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Application of biomagnetic nanoparticles for biostimulation of biogas

production from wastewater treatment

Article  in  Materials Today · March 2021

DOI: 10.1016/j.matpr.2021.01.720

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 Materials Today: Proceedings xxx (xxxx) xxx

Contents lists available at ScienceDirect

Materials Today: Proceedings

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

Application of biomagnetic nanoparticles for biostimulation of biogas

production from wastewater treatment
E. Kweinor Tetteh ⇑, S. Rathilal
Green Engineering and Sustainability Research Group, Department of Chemical Engineering, Faculty of Engineering and the Built Environment, Durban University of
Technology, Durban, 4001, South Africa

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

Article history: This study presents biomagnetic nanoparticles (BMNPs) as a biostimulant for wastewater treatment and
Received 2 January 2021 biogas upgrading to natural quality (>90% CH4). Notwithstanding, application of anaerobic digestion (AD)
Accepted 22 January 2021 in wastewater settings is still limited with slow kinetics and low methanation yield. Here, four BMNPs
Available online xxxx
(CuO, Fe2O3, TiO2, Cu/Fe-TiO2) were investigated to enhance the high-rate anaerobic system for complete
degradation of organic waste to value – added products (water and biogas). Sugar refinery wastewater
Keywords: was used as a substrate and activated sludge as inoculum. This was carried out in 800 mL working vol-
Biogas
ume bioreactors at a mesophilic temperature of 35 °C and hydraulic retention time of 30 days. Results
Biostimulation
Gompertz model
showed the substrate – inoculum degradation in the control system, when induced with the BMNPs
Magnetic nanoparticles increased the methane (CH4) potential from 63% to 100%. Likewise over 75% water index of chemical oxy-
Wastewater treatment gen demand, total suspended solids, and volatile solids were removed. Stimulatingly, the biogas produc-
tion and wastewater treatability was significantly improved upon adding the BMNPs to the bioreactors
which enriched the methanogenic activities. The post-sludge analysis showed the morphological and ele-
mental distribution of the BMNPs, and their biomagnetic interactions with the micobes which enhanced
the adsorptive removal of the contaminants and the biogas production yield. The Gompertz modified
kinetic model significantly (P < 0.05) favoured the cumulative biogas yield obtained for all the bioreactors
with a kinetic rate constant within the range of 0.182504–0.203027 d-1. The performance of Cu/Fe-TiO2
additives superseded the rest of the BMNPs. In conclusion, BMNPs revealed economic prospects of regen-
eration and reuse with external magnets for effective wastewater treatment.
Ó 2021 Elsevier Ltd. All rights reserved.
Second International Conference on Aspects of Materials Science and Engineering (ICAMSE 2021). This is
an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

1. Introduction offers great potential with environmental benefits deep-down to

Conventional exploitation and continuous usage of fossil fuel is
being associated with the rising concern about global warming, cli-
mate change and environmental pollution [1,2]. As a result, the
search for alternative energy resources in developed and under
developing countries to mitigate the ongoing energy crisis has
become a major governmental concern [3,4]. Apart from this, the
high demand and stringent regulation for wastewater treatment
ends up generating large volumes of by-products as sewage sludge
[5–7]. Sewage sludge (SS) constitutes high organic matter which
warrants its environmental attention as a resourceful material
for water–energy nexus and nutrient recovery [8–10]. Therefore,
considering the production of biogas from SS as renewable energy
⇑ Corresponding authors.
E-mail addresses: emmanuelk@dut.ac.za (E. Kweinor Tetteh), rathilals@dut.ac.za
(S. Rathilal).
irrigation farming and avoidance of landfill discharge cost.
Bioenergy such as biogas is very promising and gaining global
attention due to its economic and environmental advantages
which supersedes fossil fuel production [3,8,11]. Methane (CH4)
and carbon dioxide (CO2) happens to be the main components of
biogas, whose concentrations usually range from 30
65% CH4
and 2–40% CO2 [11,12]. The methane content of biogas can be used
to produce heat, electricity, combined heat and power, thermal
generation as well as transport fuel [1,7,11,13]. Aside the main
components, biogas might constitute some additional chemical
elements such as nitrogen (N), hydrogen (H), oxygen (O), hydrogen
sulphide (H2S) and sulphur (S) [11]. Notwithstanding, biogas in
general reduces not only greenhouse emissions but also hydrocar-
bons, nitrogen oxides and particulates [11,13]. There is a wide
range of biomass resources by which biogas can be produced in
either biodigesters or landfills or incineration. These include
municipal and industrial wastewater, livestock, slaughterhouses,

https://doi.org/10.1016/j.matpr.2021.01.720
2214-7853/Ó 2021 Elsevier Ltd. All rights reserved.
Second International Conference on Aspects of Materials Science and Engineering (ICAMSE 2021).

Please cite this article as: E. Kweinor Tetteh and S. Rathilal, Application of biomagnetic nanoparticles for biostimulation of biogas production from wastew-
ater treatment, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2021.01.720
E. Kweinor Tetteh and S. Rathilal
sewage sludge, food waste, bagasse, cow dung and so on [4,7–11].
Subsequently, from the decomposition of organic matter in the
absence of oxygen to produce biogas, the digestate can be used
as biofertlizers [8,9,14]. As in wastewater treatment settings, bio-
gas with a calorific value>36 MJ/m3 can be obtained anaerobically
and makes it a very interesting area to improve water quality and
energy recovery [1,11]. However, population and industrialisation
growth and poor water quality has far triumphed economic and
social implications [2,6]. Therefore, treatment of wastewater
comes in handy.
Conventionally, treatment of industrial wastewater via chemi-
cal, physical and biological processes ends up generating sludge
as a by-product [15]. Some of these treatment processes include
sedimentation, flotation, coagulation, filtration, reverse osmosis,
adsorption, wet oxidation, ozonation, advanced oxidation pro-
cesses and biological methods (anaerobic, aerobic, anoxic)
[4,5,15–19]. Among these methods, anaerobic digestion (AD) is
considered as an established process for wastewater treatment.
In essence, AD provides significant reduction to an input organic
matter such as chemical oxygen demand (COD) and degradation
of concentrated sewage sludge for energy recovery in the form of
biogas (CH4) [5,8]. Currently, biogas is receiving global attention
due to its economic advantage along with the AD process as cost
effective sludge stabiliser in the wastewater settings [11]. Addi-
tional recovery of energy from waste via AD could simultaneously
replace fossil fuel and address environmental problems [3,19,20].
However, AD processes are thought-provoking to maintain stable
conditions and balance a favourable microbial community to
enhance the breakdown of organic materials [21]. Also, to enhance
the microbial growth especially the methanogens with the avoid-
ance of inhibitions (intermediates and toxic by-products), critical
operating of AD without system failure becomes essential.
Currently, nanotechnology offers suitable nanomaterials for
possible microbial growth and stability in syngas production and
water purification [22–24]. Some of these nanomaterials include
metals (Ni, Cu, Fe, Mo, Zn, and Cd), nutrients (ammonia, nitrate,
nitrite, and phosphate), nanomembranes, carbon nanotubes and
nanopowders [6,23–26]. Also, nanoparticles (NPs) in the form of
metal oxides and non-metallic oxides such as titanium oxides, sil-
ver oxides, zero-valent iron and iron oxides are gaining attention in
the wastewater treatment settings as antimicrobial agents which
can balance microbial activities [23,25,27–30]. Essentially, metal
oxide–based NPs have distinctive physiochemical properties such
as high surface area to volume ratio, particle size, better surface
structure, strong catalytic action and solubility [22,31,32]. Never-
theless, the properties of NPs in AD are subjected to change with
concentration, type of NPs, hydraulic retention time (HRT), tem-
perature and substrate type, which can significantly affect the AD
process [22,31,33]. Mu et al. [27], for instance investigated the per-
formance of TiO 2, Al2O3, SiO2 and ZnO on waste activated sludge
anaerobic digestion, where ZnO showed inhibitory effects with
the same methane production as others.
Synergistically, bioaugmentation via the use of biomagnetic
nanoparticles (BMNPs) has not been given much attention for
energy recovery from sewage sludge in the wastewater settings.
In this study, BMNPs such as CuO, Fe2O3, TiO2, and Cu/Fe-TiO2 were
investigated in a lab-scale biomethane potential system with
wastewater and sludge obtained from a local South Africa sugar
refinery wastewater treatment plant in the Kwazulu Natal Pro-
vince. This was aimed at maximising the methane and biogas pro-
duction with the best BMNPs at a mesophilic temperature of 35 °C
and HRT of 30 days towards understanding the bioaugmentation
and degradation of BMNPs in AD. Additional morphological study
of the post-sludge and the BMNPs kinetic effect on the biogas pro-
duction is highlighted.
2
Materials Today: Proceedings xxx (xxxx) xxx
2. Materials and method
2.1. Chemicals and inoculum/wastewater collection
The biomagnetic nanoparticles (BMNPs) such as CuO, Fe2O3,
and TiO2 used in this study were of analytical grade acquired from
Sigma Aldrich, South Africa. Whereas, the Cu/Fe-TiO2 was synthe-
sized by co-precipitation of mesoporous Titania with CuO and
Fe2O3 NPs and calcining at 600℃ for 1 h as described by Mascolo
et al., [34] and El Ghandoor et al., [35]. The wastewater and anaer-
obic sewage sludge (inoculum) was collected from a local South
African sugar refinery wastewater treatment plant (WTP) based
in Durban in the KwaZulu-Natal Province. To enhance the biogas
potential and buffer capacity of the reactors, the collected sludge
from the WTP was of two-source residues in a volume ratio of
60:40 (anaerobic digester : secondary clarifiers). The sludge was
homogenized, kept under anaerobic conditions and stored under
room temperature of 25 ± 4℃. Characterization of the wastewater
and sludge was carried out in accordance APHA [36] and Tetteh
and Rathilal [12]. The initial results obtained include pH
(7.5 ± 0.33.), COD (666 ± 2.9 mg/L), turbidity (990 ± 2.66 mg/L),
Color (3330 ± 5.6Pt.Co), total solids (4.5 ± 2.6 g TS/L) and volatile
solids (2.8 ± 1.6 g VS/L). The analytical instruments used included
the Hannah pH–meter (HI98130, Hanna Instruments, Woonsocket
RI, USA) for pH and HI 98,703 Portable Turbidimeter (Hanna Instru-
ments, Veneto, Italy) for turbidity measurements. Likewise, HACH
DR 3900 within the wavelength of 455–635 nm (Hach Company,
Colorado – USA), was used for colour and COD measurement.
2.2. Experimental setup and procedure
A batch experiment (Fig. 1) was carried out with 5 identical
bioreactors with working volumes of 0.8 L and headspace of 0.2 L
operated for hydraulic retention times of 30 days at mesophilic
temperature of 35 ± 5℃. Each bioreactor had a content of 50%
wastewater and 30% sludge coupled with 2 g of either CuO,
Fe2O3, TiO2 or Cu/Fe-TiO2 representing setups A, B, C and D.
whereas, the control setup E had no component of the BMNPs.
After load charging, each bioreactor was purged with nitrogen for
5 min to create an anaerobic environment before placing them in
the water bath (Fig. 1). The daily biogas production of each set
up was monitored and collected via downward displacement of
water. Scanning electron microscopy (SEM, Nova NanoSEM cou-
pled with EDT and TLD detector) was employed to determine the
structural degradation of the substrates. The reactor efficiency
was assessed by monitoring the contaminants removal (1).
 
Ci
Cf
Reactor effciency ð%Þ ¼ X100 ð1Þ
Ci
Where, C i = Substrate influent and C f = Substrate effluent. The
cumulative biogas production data obtained was evaluated by
first-order and modified Gompertz eqs. (2) and (3), respectively
[12].
Y ¼ ym: exp ð
exp ½k½k
t þ 1Þ ð2Þ
where in terms of Gompertz k ¼ Rmax: e
.
ym
Y ¼ ym½1
expð
ktÞ ð3Þ
Where, Y = cumulative of specific biomethane (mL/g COD) at time
t (days), ym = the maximum methane potential (mL/g COD),
k = lag phase of producing biogas (day), e = mathematical constant
(2.718282), Rmax = the maximum specific substrate uptake rate per
maximum biogas production (mL /g COD.day) and k is the methane
production rate constant (1/d).
E. Kweinor Tetteh and S. Rathilal Materials Today: Proceedings xxx (xxxx) xxx

Biogas
Sample Tygon tube collector
collecng
BMP Set-up
valve

Biogas
downward
Water Bath
delivery

Fig. 1. Biomethane potential test setup at mesophilic temperature (35 ± 5℃) and hydraulic retention time of 30 days.

3. Results and discussions

3.1. Effect of BMNPs on biological wastewater treatment

In the AD process, the impact of the physical and chemical prop-

erties of the BMNP additives facilitated the enzymatic activity of
the microbial community for the biomethane production as well
as the catalytic enhancement of the wastewater treatability perfor-
mance. The degrees of removing COD, colour and turbidity and
other aforementioned parameters were used to assess the bioreac-
tor efficiency. Figs. 2 and 3 presents the results obtained for con-
taminant removal from the wastewater at HRT of 30 days and
mesophilic condition of 35 ± 5℃. On average, the decreasing effi-
ciencies of COD removal (Fig. 2) by the bioreactors was found as
D (78.98%) > C (74.47%) > B (70.42%) > A (57.21%) > E (35.89%),
respectively. In terms of colour removal (Fig. 2), an increase order
was observed as E (72.67%) < C (84.17%) < A (87.06%) < B (91.89%)
< D (93.33%). Similarly, the turbidity removal (Fig. 2) was quite low
for the control setup (E) as compared with others as follows; B
(80.4%) > A (77.47%) > D (65.56%) > C (60.91%) > E (43.64%). As far
as degradation of organics is concerned and COD removal effi-
ciency, the bioreactor D (78.98%) with bioaugmenting mixture Fig. 3. Effect of BMNPs on TS and VS removal CuO (A), Fe2O3 (B), TiO2 (C), Cu/Fe-
(Cu/Fe-TiO2) revealed as the best. This affirms catalytic and enzy- TiO2 (D), Control (E).

matic ability of metal–based oxides augmented the biodegradation

as compared to the control reactor (E, no additives) [29,33]. This
observation is in accordance with other reported findings, where
bioaugmentation of landfill leachate treatment improved COD
removal efficiency as compared to non-bioaugmented reactors
[37–40]. BMNP additives in the AD process could also shorten
the bioreactor’s lag phase period, whilst improving the treatment
efficiency [25,32].
Stimulatingly, significant differences were observed for the TS
and VS removal (Fig. 3). Interestingly, it was observed that the TS
removal efficiency was D(69.82%) > B(55.09%) > A(53.79%) > C
(52.76%) > E(16.95%), whereas, the VS removal was C(64.76%) > D
(51.04%) > A(50.43%) > B(49.68%) > E(30%). The increase in the TS
(4.5 ± 2.6 g TS/L) and VS (2.8 ± 1.6 g VS/L) removal by the bioaug-
mented bioreactors (A-D) can be ascribed to the fact that the
BMNPs played a major role in the degradation of the substrates.
The highest removal of %VS/TS as observed by bioreactor D can also
be attributed to the inhibition effect of the Cu/Fe-based oxide addi-
tives. These results are in line with other reports as degradation of
substrates in bioreactors were quicker with iron-based additives.
Fig. 2. . Effect of BMNPs on COD, colour and turbidity removal CuO (A), Fe2O3 (B), Besides, the BMNPs acted as either separation or reaction media
TiO2 (C), Cu/Fe-TiO2 (D), Control (E). with large surface for aggregation and adsorption of the pollutants.
3
E. Kweinor Tetteh and S. Rathilal
3.2. Morphological analysis
By observation, the morphologies of the post-sludge or diges-
tate obtained from the augmented bioreactors (Fig. 4a-d) appeared
to be aggregated, densely packed, rough and rigid compared to the
control (Fig. 4e), which seems to be very loose, agglomerated and
smoother. However, the digestate of D > B (Fig. 4b) exhibited more
densely packed aggregates followed by C > A > E, which denotes
the inhibition effects of the zero-valent iron or metal–based dis-
persion [25,27,39]. Thus, the iron in the digestate increased with
the addition of the Fe3O4 NPs, with the ability to be utilised as sub-
strate by the microbes to convert recalcitrant pollutants into other
intermediaries [23]. Notwithstanding, the addition of the BMNPs
also revealed distinctive adsorption capacities towards the pollu-
tants removal (Figs. 3 and 4), which can be attributed to their
unique reactive surface distribution sites (Fig. 4). From the SEM
images (Fig. 4), enormously small featured digestate size are pre-
sented with decreasing order as follows D (6.67 mm) > B (6.36)
> C (6.21 mm) > A (6.03 mm) > E (5.33 mm). Even though the
digestate elemental composition profiles are not present in this
study, some of the coexistence elements including C, O, Mg, P,
Ca, K, Ti, S, Cu, Fe, etc. favoured the augmented bioreactors (A-D)
as compared to the control (E). This affirms other reports of notice-
able increment in the anaerobic digestion process achieved with
the addition of Fe3O4 NPs, as the predominant element was found
to be Fe [23,41,42]. According to Suanon et al., [23], Fe2+/Fe3+ has
strong ionisation capacity for direct inter-species electron transfers
in syntrophic methanogenesis acceleration. Therefore, this
increased the methanogenic activities and digestate physical phe-
nomena of the augmented bioreactors (A-D).
Fig. 4. SEM images of post-sludge obtained for CuO (A), Fe2O3 (B), TiO2 (C), Cu/Fe-TiO2 (D), and Control (E).
4
Materials Today: Proceedings xxx (xxxx) xxx
3.3. Effects of BMNPs on biomethane production
3.3.1. Effects of pH on anaerobic digestion
Fig. 5 presents pH difference which is caused by the oxidation–
reduction potential as a result of the promotion of substrate solu-
bilisation hydrolysis and acidification [43,44]. It was found that the
initial pH of the reactors which was 7.5, after the 30 days of incu-
bation dropped to 6.8–7.2 for most of the reactors, except reactor B
(pH 7.6) where there was a slight increase. However, the difference
in the pH of reactor B and the initial was not statistically signifi-
cant. In fact, both the alkaline (pH > 7) and acidic (pH < 7) medium
favoured the methanogens. Thus, comparable levels of pH in the
bioaugmented (A-D) and non-bioaugmented (E) reactors favoured
biogas production. Conversely, acidification as the first stage in AD
for biogas production favoured most of the bioaugmented reactors
(D > C > B > E > A) including the control (E). Thus low pH enhances
volatile fatty acids (VFA) accumulation, whereas high pH can
increase free ammonia, which is very toxic for methanogenic com-
munities [44,45]. Therefore, the presence of the BMNPs, even
under the alkaline medium, facilitated the conversion of the com-
plex organics and other soluble compounds into VFA in the acido-
genic phase of the AD process.
3.3.2. Biomethane production
Fig. 6 presents the effects of the BMNPs on the cumulative bio-
gas production by the different bioreactors (A-E). The cumulative
biogas obtained with increasing order are D (1450 mL/g.d COD)
> C (1290 mL/g.d COD) > B (1095 mL/g.d COD) > E (920 mL/g.d
COD) > A (830 mL/g.d COD). The high biogas production was
observed within the 5th to 21st day after which there was a daily
E. Kweinor Tetteh and S. Rathilal Materials Today: Proceedings xxx (xxxx) xxx

subsequent nutritional enrichment. Mu et al. [27], also indicated

that the BMNP additives enhanced the biogas and methane pro-
duction, which agrees with this study.

3.4. 3 Biogas composition

Stimulatingly, the BMNPs addition did not only have a positive

influence on the biogas volume produced, but also the quality of
the biogas composition presented as a percentage of methane
(CH4) and Carbon dioxide (CO2) as shown in Fig. 7. The CH4 compo-
sition for all the bioaugmented reactors (A-D) were close to 100%,
whereas the control reactor E showed 63% and 37% of CH4 and CO2,
respectively. The methane production can be linked to the soluble
COD, which was available for the methanogens consortium
involved in the degradation [3,11]. Thus, the breakdown of the
COD and organic materials by the microorganisms resulted in the
methane production, whereby most of the BMNPs aided such
mechanism [47,48]. According to Lombi et al. [24], methanogenesis
is the rate-limiting phase, hence the addition of the BMNPs influ-
enced the acetorophic and hydrogenotrophic microbes.
Fig. 5. Effect of AD on PH anaerobic digestion; CuO (A), Fe2O3 (B), TiO2 (C), Cu/Fe-
TiO2 (D), and Control (E).

3.4.1. Kinetics modes (First-order and modified Gompertz model)

Table 1 presents the summarised predicted parameters of the
two kinetic models studied. The First-order and modified Gom-
pertz models were evaluated via non-linear regression coupled
with minimum sum of square errors (SSE). Among the predictive
models used, the modified Gompertz model exhibited the lowest
difference (<10%) between the experimental measured values
and estimated biomethane production (Y). The low deviations
(<10%) signifies the accuracy of the models and predictability of
the reactor behaviour [49–51]. The value of the kinetic constant
(k), was used to estimate the rate of the biogas production per
day. As seen in Table 1, the k values of the Gompertz modified
model (0.182504–0.203027 d-1) are higher than the First-order
kinetic model (0.008497–0.021019 d-1). The higher and positive
k-values obtained in this study harmonises with the observation
of Kafle et al., [52], that higher positive values of k are related to
the faster biogas production rate. Thus, the minimum time
required for biogas to be produced or the methanogens to be accli-
matised with the BMNPs in the digester for the biogas production.
Apparently that of reactor D was very low as compared with the
rest of the augmented reactors (A-C). Also, the swiftness observed
Fig. 6. Cumulative biogas production at HRT of 30 days: CuO (A), Fe2O3 (B), TiO2 (C),
Cu/Fe-TiO2 (D), and Control (E).

decrease in production rate until the termination at the 30th day.

The average daily volume of biogas produced differed significantly
within the five bioreactors as follows D (50 mL/d) > C (45 mL/d) > B
(40 mL/d) > E (35 mL/d) > A (30 mL/d). Interestingly, the daily bio-
gas of the control reactor performed better than reactor A (with
CuO additives), thus the metal–based Cu NPs could have inhibited
or poisoned the microbes in the reactor making them underper-
form [27,38,46]. This fluctuated the manner of biogas production
with respect to the response by the methanogenic activity. In gen-
eral, reactor D (containing Cu/Fe-TiO2) outperformed other reac-
tors with consistent high biogas productivity (50 mL/d) over the
entire period. Even though there was a dramatic drop of biogas
production in the reactors, their declination appeared at different
times. This phenomenon might be due to the stimulating effects
by the BMNPs which affected the methanogen cellular uptakes
and metabolic co-enzymes responsible for the hydrolysis, acidifica-
tion and methanation phases of AD for biogas production [25,27].
Suanon et al. [23], reported that BMNPs strongly affect the binding
Fig. 7. Biogas composition; CuO (A), Fe2O3 (B), TiO2 (C), Cu/Fe-TiO2 (D), and Control
and activation of microorganism receptors for methanation and (E).

5
E. Kweinor Tetteh and S. Rathilal Materials Today: Proceedings xxx (xxxx) xxx

Table 1
Summary of First-order and Gompertz kinetics model parameters obtained.

Bioreactor setup A B C D E
First -order model
Measured (Y, mL/g.d COD) 830 1095 1290 1450 920
Predicted (Y, mL/g.d COD) 894.767 1198.166 879.5519 1617.024 1013.382
Maximum methane (ym, mL/g COD) 1913.044 2717.494 2698.364 5044.592 4503.575
k (d-1) 0.021019 0.019381 0.013149 0.012882 0.008497
R2 0.957817 0.965689 0.961581 0.957335 0.957528
SSE 140765.3 261930.7 3,768,778 456617.6 182354.8
Modified Gompertz model
Measured (Y, mL/g.d COD) 830 1095 1290 1450 920
Predicted (Y, mL/g.d COD) 800.8762 1072.893 1730.771 1462.179 905.5526
Maximum methane (ym, mL/g COD) 813.4178 1090.574 1779.154 1502.279 928.7097
k (d-1) 0.203027 0.2022 0.182504 0.183524 0.188926
k (d) 9.488217 9.654598 10.32371 10.33017 10.52732
R2 0.997947 0.999077 0.999464 0.998645 0.99967
SSE 5233.549 4276.004 2,771,021 11411.63 1088.225

R2-Regression coefficient SSE-Sum of Square errors k –Lag of phase k – Rate constant.

the bioreactors (A-D) with 2 g of the BMNPs (CuO, Fe2O3, TiO2 or

Fig. 8. Comparing the First-order and Gompertz kinetic models for reactor D
(Cu/Fe-TiO2).
Cu/Fe-TiO2) resulted in 75–90% treatability performance (COD, col-
our, turbidity, TS and VS removal) compared to 45–65% of the con-
trol (E). From the results obtained over the operating hydraulic
retention time (HRT) of 30 days, the bioreactor D (Cu/Fe-TiO2)
showed a stable performance with the highest biogas yield
(1450 mL/g.d COD). The methane composition of the bioaug-
mented reactors (A-D) evaluated were 100% CH4, when compared
to the control (E) of 63% CH4. From the morphological results
(SEM images), high fragmentation structures were noticed in the
digestate or sludge samples obtained with the BMNP additives as
compared to the control. The predicted results obtained from the
cumulative experimental data using the kinetic models (First-
order and modified Gompertz model) were within a deviation of
<10% with acceptable regression index. The modified Gompertz
model performance surpassed that of the First-order kinetic model
as the cumulative biogas results obtained by the all reactors were
fitted with agreeable predictability. In conclusion, the prospect of
incorporating BMNPs into wastewater treatment settings and
bioenergy production from sewage sludge is very encouraging
whereby their toxicity needs to be given attention.
Author contributions

in the cumulative biogas production (Fig. 7) may be attributed to
the high lag of phase (k) in Table 1. According to Kafle et al. [52],
and Mu et al. [27], the inactiveness of the inoculum and the BMNPs
inhibitory effects towards the microbial activity on the degradation
of the organics might have resulted in the high lag of phase. Above
all, the models fitness as evaluated by the regression coefficient
(R2) and sum of square errors (SSE) were proven to be significant
(P < 0.05). Furthermore, using the best performing reactor D, the
best model fitness as observed (Fig. 8) from the modified Gompertz
model was proven to perform better by all indices (fitness indica-
tors such as SSE, R2 and predictability) presented in Table 1. Promi-
nently, the high lag of phase (10.33 days) detected for the reactor
D, compels the need for further investigation on the activeness of
methanogens or the possibility of toxicity. As all the kinetics indi-
cator information obtained are very important for the avoidance of
any form of impending reactor failures or poor operations
[12,27,49,52].
Conceptualization, methodology, investigation, and writing of
the original draft preparation was done by EKT, whereas supervi-
sion, review, and editing was done by SR. All authors have read
and agreed to the published version of the manuscript.
Funding
This research was funded by the Water Research Commission of
South Africa under project identification WRC Project:
C2019/2020–00212.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.

4. Conclusion Acknowledgments

In this study, the impact of adding biomagnetic nanoparticles
(BMNPs) for the enhancement of anaerobic digestion of wastewa-
ter into bioenergy was seen as very promising and a viable
approach for organic waste management. The augmentation of
6
The authors wish to thank the Durban University of Technology,
Green Engineering and Sustainability Research Group, and the
Water Research Commission of South Africa for their support on
the project identification WRC Project: C2019/2020-00212.
E. Kweinor Tetteh and S. Rathilal Materials Today: Proceedings xxx (xxxx) xxx

References [27] H. Mu, Y. Chen, N. Xiao, Effects of metal oxide nanoparticles (TiO 2, Al 2O 3, SiO
2 and ZnO) on waste activated sludge anaerobic digestion, Bioresour. Technol.
(2011).
[1] A. Muratoglu, M.I. Yuce, World Energy Outlook and Place of Renewable
[28] J. Luo et al., Potential influences of exogenous pollutants occurred in waste
Resources (2015).
activated sludge on anaerobic digestion: A review, J. Hazard. Mater. (2020).
[2] A. McMillan, Global Warming 101 - Definition, Facts, Causes and Effects of
[29] E. Abdelsalam, M. Samer, Y.A. Attia, M.A. Abdel-Hadi, H.E. Hassan, Y. Badr,
Global Warming | NRDC.org, March 11, 2018.
Effects of Co and Ni nanoparticles on biogas and methane production from
[3] Y. Rodríguez, P.I.M. Firmino, V. Pérez, R. Lebrero, R. Muñoz, Biogas valorization
anaerobic digestion of slurry, Energy Convers. Manag. (2017).
via continuous polyhydroxybutyrate production by Methylocystis hirsuta in a
[30] J.J. Ambuchi, Z. Zhang, L. Shan, D. Liang, P. Zhang, Y. Feng, Response of
bubble column bioreactor, Waste Manag. (2020).
anaerobic granular sludge to iron oxide nanoparticles and multi-wall carbon
[4] E. Posadas, R. Muñoz, B. Guieysse, Integrating nutrient removal and solid
nanotubes during beet sugar industrial wastewater treatment, Water Res.
management restricts the feasibility of algal biofuel generation via wastewater
(2017).
treatment, Algal Res. (2017).
[31] A.A. Zaidi, F. RuiZhe, Y. Shi, S.Z. Khan, K. Mushtaq, Nanoparticles augmentation
[5] Eurostat, Sewage sludge production and disposal, 24-02-2020, 2020.
on biogas yield from microalgal biomass anaerobic digestion, Int. J. Hydrogen
[6] A. M. Mahon, R. Officer, R. Nash, and I. Ian O’Connor, EPA Research Programme
Energy 43 (31) (2018) 14202–14213.
2014-2020; Scope, Fate, Risks and Impacts of Microplastic Pollution in Irish
[32] H. Baniamerian et al., Application of nano-structured materials in anaerobic
Freshwater Systems, EPA Final Report. EPA Res. Rep. 210., 2017.
digestion: Current status and perspectives, Chemosphere (2019).
[7] A. Callegari, P. Hlavinek, A.G. Capodaglio, Production of energy (biodiesel) and
[33] Y. Wu, S. Wang, D. Liang, N. Li, Conductive materials in anaerobic digestion:
recovery of materials (biochar) from pyrolysis of urban waste sludge, Rev.
From mechanism to application, Bioresour. Technol. (2020).
Ambient. e Agua (2018).
[34] M.C. Mascolo, Y. Pei, T.A. Ring, Room Temperature Co-Precipitation Synthesis
[8] A.G. Capodaglio, A. Callegari, Feedstock and process influence on biodiesel
of Magnetite Nanoparticles in a Large ph Window with Different Bases,
produced from waste sewage sludge, J. Environ. Manage. (2018).
Materials (Basel) (2013).
[9] A. Kelessidis, A.S. Stasinakis, Comparative study of the methods used for
[35] H. El Ghandoor, H.M. Zidan, M.M.H. Khalil, M.I.M. Ismail, Synthesis and some
treatment and final disposal of sewage sludge in European countries, Waste
physical properties of magnetite (Fe 3O 4) nanoparticles, Int. J. Electrochem.
Manag. (2012).
Sci. (2012).
[10] A. Russo, Innovation and circular economy in water sector: The CAP group, The
[36] APHA, Standard Methods for the Examination of Water and Wastewater, no. 1.
Italian Water Industry: Cases of Excellence (2018).
2012.
[11] H. Métivier, H. Benbelkacem, V. Chatain, L. Culleton, N. Dumont, Biogas, in
[37] K. Peeters, G. Lespes, T. Zuliani, J. Ščančar, R. Milačič, The fate of iron
Handbook on Characterization of Biomass, Biowaste and Related By-products
nanoparticles in environmental waters treated with nanoscale zero-valent
(2020).
iron, FeONPs and Fe3O4NPs, Water Res. (2016).
[12] E.K. Tetteh, S. Rathilal, Kinetics and nanoparticle catalytic enhancement of
[38] X.Y. Er, T.W. Seow, C.K. Lim, Z. Ibrahim, Natural attenuation, biostimulation
biogas production from wastewater using a magnetized biochemical methane
and bioaugmentation of landfill leachate management, IOP Conference Series:
potential (Mbmp) system, Catalysts (2020).
Earth and Environmental Science (2018).
[13] T. Lönnqvist, A. Sanches-Pereira, T. Sandberg, Biogas potential for sustainable
[39] A. Baiju, R. Gandhimathi, S.T. Ramesh, P.V. Nidheesh, Combined heterogeneous
transport - A Swedish regional case, J. Clean. Prod. (2015).
Electro-Fenton and biological process for the treatment of stabilized landfill
[14] G.E.D. Oldroyd, R. Dixon, Biotechnological solutions to the nitrogen problem,
leachate, J. Environ. Manage. (2018).
Curr. Opin. Biotechnol. (2014).
[40] S.C. Bolyard, D.R. Reinhart, S. Santra, Behavior of engineered nanoparticles in
[15] E. Kweinor Tetteh, S. Rathilal, M. Chetty, E. Kwaku Armah, D. Asante-Sackey,
landfill leachate, Environ. Sci. Technol. (2013).
Treatment of water and wastewater for reuse and energy generation-emerging
[41] Y. Yang, C. Zhang, Z. Hu, Impact of metallic and metal oxide nanoparticles on
technologies, Water and Wastewater Treatment (2019).
wastewater treatment and anaerobic digestion, Environmental Sciences:
[16] S. Longo et al., Monitoring and diagnosis of energy consumption in wastewater
Processes and Impacts. (2013).
treatment plants. A state of the art and proposals for improvement, Appl.
[42] E. Abdelsalam, M. Samer, Y.A. Attia, M.A. Abdel-Hadi, H.E. Hassan, Y. Badr,
Energy (2016).
Influence of zero valent iron nanoparticles and magnetic iron oxide
[17] A. Rodríguez et al., Environmental optimization of continuous flow ozonation
nanoparticles on biogas and methane production from anaerobic digestion
for urban wastewater reclamation, Sci. Total Environ. (2012).
of manure, Energy (2017).
[18] D. Asante-Sackey, S. Rathilal, V.L. Pillay, E.K. Tetteh, Effect of ion exchange
[43] Y. Li, Y. Chen, J. Wu, Enhancement of methane production in anaerobic
dialysis process variables on aluminium permeation using response surface
digestion process: A review, Appl. Energy (2019).
methodology, Environ. Eng. Res. (2020).
[44] Y. Li, Y. Jin, Effects of thermal pretreatment on acidification phase during two-
[19] S. Vinardell et al., Advances in anaerobic membrane bioreactor technology for
phase batch anaerobic digestion of kitchen waste, Renew. Energy (2015).
municipal wastewater treatment: A 2020 updated review, Renew. Sustain.
[45] P. Rivas-García, J.E. Botello-Álvarez, A. Estrada-Baltazar, J.L. Navarrete-Bolaños,
Energy Rev., 2020.
Numerical study of microbial population dynamics in anaerobic digestion
[20] P. Mandal, A.K. Gupta, B.K. Dubey, A review on presence, survival, disinfection/
through the Anaerobic Digestion Model, Chem. Eng. J. 1 (2013).
removal methods of coronavirus in wastewater and progress of wastewater-
[46] E. Abdelsalam, M. Samer, Y.A. Attia, M.A. Abdel-Hadi, H.E. Hassan, Y. Badr,
based epidemiology, J. Environ Chem. Eng. (2020).
Comparison of nanoparticles effects on biogas and methane production from
[21] D. Pečar, A. Goršek, Kinetics of methane production during anaerobic
anaerobic digestion of cattle dung slurry, Renew. Energy (2016).
digestion of chicken manure with sawdust and miscanthus, Biomass
[47] A. Montusiewicz, Co-digestion of sewage sludge and mature landfill leachate
Bioenergy (2020).
in pre-bioaugmented system, J Ecol. Eng. (2014).
[22] Y.J. Lee, D.J. Lee, Impact of adding metal nanoparticles on anaerobic digestion
[48] J.H. Miller et al., Effect of silver nanoparticles and antibiotics on antibiotic
performance – A review, Bioresour. Technol. (2019).
resistance genes in anaerobic digestion, Water Environ. Res. (2013).
[23] F. Suanon, Q. Sun, D. Mama, J. Li, B. Dimon, C.P. Yu, Effect of nanoscale zero-
[49] A. A. Zaidi, F. RuiZhe, Y. Shi, S. Z. Khan, and K. Mushtaq, ‘‘Nanoparticles
valent iron and magnetite (Fe3O4) on the fate of metals during anaerobic
augmentation on biogas yield from microalgal biomass anaerobic digestion,”
digestion of sludge, Water Res. (2016).
Int. J. Hydrogen Energy, 2018.
[24] E. Lombi et al., Fate of zinc oxide nanoparticles during anaerobic digestion of
[50] A. Donoso-Bravo, S.I. Pérez-Elvira, F. Fdz-Polanco, Application of simplified
wastewater and post-treatment processing of sewage sludge, Environ. Sci.
models for anaerobic biodegradability tests. Evaluation of pre-treatment
Technol. (2012).
processes, Chem. Eng. J. (2010).
[25] M. Luna-delRisco, K. Orupõld, H.C. Dubourguier, Particle-size effect of CuO and
[51] I. Syaichurrozi Budiyono, S. Sumardiono, Biogas production kinetic from
ZnO on biogas and methane production during anaerobic digestion, J. Hazard.
vinasse waste in batch mode anaerobic digestion, World Appl. Sci. J. (2013).
Mater. (2011).
[52] G.K. Kafle, S.H. Kim, K.I. Sung, Ensiling of fish industry waste for biogas
[26] C.M. Ajay, S. Mohan, P. Dinesha, M.A. Rosen, Review of impact of nanoparticle
production: A lab scale evaluation of biochemical methane potential (BMP)
additives on anaerobic digestion and methane generation, Fuel (2020).
and kinetics, Bioresour. Technol. (2013).

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