAA-MNP hydrogels demonstrated high ammonium sorption efficiencies (80
e93%) in real sewage and achieved rapid ammonium recovery of 73 ± 1.1% within 15 min of mild acid
washing (pH 4) 15 min at a maximum recovery.
© 2021 The Authors. Published by Elsevier B.V. on behalf of Chinese Society for Environmental Sciences,
Harbin Institute of Technology, Chinese Research Academy of Environmental Sciences. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction Adsorption is one of the most suitable techniques to recover

ammonium from diluted streams (30e50 mg/L) such as sewage.
Sewage comprises 20 million tons of ammonium annually [1]. Ammonium sorbents such as zeolites and ion-exchange resins have
As a means to create a more sustainable society for the 21st century, been tested in both lab- and full-scale, reporting excellent results in
ammonium recovery technologies are being developed to move terms of ammonium removal (>98%) and reducing ammonium
away from the traditional biological conversion of ammonium to concentrations to below 1 mg/L [3e5]. Ammonium recovery using
inert N2 gas and shift toward the circular use of ammonium as a zeolites and ion-exchange resins typically takes place in packed
valuable resource. In addition to recovering a valuable resource, columns [3,6e11]. However, ammonium recovery in packed col-
recovering ammonium potentially avoids N2O emissions, environ- umns is limited to either batch or semi-continuous mode which
mental externalities, and technological limitations associated with disqualifies it as an option for existing wastewater infrastructures
existing biological ammonium conversion processes, as discussed since it cannot be retrofitted into the mainline operation of most
in our previous study [2]. treatment plants. An alternative strategy would be to introduce a
suitable sorbent into mainstream wastewater treatment line in
stirred tanks (and also in carousels and activated sludge tanks). This
would eliminate the need for backwashing and allow for sorption
* Corresponding author.
E-mail address: [email protected] (I. Pikaar).
in a simple configuration that can easily be incorporated into

https://doi.org/10.1016/j.ese.2021.100097
2666-4984/© 2021 The Authors. Published by Elsevier B.V. on behalf of Chinese Society for Environmental Sciences, Harbin Institute of Technology, Chinese Research
Academy of Environmental Sciences. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
H. Cruz, M. Yap Gabon, S. Salehin et al. Environmental Science and Ecotechnology 6 (2021) 100097

existing wastewater treatment plants [12]. An important require- the hydrogels, swelling properties, ammonium sorption perfor-
ment for such a configuration is a means to separate the sorbents mance, and recoverability of ammonium from the hydrogels
from the liquid stream efficiently once the process is complete. through mild acid washing at pH 4.
While filtration and centrifuge-based techniques are suitable, they
are relatively energy-intensive and have a high maintenance 2. Materials and methods
requirement due to filter fouling and caking [13]. Moreover,
centrifuge-based separation methods would incur enhanced attri- A complete set of detailed materials, experiments, spectral data,
tion of the sorbents, thus reducing their overall service life. and sorption experiments are available in the Supplementary
In our previous study, PAA-based hydrogel sorbents were shown Information.
to achieve rapid ammonium sorption from sewage at a very short
retention time (~10 min) [14]. PAA hydrogels also demonstrated 2.1. Materials
reusability with minimal decrease in sorption capacity after five
sorption-desorption cycles using 1 M HCl as desorbing agent and Acrylic acid (AA) containing 200 mg/L monomethyl ethyl hy-
regenerant. The promising properties of PAA hydrogels as ammo- droquinone inhibitor (Sigma Aldrich, Australia) was used as the
nium sorbents, coupled with their low density (1 g/mL), would monomer. The initiator, ammonium persulfate (APS) and cross-
make them suitable for use in continuously stirred tanks, provided linker, N,N0 -methylenebisacrylamide (MBA) were purchased from
that a practical sorbent separation method is available. The other Sigma Aldrich. For synthetic wastewater preparation, reagent grade
advantage of PAA hydrogels, and hydrogels in general, is their calcium chloride dehydrate was purchased from Sigma Aldrich,
expandable polymer network [15e17]. This allows the hydrogels to Australia; potassium dihydrogen orthophosphate and magnesium
take up inorganic components as long as their size is smaller than sulfate heptahydrate from Chem Supply, Australia; sodium chloride
the hydrogel network. In theory, magnetic nanoparticles could be and ammonium chloride were purchased from Merck, Australia.
entrapped within the hydrogel network thereby opening up op- Sulfuric acid (98 w/w%) from Merck (Australia) was used as the
portunities for solid-liquid separation by magnetic pulldown regenerant. All materials were used as received.
[18e21]. Indeed, solid-liquid separation by magnetic pulldown is
being implemented as a pre-treatment for dissolved organic carbon 2.2. Synthesis and characterization of PAA-MNP hydrogels
removal in 37 full-scale drinking water production plants using
macro-porous resin beads incorporated with magnetic iron oxide PAA hydrogels and MNPs were synthesized separately following
nanoparticles (MIEX®) [22e24]. We, therefore, hypothesized that it the procedures detailed in the sections below.
would be possible to produce magnetic ammonium sorbents from
PAA with magnetic nanoparticles, which could be used for main- 2.2.1. Synthesis of PAA hydrogels
stream ammonium sorption followed by in-line sorbent separation The PAA hydrogels were synthesized by free radical polymeri-
using magnetic pulldown. This would eliminate the need for zation using solution polymerization [38]. A 20 g monomer solu-
filtration systems and other complex separation techniques for tion containing 6.87 g AA, 0.011 g APS, 0.71 g MBA and 12.42 g
recovering the sorbents from mixing tanks [25e32]. distilled water was mixed thoroughly using a magnetic stirrer at
A recent study demonstrated a cost-effective and scalable, room temperature. Once dissolved, the monomer solution was
electrochemical method to produce magnetic nanoparticles deoxidized by bubbling with N2 gas for 20 min, and then the so-
(MNPs) in the form of hexagonal platelet-like Fe3O4 particles at lution was poured into silicone-coated test tubes with 15 mm in-
industrially relevant concentrations (e.g. 10 g MNP-Fe/L) [33]. These ternal diameter and 125 mm length. The glass tubes were then
MNPs could be incorporated into the PAA hydrogels in two ways. capped and placed in an oil bath at 60  C for 2 h to allow poly-
First, the MNPs could be added during the free-radical polymeri- merization. After polymerization, the hydrogels were cut into
zation and crosslinking of acrylic acid with a crosslinking agent of 3 mm-thick discs and then immersed in 200 mL 100% w/v ethanol
choice. The MNPs can also be chemically reacted to the polymer for 8 h, then 500 mL distilled water for 8 h. This washing procedure
matrix leading to a stable and even dispersion of MNPs inside the was repeated three times. After final washing with 200 mL ethanol,
polymer beads, the latter being similar to the patented synthesis the hydrogels were filtered using a Büchner funnel with 120 mm
design for MIEX® resins [34]. However, such an approach is not Whatman filter paper and dried for 24 h at 60  C. The dried
suitable for synthesizing PAA hydrogels as MNPs could potentially hydrogel discs were crushed into small particles using mortar and
disrupt the polymerization and gelation process of PAA, which may pestle. The hydrogels were then immersed in 1 M NaOH solution
result in unpredictable properties such as brittleness, incomplete (20 g dry hydrogel per L of NaOH solution) for 1 h at room tem-
crosslinking, and inhomogeneous hydrogel structure [20,35]. The perature. Finally, the hydrogels were filtered using a Büchner fun-
second method would be to incorporate MNPs into pre-formed PAA nel with a Whatman filter paper (120 mm) and soaked in 500 mL
hydrogels. This preparation method is a common practice and the distilled water for 4 h to remove residual NaOH and then dried for
preferred approach when loading nano-sized drug compounds 24 h at 60  C.
inside hydrogels for biomedical applications because it does not
require chemical alteration to entrap drug compounds [36,37]. 2.2.2. Electrochemical production of magnetite (Fe3O4)
Based on the above, it was hypothesized that MNPs can be nanoparticles
loaded into the pre-formed PAA hydrogels by particle diffusion in Magnetite nanoparticles (MNPs) were synthesized using an
water and at room temperature and then be physically entrapped electrochemical-based production method, according to the pro-
by the hydrogel network. To prove this concept, MNPs were inte- cedures described in detail elsewhere [33]. In summary, MNPs were
grated into the PAA hydrogel network using a simple, chemical- synthesized via electrochemical oxidation of sacrificial iron elec-
free, heat-free, and diffusion-driven method, whereby the MNPs trodes. The two iron plates used as both anode and cathode were
and PAA hydrogels were synthesized independently. To the best of submerged in 250 mL of 2 g/L NaCl solution in tap water as the
our knowledge, the feasibility of such a straightforward approach in electrolyte, with an applied current density fixed at 8 mA/cm2 for
the preparation of magnetic hydrogel sorbents for wastewater ap- 24 h. At the end of the experiment, a suspension of 10 g Fe3O4eFe/L
plications has not been demonstrated before. This study also in NaCl solution was obtained as a product. The electrolyte was
explored the effect of MNPs on the magnetic response behaviour of discarded and the obtained MNPs were subsequently washed with
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H. Cruz, M. Yap Gabon, S. Salehin et al. Environmental Science and Ecotechnology 6 (2021) 100097

distilled water three times and dried in the oven at 50  C for 12 h to semi-quantitative XRD analysis was conducted to determine the
obtain dried MNP powder. concentration (%) of MNPs bound inside the hydrogels as a result of
PAA-MNP synthesis. Corundum (a-Al2O3, an internal standard) was
2.2.3. Preparation of PAA-MNP hydrogels used for all semi-quantitative measurements following a procedure
Fig. 1a illustrates the preparation of PAA-MNP hydrogels. described elsewhere [39].
Aqueous suspensions of MNPs (0.06%, 0.12%, and 0.24% w/w) were The equilibrium swelling ratios of PAA-MNP hydrogels were
prepared by dispersing dried MNP powder in 50 mL deionised evaluated in the following media: (i) distilled water, (ii) aqueous
water using an ultrasonic bath for 5 min 3 g of dried PAA hydrogels NH4Cl solution (40 mg/L NH4eN), (iii) synthetic wastewater, and
were immersed in each dispersed MNP suspension immediately (iv) sewage. The hydrogels were placed in a drying oven at 60  C for
after sonication. The MNP particles were allowed to migrate into 12 h before all swelling experiments. Dry PAA-MNP hydrogels
the PAA hydrogels via osmosis for 30 min, which was marked by a (100 mg) were immersed in a 50 mL solution for 24 h and then
rapid change of colour in the PAA hydrogels from transparent to separated using a vacuum-assisted filter unit with a 120 mm
black and the solution turning from pitch black to grey. Lastly, the Whatman filter paper. The swelling degree of the hydrogels was
PAA-MNP hydrogels were dried in an oven at 60  C for 48 h. determined from the average of three measurements as the ratio of
the mass of swollen hydrogel over dry hydrogel [40].
2.2.4. Characterization
Solid-State NMR was performed to characterize the PAA 2.3. Batch sorption studies
hydrogels (Bruker Avance III). X-ray diffraction (XRD) (qualitative
and semi-quantitative) analysis of dried PAA-MNP hydrogels was 2.3.1. Synthetic wastewater and sewage preparation
performed to confirm the presence of Fe3O4 and to quantify the Synthetic wastewater was prepared using reagent grade calcium
corresponding concentration of bound MNPs inside the PAA-MNP chloride dihydrate, potassium dihydrogen orthophosphate, mag-
hydrogels. The XRD patterns were recorded in Bruker D8 diffrac- nesium sulfate heptahydrate, sodium chloride, and ammonium
tometer equipped with a (q, 2q) goniometer and a position- chloride. Characterizations of the synthetic wastewater used in the
sensitive detector (Cu K a1 radiation at l ¼ 1.55  A). Reflections experiments are summarized in Table S1.
were collected within the [5e80 ] 2q range, with a step width of Sewage was collected from a local wet well in a residential zone
0.02 and 1.2 s/step of collecting time. The resultant 2q peaks were in Brisbane, Australia. The collected sewage was immediately
analysed with the embedded XRD software Diffrac.Eva (version 4) stored at 4  C and used within seven days of collection. Before each
and matched with the ICDD PDF4þ 2019 database. Additionally, sorption experiment, the wastewater was warmed up to ambient

Fig. 1. (a) Schematic presentation of PAA-MNP hydrogel preparation (b) X-ray diffractograms of bare PAA hydrogels, PAA-MNP hydrogels, magnetic nanoparticles (MNPs) used in
this study, and standard MNP from ICDD 2019 database(c) Demonstration of magnetic separation of PAA-MNP hydrogels from a 1.5% w/w aqueous suspension using a 25 mm
neodymium magnet.

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H. Cruz, M. Yap Gabon, S. Salehin et al. Environmental Science and Ecotechnology 6 (2021) 100097

temperatures (22e24  C). Table S2 shows the composition of the peaks, indicating that the PAA hydrogel has an amorphous struc-
sewage used in the experiments. ture. In contrast, the XRD spectrum of MNPs has clearly defined and
sharp peaks, which is consistent with a highly crystalline structure
2.3.2. Sorption experiments [43,44]. The PAA-MNP hydrogel spectrum displays features of both
Three sets of ammonium sorption experiments were performed amorphous and MNP crystalline structures, indicating that the
in three media: (i) aqueous NH4Cl solution (40 mg/L NH4eN), (ii) MNPs have been successfully loaded into the PAA hydrogel.
synthetic wastewater (40 mg/L NH4eN) and other competing cat- Quantitative XRD analysis showed that loadings of 0.4e0.9 g
ions, and (iii) real sewage. The pH of both synthetic wastewater and MNP were entrapped per 100 g PAA hydrogel (Table S3). The low
sewage were kept at circumneutral pH 7 ± 0.2 during all sorption loadings may be due to the poor diffusion of MNPs into the PAA
experiments since our previous study demonstrated that varying hydrogels [41], as well as the presence of larger size or aggregated
the initial pH did not impact the ammonium sorption performance MNPs [45,46] that are larger than the hydrogel matrix. The latter
of PAA hydrogels [14]. Furthermore, for this study, the duration of could not be confirmed with the experimental procedures per-
sorption was maintained at 60 min, owing to the rapid kinetics of formed in this study. Nevertheless, the MNP loadings achieved in
the hydrogels in reaching equilibrium (<30 min), as previously this study were sufficient to impart strong magnetic properties to
demonstrated in our preceding studies [14,38]. enable hydrogels to be separated efficiently and rapidly from the
PAA-MNP hydrogels (250 mg) were placed in 70 mL gamma liquid stream using a simple setup using a standard neodymium
sterile polypropylene cylindrical containers together with 50 mL of magnet, as visualized in Fig. 1c. Lastly, the swelling experiments
influent, corresponding to a hydrogel loading of 5 g/L. The mixture confirmed that the incorporation of MNP did not affect the swelling
was gently stirred using an overhead stirrer at 90 rpm for 60 min. ratios of the hydrogels when submerged in synthetic wastewater
After sorption, the magnetic hydrogels were immediately pulled (p ¼ 0.8) and real sewage (p ¼ 0.6) (Figure S2, Supplementary
down using a 25 mm diameter neodymium-based disc magnet Information).
with a 22 kg pull force (Supplementary video). Subsequently,
samples were taken from the supernatant via a syringe and filtered 3.2. Ammonium sorption performance of PAA-MNP hydrogels
immediately using a 0.45 mm filter to measure the ammonium
concentration. The filtration of the remaining supernatant using a Fig. 2 shows the ammonium sorption performance of PAA-MNP
120 mm Whatman filter paper confirmed that all hydrogel particles hydrogels in NH4Cl solution and synthetic and real sewage at a
were pulled down by the magnet (data not shown). hydrogel loading of 5 g/L. Findings show that the ammonium
Supplementary video related to this article can be found at sorption of the PAA-MNP hydrogels was the highest in the NH4Cl
https://doi.org/10.1016/j.ese.2021.100097 solution (89e93%) and decreased to 80e83% range in synthetic and
real sewage. Our findings are in agreement with previous studies
2.4. Ammonium recovery and material regeneration on PAA hydrogels, attributing the satisfactory sorption ammonium
performance of PAA hydrogels to electrostatic interactions between
Further experiments were performed to determine the regen- COO groups and NHþ 4 and other cations [14,47]. Due to this
eration ability of PAA-MNP hydrogels. A small volume of 1 M H2SO4 mechanism, other cations in sewage (Mg2þ, Ca2þ and Kþ) can also
(250 g dry hydrogel per L of regenerant) was dropped on the compete with COO sorption sites in the hydrogel, which resulted
ammonium-loaded hydrogels from the synthetic wastewater in lower sorption performance in sewage than in pure ammonium
sorption experiment above. The hydrogels were slowly stirred with chloride solution [14,47]. Despite this, the ammonium sorption
the regenerant by hand until they released the absorbed liquid, as performance of PAA-MNP hydrogels in sewage (80e83%) within
signalled by a significant collapse of the hydrogel volume shortly 30 min, is already well within the range of the sorption perfor-
after stirring. Subsequently, the released liquid from the hydrogels mance of existing polymer sorbents, as detailed elsewhere [48].
and the regenerant reached pH 4. After 15 min, the samples were The inclusion of MNP, regardless of loading concentration, did
collected from the liquid to determine the concentration of the not significantly impact the ammonium sorption performance of
recovered ammonium. PAA-MNP hydrogels in synthetic wastewater (p ¼ 0.8) and real
sewage (p ¼ 0.6). The average sorption capacities in synthetic
2.5. Chemical analysis and calculations wastewater and sewage were 6.6 ± 0.02 and 6.5 ± 0.02 mg NH4eN
per g hydrogel, respectively (Figure S3, Supplementary Informa-
Flow injection analysis (FIA) was used to determine the con- tion). In comparison, the sorption performance of bare PAA
centrations of NH4eN, NO3eN, NO2eN, and PO4eP (QuickChem hydrogels from our preceding study was reported to be
8000, Lachat Instruments, USA). Soluble COD concentrations were 6.3 ± 0.1 mg/g in real sewage [38], suggesting that MNP added
determined using COD cuvette tests (Merck, range 25e1500 mg/L). magnetic property without compensating the ammonium sorption
Elements (e.g. Naþ, Ca2þ, Kþ, Mg2þ, total Fe) were measured using properties of the sorbents. Equally important, the ammonium
inductively coupled plasma optical emission spectrometry (Optima sorption capacities and removal efficiencies achieved in this paper
7300DV, PerkinElmer, USA). were within the range of the sorption capacities of various natural
The statistical difference in the swelling and sorption capacities zeolite-based ammonium sorbents (1.5e30.6 mg NH4eN/g) [48].
between different PAA-MNP hydrogels was determined using one- The unaffected sorption performance of PAA hydrogels after the
way ANOVA at a 95% confidence level. addition of MNPs could be attributed to the positive surface charge
of MNPs at circumneutral pH, at which sewage is typically observed
3. Results and discussion which makes the MNP ineffective for binding cations such as NHþ 4
[28,49]. For this reason, MNPs have been increasingly studied for
3.1. PAA-MNP hydrogels characterization their capability in removing anions such as phosphate and sulfate
from sewage [30,33]. In theory, the positive surface charge of MNPs
Electrochemically-synthesized MNPs were integrated inside could also bind with the negatively charged COO groups in the
post-polymerized PAA hydrogels by osmosis to add magnetic PAA hydrogels. However, since the ammonium sorption perfor-
responsiveness to the PAA hydrogels [20,41,42]. As shown in Fig. 1b, mance of the hydrogels was unaffected by the addition of MNP, this
the XRD spectrum of pure PAA hydrogel is broad and lacks sharp suggests that the MNPs were only physically entrapped by the
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H. Cruz, M. Yap Gabon, S. Salehin et al. Environmental Science and Ecotechnology 6 (2021) 100097

Fig. 2. Ammonium sorption performance of PAA-MNP hydrogels in various media. Hydrogel loading ¼ 5 g/L, contact time ¼ 60 min, room temperature, circumneutral pH. All
experiments were conducted in triplicates. Error bars represent the standard deviation at a 95% confidence interval.

hydrogel matrix.
ICP analysis also revealed that the PAA-MNP hydrogels lost
0.7e2.0% of the initially loaded MNPs after one sorption experi-
ment (Table S4, Supplementary Information). Lower MNP losses of
0.7% were observed in hydrogels with higher initial MNP loading
(PAA-MNP 0.9%). This could be due to the mobility of MNP in the
hydrogel network, in that at higher MNP loading, the nanoparticles
have less mobility to leach out from the hydrogel matrix. However,
this could not be confirmed with the experimental procedures
performed in this study. Leaching of MNPs to a certain degree may
be unavoidable due to the presence of physically unbound particles
on the surface and around the pores.

3.3. Ammonium recovery performance

Preliminary recovery experiments show that ammonium can be

effectively recovered from the PAA-MNP hydrogels with 1 M H2SO4
Fig. 3. Ammonium recovery performance of PAA-MNP hydrogels after sorption ex-
solution within 15 min (Fig. 3). Ammonium streams with concen- periments from synthetic wastewater. Regenerant: 1 M H2SO4, contact time ¼ 15 min,
trations of 450e689 mg/L NH4eN were recovered, corresponding room temperature. All experiments were conducted in triplicates. Error bars represent
to recovery efficiencies ranging from 61.8 to 97.6%, respectively. the standard deviation at a 95% confidence interval.
Unlike the sorption process, the PAA-MNP hydrogels exhibited
lower recovery efficiencies in comparison to bare PAA hydrogels.
The highest ammonium recovery at 97.6 ± 0.9% was achieved with 4. Implications for practice
bare PAA hydrogels, while the ammonium recovery efficiencies of
the PAA-MNP hydrogels were 61.8 ± 0.5%, 73.0 ± 1.1%, and This proof-of-concept describes a practical and effective method
72.5 ± 1.4%, increasing in proportion to MNP loading (0.4%, 0.6%, for preparing magnetic ammonium sorbents by physically entrap-
and 0.9%, respectively). This could be due to the physical obstruc- ping MNPs. By combining MNPs and PAA hydrogels in water, the
tion of NHþ MNPs were successfully integrated into the hydrogel matrix to form
4 ions by the nanoparticles within the hydrogel network.
Since ammonium recovery was conducted using acid washing at magnetic hydrogels that can be readily separated from liquid
very short contact times and mild conditions (pH 4; 15 min), the streams such as sewage using a compact magnet.
release of NHþ While successful in proving the concept, the stability of MNPs in
4 ions from the hydrogel matrix might have been
restricted by the nanoparticles, which might lead to a slower the hydrogels needs to be improved and investigated further.
release of NHþ Leaching is a critical issue that needs to be addressed for the
4 ions into the regenerant.

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H. Cruz, M. Yap Gabon, S. Salehin et al. Environmental Science and Ecotechnology 6 (2021) 100097

Fig. 4. Schematic illustration of ammonium removal coupled with magnetic separation of PAA-MNP hydrogels in mainline wastewater treatment.

hydrogels to be fully reusable for multiple cycles. Approaches such ranging from 61.8 to 97.6%, respectively by washing the hydro-
as adjusting the crosslinking density of the hydrogels to prevent the gels with 1 M H2SO4.
leaching of MNPs from the hydrogels could be an interesting  The confinement of MNPs inside the hydrogels needs further
investigation [47,50,51]. The introduction of a copolymer with a improvement since 0.7e2.0% of the MNP loading leached from
higher affinity to MNPs could also be explored to increase the the hydrogels after 1 h of sorption.
stability of the MNPs within the hydrogels. Equally important to
fully understand the stability of the PAA-MNPs, a detailed charac- Overall, this study can be seen as a step forward toward a cir-
terization of the magnetic properties of the hydrogels depending cular economy through the development of approaches enabling
on MNP loading, sorption cycles, and regeneration conditions mainstream recovery of ammonium from sewage.
should also be performed.
The significance of the use of magnetic ammoniums sorbents Funding sources
lies in their versatility. PAA-MNP hydrogels can be mixed with raw
wastewater suspended in a completely mixed reactor where a This work was supported by The University of Queensland
significant fraction of the incoming ammonium load can be sorbed scholarship award and UQ New Staff Startup-up Grant scheme.
(~75%) before conventional activated sludge processes to treat or-
ganics and residual ammonium. After the sorption process, PAA- Declaration of competing interest
MNP hydrogels will be separated magnetically from the same
vessel and the treated wastewater is separated from the resin in the The authors declare that they have no known competing
upper section of the vessel, as described in Fig. 4 below. This financial interests or personal relationships that could have
configuration is similar to the MIEX® process, which has been appeared to influence the work reported in this paper.
successfully implemented at full-scale for the removal of natural
organic matter during the production of drinking water [52]. The Acknowledgements
captured magnetic hydrogels that settle in the reactor can be re-
generated in a completely independent process from the main- Heidy Cruz thanks The University of Queensland for the schol-
stream. Such a concept allows for a continuous ammonium arship support. The authors acknowledge Dr Beatrice Keller-
sorption process in which the PAA-MNP hydrogels only have a very Lehmann and Mr Nathan Clayton for their helpful assistance with
short contact time with the sewage (~10mins) followed by a pro- the chemical analysis and Mr Markus Fluggen for the technical
longed regeneration process to enable efficient regeneration. assistance.

Appendix A. Supplementary data

5. Conclusions
Supplementary data to this article can be found online at
This paper demonstrated the simple and effective preparation of https://doi.org/10.1016/j.ese.2021.100097.
magnetic poly(acrylic acid)-based ammonium adsorbents through
the incorporation of MNP produced from scalable and cost- References
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