Zaidi 2018

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 2
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Nanoparticles augmentation on biogas yield from

microalgal biomass anaerobic digestion
Asad A. Zaidi a, Feng RuiZhe a, Yue Shi a,*, Sohaib Z. Khan b,c,
Kashif Mushtaq d
a
College of Power and Energy Engineering, Harbin Engineering University, Harbin 150001, PR China
b
Department of Mechanical Engineering, Faculty of Engineering, Islamic University of Madinah, Madinah, P. O. Box
170, Saudi Arabia
c
Department of Engineering Sciences, PN Engineering College, National University of Sciences and Technology,
Karachi 75350, Pakistan
d
Massachusetts Institute of Technology Portugal Program, Faculty of Engineering, University of Porto (FEUP),
Portugal
article info abstract
Article history: This study evaluates the influence of metal and metal-oxide nanoparticles (NPs) on biogas
Received 22 March 2018 production from green microalgae Enteromorpha. The concentration of metallic NPs (Ni, Co)
Received in revised form was 1 mg/L and oxides NPs (Fe3O4, MgO) was 10 mg/L. An anaerobic digestion was carried
5 May 2018 out batch-wise with working volume, operating temperature, mixing rate and hydraulic
Accepted 23 May 2018 retention time as 500 ml, 37 C, 150 rpm and 170 h, respectively. The measurements of
Available online xxx chemical oxygen demand (COD), volatile fatty acids (VFAs), reducing sugar and biogas
production were observed to monitor effectivity of nanoparticles. The results showed that
Keywords: NPs has moderate positive influence in biogas production until 60 h of retention time but
Anaerobic digestion significantly improve afterward. The maximum total biogas yield of 624 ml was achieved
Biogas by Fe3O4 NPs whereas highest biohydrogen, 51.42% (v/v) was achieved by Ni NPs. The cu-
Green microalgae mulative increase in biogas production for Fe3O4, Ni, Co and MgO NPs was 28%, 26%, 9% and
Kinetic models 8%, respectively. A modified Gompertz and Logistic function model were used to determine
Nanoparticles (NPs) kinetic constants of the reaction. The logistic model has the better predicting ability for
microalgae anaerobic digestion.
© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
anaerobic digestion [2]. It can also be used to treat animal

Introduction manure, energy crops, food waste, microalgae and agricul-
tural residues [3].
Anaerobic digestion is the biochemical and microbiological The anaerobic digestion process consists of four main
degradation process of organic substrates which takes place conversion phases of organic matter into biogas namely; hy-
in the absence of oxygen [1]. Liquid and solid waste such as drolysis, acidogenesis, acetogenesis and methanogenesis [4].
high organic content waste water, sewage sludge and organic In the first phase large and complex organic matter such as
fraction of municipal solid waste (MSW) can be treated by
* Corresponding author. College of Power and Energy Engineering, Harbin Engineering University, Harbin 150001, PR China.
E-mail address: shiyue@hrbeu.edu.cn (Y. Shi).
https://doi.org/10.1016/j.ijhydene.2018.05.132
0360-3199/© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article in press as: Zaidi AA, et al., Nanoparticles augmentation on biogas yield from microalgal biomass anaerobic
digestion, International Journal of Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.05.132
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 2
carbohydrates, fats and proteins react with water to form production of methanogens in digester sludge [11]. In
monomers by the assistance of hydrolytic bacteria. During the another study, Qiang et al. [9] stated that the development of
second phase conversion of monomers into volatile fatty acids anaerobic bacteria during enzyme synthesis is reliant on the
(VFAs) is carried out by the aid of fermentative bacteria. The presence of iron, nickel, and cobalt. Comparison of the ef-
third phase involves the transformation of VFA into acetic fects of micronutrients of NiCl2, Fe2O3, CoCl2, (NH4)6Mo7O24
acid, carbon dioxide (CO2) and hydrogen under the action of along with their NPs with cattle manure slurry on biogas
acetogenic bacteria. During the final phase, methanogenic production is carried out by Juntupally et al. [12]. They
bacteria convert acetic acid and hydrogen into methane (CH4) concluded that all NPs have an increasing effect on biogas as
and CO2 [5]. Biogas is produced by anaerobic digestion and compared to their micronutrients. NiCl2 micronutrient and
typically has a calorific value of 21e24 MJ/m3 [6]. The pro- Ni NPs produced the highest biogas production. In another
duction of biogas has increased rapidly since 2000 [7]. Conti- study conducted by Abdelsalam et al. [13], comparison of Ni,
nent wise global biogas production contribution from Global Co and Fe3O4 NPs on biogas production was obtained with
Bioenergy Statistics 2017 by World Bioenergy Association anaerobic digestion of livestock manure. This study also
(WBA) is shown in Fig. 1. showed an increase in biogas production by NPs of these
The concerns about expansion in bioenergy sector during trace metals during anaerobic digestion. Ambuchi et al. [14]
past decade have driven a number of scientists and re- studied the response of Fe2O3 NPs on anaerobic granular
searchers to pursue innovative solutions for its production. sludge during beet sugar industrial wastewater treatment.
Nanotechnology is one of the emerging branches of science. He reported that due to the utilization Fe2O3 NPs as conduits
From a materials point of view, it deals with materials having for electron transfer toward methanogens improves biogas
one of the dimensions less than 100 nm. Nanotechnology can production.
be applied in bioenergy field for the purpose of feedstock An intriguing raw biomass, other than conventional
modification and catalysis that is more efficient. Nano- organic wastes used for the production of bioenergy, is
materials include nanoparticles (NPs), nanofibers, nanotubes; Aquatic Algal [15]. It can be sourced from natural algal bloom
nanosheets and others have been employed for bioenergy or mass cultivation, is considered a promising substrate for
production [8]. hydrogen fermentation [16]. Hydrogen has high energy con-
NPs have a high surface to volume ratio, which increases tent on a mass basis as compared to hydrocarbon fuels [17].
the chemical reaction sites. It is generally hypothesized that The main benefit of hydrogen as a fuel is the absence of CO2,
trace metals improve the digestion process by exciting the CO and hydrocarbon emissions. Photo-fermentation is
bacterial action causing an increase in biogas production commonly applied process to treat microalgae for bio-
during anaerobic digestion [6]. Trace metals worked as an hydrogen production. However, hydrogen production through
electron donor in an anaerobic digestion process. They in- this process remained less effective as the oxygen production
crease the total consumption of hydrogen methanogens and during photo-fermentation impede the activity of hydroge-
activity. They release ions and contribute to the production nase enzymes and eventually stop the hydrogen production
of key enzymes [9]. They can also optimize the microbial [18]. In recent years, dark fermentation of microalgae biomass
population, change the hydrolysis fermentation types and for biohydrogen production has received increasing consid-
stimulate the acetic acid content [10]. It has been reported eration [19]. Low biohydrogen potential were obtained
that iron, cobalt and nickel were successfully exciting the through the dark fermentation method, therefore, a
Fig. 1 e Global biogas production contribution [7].
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 2 3
pretreatment step is frequently needed to convert organic

matter to sugars which increase biohydrogen production [16]. Materials and methods
An alternative process for collective bioenergy production and
depollution is linking an anaerobic digester to a microalgal Raw material
culture [20]. Studies have shown that anaerobic sludge and
microalgae were co-cultured to enhance the energy conver- An anaerobic sludge acquired from an Anaerobic-Anoxic-Oxic
sion for hydrogen production as well as nutrients removal (AAO) reactor at Harbin Wenchang Sewage Treatment Plant,
from starch wastewater [21]. Biohydrogen production, in Harbin, China. It had been aeration cultured for two weeks,
particular, is aided by hydrogenase enzymes which can be according to the ratio of 300:5:1 plus glucose, NH4Cl, KH2PO4
categorized into two types, [NieFe] hydrogenases and [FeeFe] [28]. Total suspension solids (TSS) and Volatile Suspension
hydrogenases, in accordance with the metal content present Solids (VSS) of sludge were 6420 mg/L, 2530 mg/L, respectively.
at their active site. The [NieFe] hydrogenases are widely The Enteromorpha was from the freshwater algae and acquired
disseminated among bacteria, and on the other hand, the from the Institute of Hydrobiology of The Chinese Academy of
[FeeFe] hydrogenases are confined to a few bacteria [22]. Since Science, Wuhan, China. I had been air-dried in the drying
nickel is the key component of the [NieFe] hydrogenases, it oven, and sealed with a breathable film in the bottle. Each
plays an imperative role in fermentative hydrogen production biodigester inoculated with 60 ml of sludge and 20 g of
[23]. Enteromorpha powder. The amounts were selected based on
Taherdanak et al. [24] have investigated the effects of Fe the previous study conducted by us using response surface
and Ni NPs versus Fe2þ and Ni2þ ions at concentrations methodology (RSM) for optimization of Enteromorpha and
ranging from 0 to 50 mg/L on hydrogen production from anaerobic sludge digestion [29].
anaerobic sludge from glucose as feed. The results showed Four different types of NPs were used in this study. Two
that both Fe NPs and Fe2þ ion increase hydrogen production were metal NPs (Ni, Co) while other two were metallic-oxide
15% and 37% at dosages of 10 mg/L and 25 mg/L in comparison NPs (Fe3O4, MgO). NPs were purchased from China Metallur-
with control. The Ni2þ ions showed 55% enhancement in gical Research Institute, Beijing. The average size of the NPs
hydrogen yield at 25 mg/L concentration, whereas Ni NPs did was less than 100 nm with a spherical shape. Most of the
not show any significant improvement. In another study, Li studies in literature reported spherical shape NPs; smaller
et al. [25] examined the effect of Fe2O3 NPs using Enterobacter nano-sizes with minor dosages are better for anaerobic
aerogenes on hydrogen production from dark fermentation of digestion of organic matter. However, no study reported NPs
glucose. An increase of 17% in biohydrogen production was with other morphology. The concentration of NPs in the
observed at a concentration of 200 mg/L Fe2O3 NPs from biomass was 1 mg/L for Ni and Co NPs whereas the concen-
glucose. The authors reported that hydrogenase activity was tration of NPs for Fe3O4 NPs and MgO NPs was 10 mg/L. Similar
enhanced by ferric oxide NPs. Liu et al. [26] examined the ef- concentrations have been used in other studies for these NPs
fect of TiO2, ZnO and SiC NPs on photo-fermentative hydrogen by Qiang et al. [9] and Abdelsalam et al. [30]. The suspensions
production form photo-fermentative bacteria (Rhodop- of NPs for above mentioned concentrations were prepared by
seudomonas sp. nov. strain A7). The outcomes revealed that all adding distilled water containing sodium dodecylbenzene
NPs improved the hydrogen production. The authors sulfonate (SDS) 0.1 mM to reduce the agglomeration of NPs
mentioned that combining NPs with photo-fermentative [31].
bacteria is one promising method to improve hydrogen
yield. Recently, Keskin et al. [27] investigated the influence of
Experimental procedure
trace metals on biohydrogen yield from the dark fermentation
The experiments were carried out via anaerobic batch system.
of fruit and vegetable waste. The authors inspected eleven
Anaerobic glass lab-scale bottles with a working volume of
diverse trace metals micro particles such as Fe, Ni, Zn, Co, Cu,
500 ml were used as biodigesters and operated for 170 h. The
Mn, Al, B, Se, Mo and W. The results showed that biohydrogen
digesters were sealed with rubber stoppers, purged with ni-
production was enhanced by 1.1e2.8 times in comparison
trogen gas for 5 min to create anaerobic condition inside
with control. The study concluded that out of all trace metal
digester [32]. The digestion environment has been maintained
micro particles Fe, Ni, Cu and Zn produced more biohydrogen.
at 37 C [13] and 150 rpm mixing speed. Each experiment was
A number research works that have been conducted using
repeated three times to minimize possible errors, and the
different NPs on various kinds of waste and resources; how-
average values are reported here. One-way ANOVA was done
ever, to the best of the authors' knowledge, NPs interaction
by using Origin Pro 8 software, p < 0.05 was considered to be
with microalgal biomass for biogas and biohydrogen produc-
statistically significant.
tion has not been studied yet.
The present study aims to explore the influence of trace
Analytical methods
metal and metal-oxide NPs such as Ni, Co, Fe3O4 and MgO on
biogas and hydrogen production from green microalgae
The measurements of soluble indexes, including chemical
Enteromorpha. To understand the effectiveness of the NPs,
oxygen demand (COD), pH, volatile fatty acids (VFAs) and
measurements of soluble indexes including chemical oxygen
reducing sugar were determined according to standard
demand (COD), volatile fatty acids (VFAs), reducing sugar was
methods [33]. Biomass concentration like glucose concentra-
carried out. Established prediction models have been studied
tion was estimated by 3,5-dinitrosalicylic acid (DNS) method
from the experimental results for the estimation of the biogas
using spectrophotometer (DR 3900, HACH, USA) at a
production with the NPs.
maximum wavelength (lmax) of 550 nm. Proteins were Levenberg-Marquardt (L-M) algorithm. The algorithm com-
measured by the Bradford method [34] whereas carbohydrates bines the Gauss-Newton method and the steepest descent
were measured by sulfuric acid e UV method [35]. The pH was method.
recorded using a pH analyzer (PHS-3C, INESA, China). Volatile To find out which model is closely matching with the
fatty acids (VFA) were analyzed using gas chromatography (GC experimental data a second order Akaike Information Crite-
7820A, Agilent Technologies, USA) with Flame Ionization De- rion (AIC) test was carried out [45]. The lower value of the AIC
tector (FID). The hydrogen content of the biogas was analyzed suggests a better fit and predicting capability of the model. For
by gas chromatography (SP-2100A, BFRL, USA) with Thermal each model, the AIC value and Akaike's weight value was
Conductivity Detector-Flame Ionization Detector (TCD-FID). calculated by using Eqs (3) and Eq (4) [46]:
Gas samples were taken using a 50 ml syringe to measure the 8
> RSS þ 2K N
gas composition. A volume of 0.5 ml of biogas was injected >
< Nln ; when 40
N K
into a gas chromatography (SP-2100A, BFRL, USA) to measure AIC ¼ (3)
>
> RSS 2KðK þ 1Þ N
biogas composition. The biogas production was observed : Nln þ 2K þ ; when < 40
N NK1 K
twice a day and its composition was measured once during
the experiment. The samples were taken using typical medi-
Þ
ð0:5DAICÞ
cal type syringe with a long needle; 4 ml of sample was Akaike's weight ¼ eð0:5DAICÞ=ð1þe (4)
collected from each digester by injecting the needle through where:
sealed rubber caps and immediately transferred to the small
tubes sealed with rubber stoppers to avoid gas losses. The N ¼ Number of points
sample tubes were then stored in a refrigerator at a temper-
RSS ¼ Residual sum of square
ature of 80 C and used for analysis.
K ¼ Number of model parameters
DAIC ¼ The relative difference between two AIC values.
Mathematical kinetic models
Multiple models are available for anaerobic digestion of

Results and discussion
various biomasses. The forerunners of these models were
Graef and Andrews [36,37] in the late 1960's. In the year 2002,
Influence of nanoparticles on biogas and hydrogen
the Anaerobic Digestion Model No.1 (ADM1) [38] was devel-
production
oped by the International Water Association (IWA) group.
The plus point of ADM1 model was its capability of simu-
All NPs showed a positive effect on biodegradability of
lating the anaerobic digestion of different biomasses. The
microalgal biomass (Enteromorpha), which is certain by the
disadvantage, however, is that it is aided through many
enhanced biogas production compared with the control
input parameters. This is not only time-consuming but also
experiment as shown in Fig. 2. It can be observed that during
takes a toll on expense from an experimental point of view.
the initial 60 h, biogas production had a low significant posi-
For such inconveniences to be eliminated, statistical linear
tive influence of NPs in comparison with the control sample.
and nonlinear regression models (modified Gompertz model,
The production of biogas then significantly increased, with
Logistic function, Transference function e Reaction curve
the passage of time, for all the samples containing NPs in
type model, etc.) were established so that the anaerobe
comparison to the control sample. The initial duration of the
digestion performances can be both described and predicted
[39e42].
The calculation and comparison of biogas production ki-
netic during digestion of algal biomass with different NPs
were modeled via modified Gompertz model Eq. 1 [43] and
Logistic Function model Eq. 2 [44].

B ¼ Bp :exp exp MBPR:2:7183 Bp :ðBPDT tÞ þ 1 (1)

B ¼ Bp 1 þ exp 4MBPRðBPDT tÞ Bp þ 2 (2)
where:
B ¼ Cumulative biogas volume at digestion time t (ml)

BP ¼ Biogas production potential (ml)
MBPR ¼ Maximum biogas production rate (ml/h)
BPDT ¼ Biogas production delay time (hrs)
t ¼ Total digestion time (hrs).
The parameters for both the models were determined by

using Origin Pro 8 software. The software calculates and ad- Fig. 2 e Biogas production influenced by nanoparticles,
justs the parameter values in the iterative procedure based on standard deviations are represented by error bars.
experiments can be categorized as less-effective domain and conducted by Elreedy et al. [52] showed 23% increase in biogas
later part as a high-effective domain. The less effective production by 60 mg/L Ni NPs on anaerobic digestion of in-
domain is attributed to the presence of a highly resistant cell dustrial wastewater containing mono-ethylene glycol. The
wall of microalgae biomass [47]. This cell wall comprises two ability of iron to gain or lose electrons makes it a potential
layers. The external layer is electron dense polymeric matrix candidate to be used as an additive in anaerobic digestion
composed of protein and carbohydrates. The internal layer process [6]. An increase of 1.25 times in biogas production by
composed of cellulose and hemicellulose [48]. In the high Fe3O4 NPs on anaerobic digestion of waste water sludge
effective domain, the mechanism behind the increase in identified by Suanon et al. [53]. Casals et al. [54] reported that
biogas is credited to NPs stimulating effect responsible for the 100 ppm of 7 nm Fe3O4 NPs showed a considerable increase in
dissolution of proteins, carbohydrates and cellulose. NPs biogas production in an anaerobic waste treatment reactor.
dissolve the microalgae organics and increase the lysis rate The authors showed that iron oxide NPs act as a source to
which is attributed to the increasing effect on biogas pro- produce Fe2þ ions and increase biogas production. This
duction. These dissolvable organics released intracellular observation accords with Feng et al. [55], who reported an
components into the liquid phase due to microalgae disinte- improved digestion performance due to the presence of Fe2þ/
gration by NPs. Initially, NPs thrashes the external layer Fe3þ ions present in the reactor in the form of NPs. Fe2þ ions
(protein and carbohydrates) and then solubilize the internal are essential for power generation and DNA replication. The
layer (cellulose and hemicellulose) [49]. The glycosidic bond in effortlessness with which iron ions gain or lose electrons
carbohydrates and polysaccharides hydrolyze by NPs which makes them a perfect and adaptable cofactor for various
turn into simple sugars. This effect resulted in increased proteins. The surplus iron can easily produce very reactive
permeability of external layer. Later, NPs attacks the internal and toxic free radicals that are harmful to different bio-
layer and hydrolyze cellulose into oligosaccharides such as molecules (nucleic acids and lipids, amongst others) [54]. Our
cellobiose and cellodextrin [50]. The release of biopolymers results are also in agreement with Ambuchi et al. [14], the
(Carbohydrates and proteins) is shown in Fig. 3. The carbo- authors reported an increase of 1.25 times in biogas produc-
hydrates and proteins released by dissolution of the cell tion by Fe3O4 NPs as compared to control experiment. The
structure of microalgae are then converted into amino acids, effect of nZVI (nanozero-valent iron), Ag, Fe2O3 and MgO NPs
simple sugars, peptides and volatile fatty acids [51]. The on waste activated sludge was conducted by Wang et al. [56].
maximum cumulative biogas and the amount of hydrogen The average concentrations of Fe2þ, Agþ and Mg2þ released
produced during the experiment are presented in Fig. 4. Ni NPs were 1.3, 3.3 and 9.8 mg/L, respectively. They reported that
produced highest biohydrogen i.e, 51.42% (v/v) followed by lower concentrations of Fe2þ facilitate the anaerobic digestion
Fe3O4 NPs, 44.61% (v/v). of sludge whereas high concentrations of Agþ and Mg2þ ions
The results show that Fe3O4 and Ni NPs have a high biogas inhibit the anaerobic digestion. The concentration of MgO NPs
and biohydrogen yield as compared to other two and control used was 500 mg/g of the total suspended solids. Our result
samples. Our results obtained by microalgae interaction with shows 8% increase in biogas production by MgO NPs as low
NPs are in agreement with multiple studies available in liter- concentration used in present study released the lower
ature with the different feedstock. Similar trends were ob- amount of Mg2þ ions in the digester and improves gas pro-
tained by the study conducted by Abdelsalam et al. [13], it duction. Our results also agrees with Guo et al. [57], the au-
showed that Ni, Fe3O4 and Co NPs produced 1.8, 1.7 and 1.7 thors considered Fe2þ and Mg2þ as the most critical nutrient
times enhancement in biogas yield from anaerobic digestion salts for hydrogen fermentation. They studied the effect of
of cattle manure slurry, respectively. Another study these nutrition components on Hydrogen producing strain E.
harbinense B49 and found a positive effect of these nutritions
on hydrogen production. The optimal condition (glucose
14,500 mg/L, Fe2þ 180 mg/L and Mg2þ 690 mg/L) provided -
production of 0.024H2 g/g - glucose. In another study, Liu et al.
[58] investigated the effect of Ni2þ, Fe2þ and Mg2þ concentra-
tions on hydrogen production from Rhodopseudomonas faecalis
RLD-53. The results showed that Ni2þ (236 mg/L) and Fe2þ
(4480 mg/L) produced maximum hydrogen production of
0.032 and 0.031 g H2/g glucose -, respectively. However, Mg2þ
did not affect hydrogen production yield. The study indicated
that the presence of metal ions (Ni2þ and Fe2þ) stimulated the
bioactivity of hydrogen producing bacteria. The hydrogen
production could be affected by supplementation of Ni2þ and
Fe2þ ions into the active sites of [Ni-Fe] hydrogenase by
prompting the [Ni-Fe]- hydrogenase activity. Ni2þ and Fe2þ are
the essential components of [Ni-Fe] hydrogenase and have an
integral role in the production of hydrogen. Mg2þ ion, how-
ever, does not in any way contribute to hydrogen production
Fig. 3 e Proteins and carbohydrates production influenced [58]. The authors also mentioned that higher concentrations
by nanoparticles, standard deviations are represented by of these metal ions decrease hydrogen yield; our results agree
error bars. with these findings.
Fig. 4 e (A) Cumulative Biogas Production, (B) Hydrogen content % (v/v) from green microalgae Enteromorpha with the
presence of NPs, standard deviations are represented by error bars.
COD, reducing sugar and pH change The rising trend indicated the cell lysis and production of
inter-cellular segments (glycoproteins, carbohydrates and
The influence of NPs on biogas production during anaerobic cellulose) due to disruption of cell walls of microalgal biomass
digestion is noticeable by the evolution of COD. It is shown in by the addition of metal and metal oxide NPs. The peaks show
Fig. 5 (A) that concentration of COD increases for the first the higher COD level which indicates that more substantial
60 h of digestion. COD becomes stable for the next 48 h. COD oxidizable organic matter is present in the digesters which
concentration decreased for control, Co NPs and MgO NPs reduce the dissolved oxygen level and promotes anaerobic
during the last 72 h, however it increases for Ni NPs and conditions. The results presented in Figs. 2 and 5 (A) shows
Fe3O4 NPs. The highest amount of COD is provided by Fe3O4 that digesters inoculated with Fe3O4 NPs and Ni NPs had better
and Ni NPs which are 14,760 mg/L and 14,745 mg/L, performance than other digesters which shows that additive
respectively. amounts of these NPs promoted the dissolution of COD.
a high gas production meant most reducing sugar had been

used to produce the biogas in this period. The reducing sugar
consumption was slower for control after 72 h whereas the
consumption of sugar by anaerobic bacteria was faster for
groups with NPs.
The pH value continuously decreases during the digestion
period for all groups as shown in Fig. 5 (C). The pH value
maintained at the level at 5.6e6.6. The decline in the pH value
attributes to the production of organic acids during the
anaerobic digestion process.
VFA production during fermentation
Volatile fatty acids (VFAs) contents revealed the influence of

NPs on biogas production. VFA production was measured at
the beginning and the end of digestion. At the start, after in-
cubation of NPs and before anaerobic digestion, VFA produc-
tion values were relatively low and almost the same among
each group except for oxide NPs. Both oxide NPs had greater
amount butyric acid at the start. It is clear from Fig. 6 that after
a hydraulic retention time of 170 h, the digestion process
significantly increased VFA production content for all groups,
indicating that the digestion was surely hydrolyzing some
insoluble components of algae biomass. This tendency was in
accordance with the gas production profile during the diges-
tion shown in Fig. 2. The amount of increase can reach
1988 mg/L and 1865 mg/L in a group of Ni NPS, and Fe3O4 NPs,
respectively. The amount of butyric acid had the most sig-
nificant effect on algal biomass digestion. High amounts of
acetic acid and butyric acid caused more biogas yield [29].
According to Dareioti et al. [59] higher biogas and biohydrogen
production depend on the final amount of acetic acid and
butyric acid production. The high COD peaks for Fe3O4 and Ni
NPs and more biogas production along with the VFAs gener-
ation attributes to more cell wall disruption and dissolution of
glycoproteins, carbohydrates and cellulose as compared to
other groups and control. This observation is in agreement
with Greden et al. [60] who stated that rising of COD value in
anaerobic digestion is accompanied by cell membranes
disruption and VFAs generation.
Mathematical kinetic models
Modified Gompertz and Logistic models were used to conduct

the kinetic study for the cumulative biogas produced [43,44].
The kinetic study results obtained from modified Gompertz
and Logistic model are given in Tables 1 and 2, respectively.
Fig. 5 e Measurement of soluble indexes (A) COD change (B) The comparison of experimental and predicted cumulative
Reducing sugar change (C) pH change affected by biogas production by all groups is shown in Figs. 7 and 8.
nanoparticles, standard deviations are represented by While using modified Gompertz model, maximum biogas
error bars. production rate (MBPR) for the control was 4.21 ml/hr. For Ni,
Co, Fe3O4 and MgO NPs, the MBPR increased to 5.40, 4.67, 5.18
and 4.32 ml/hr, respectively. Similarly, for the Logistic model,
The evolution of reducing sugar during the digestion pro- the maximum biogas production rate (MBPR) for the control,
cess is presented in Fig. 5 (B). The reducing sugar concentra- Ni, Fe3O4, Co and MgO NPs were 4.71, 6.00, 5.19, 5.75 and 4.77
tions at 24 h in the digestion medium with NPs was about ml/hr respectively. It is identified by both the kinetic models
0.35 g/L whereas for control it had a higher value of about that Ni NPs and Fe3O4 NPs had enhanced the biogas produc-
0.47 g/L. Reducing sugar value increased for all groups during tion rate and shorten the lag phase period compared to other
the next 24 h. It decreased for all NPs afterwards, however, groups. The reason for reduction in lag was due to cell walls
kept on increasing for control. Low reducing sugar value with disruption occurred during more effective domain of biogas
Fig. 6 e VFA production affected by NPs at Start and End of the experiment, standard deviations are represented by error
bars.
Table 1 e Parameters of modified Gompertz model.

Parameter Treatments
Control Ni NPs Co NPs Fe3O4NPs MgO NPs
BP (ml) 608.45 772.18 656.44 802.55 664.08
MBPR (ml/hr) 4.21 5.40 4.67 5.18 4.32
BPDT (Hrs) 1.14 1.40 1.25 1.23 1.05
R2 0.99246 0.99719 0.99493 0.99739 0.99716
Predicted Biogas Yield (ml) 505.50 629.73 547.50 636.68 540.62
Measured Biogas Yield (ml) 488 618 535 624 529
Difference between measured and predicted biogas yield (%) 3.58 1.89 2.33 2.03 2.19
Remarks: BP, Biogas production potential; MBPR, Maximum biogas production rate; BPDT, Biogas production delay time; R2, Correlation
Coefficient.
Table 2 e Parameters of Logistic Function model.

Parameter Treatments
Control Ni NPs Co NPs Fe3O4NPs MgO NPs
BP (ml) 517.42 651.76 560.14 667.89 561.38
MBPR (ml/hr) 4.71 6.00 5.19 5.75 4.77
BPDT (Hrs) 1.45 1.69 1.58 1.53 1.30
R2 0.99766 0.99796 0.99742 0.99764 0.99824
Predicted Biogas Yield (ml) 491.04 612.95 531.76 620.95 526.74
Measured Biogas Yield (ml) 488 618 535 624 529
Difference between measured and predicted biogas yield (%) 0.62 0.82 0.60 0.49 0.42
Remarks: BP, Biogas production potential; MBPR, Maximum biogas production rate; BPDT, Biogas production delay time; R2, Correlation
Coefficient.
production, high COD and faster consumption of sugar by The results for Akaike Information Criterion (AIC) test
anaerobic bacteria. The correlation coefficient for modified performed for two models are shown in Table 3. In this study,
Gompertz model and Logistic Function model was above Logistic function model has lower AIC value which is sug-
99.58% and 99.77% respectively. gesting to be a better model to use in this case.
Fig. 7 e Non-linear Fit of cumulative biogas production for Gompertz model.
Fig. 8 e Non-Linear Fit of cumulative biogas production for Logistic Function model.
Table 3 e Results for Akaike's information criterion (AIC) test.

Model RSS N AIC Akaike Weight
Modified Gompertz Model 2408.60702 14 84.5129 2.79964E-4
Logistic Function Model 748.55971 14 68.15176 0.99972
Remarks: RSS, the Residual sum of the square; N, Number of Points; AIC, Akaike's Information Criterion.
[10] Liu C, Yuan H, Zou D, Liu Y, Zhu B, Li X. Improving

Conclusions biomethane production and mass bioconversion of corn
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Nanoparticles augmentation on biogas yield from

article info abstract

anaerobic digestion [2]. It can also be used to treat animal

Fig. 1 e Global biogas production contribution [7].

pretreatment step is frequently needed to convert organic

Multiple models are available for anaerobic digestion of

B ¼ Cumulative biogas volume at digestion time t (ml)

The parameters for both the models were determined by

a high gas production meant most reducing sugar had been

VFA production during fermentation

Volatile fatty acids (VFAs) contents revealed the influence of

Mathematical kinetic models

Modified Gompertz and Logistic models were used to conduct

Table 1 e Parameters of modified Gompertz model.

Table 2 e Parameters of Logistic Function model.

Fig. 7 e Non-linear Fit of cumulative biogas production for Gompertz model.

Table 3 e Results for Akaike's information criterion (AIC) test.

[10] Liu C, Yuan H, Zou D, Liu Y, Zhu B, Li X. Improving

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