Journal of the Saudi Society of Agricultural Sciences 22 (2023) 535–545

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Synthesis and surface morphology of banana biochar-based nano-

fertilizer and its effect on first stages of growth parameters of cucumber,
broccoli, and red okra
Osama Farooq Tarar a, Amina Asghar a, Sohaib Ahmad Qayyum b, Humaira Kanwal b, Ambreen Lateef b,
Rabia Nazir b,⇑, Syed Hussain Imam Abidi c, Muhammad Kashif Naeem d, Bilal Shahid a
a
Department of Chemistry, Division of Science and Technology, University of Education, Township, Lahore 54770, Pakistan
b
Applied Chemistry Research Center, Pakistan Council of Scientific and Industrial Research Laboratories Complex, Ferozepur Road, Lahore 54000, Pakistan
c
Pakistan Council of Scientific and Industrial Research Council, 01 Constitution Avenue, G-5/2, Islamabad, Pakistan
d
National Institute for Genomics and Advanced Biotechnology (NIGAB), NARC, Park Road, 45500, Islamabad, Pakistan

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

Article history: Smart agro-practices over the years have revolutionized the agriculture sector and promoted the concept
Received 18 October 2022 of sustainable agriculture. One such practice is use of agro-waste biochar in agricultural, environmental,
Revised 7 June 2023 and climatic operations. The viability of using a biochar-based nanocomposite as a support fertilizer for
Accepted 11 June 2023
the gradual release of nitrogen, potassium, and phosphorus in various media is examined in this study.
Available online 6 July 2023
The banana peel biochar (BPBC) and its nanocomposite (BNF) were prepared using a simple yet compre-
hensive chemical process. Synthesized materials were evaluated using FT-IR and SEM/EDX. Physical attri-
Keywords:
butes as well as fertilizer basic characteristics were determined and prepared nanocomposite
Biochar
Nanocomposite
demonstrated noticeably better water absorbance ratio (68%), equilibrium water content (78.97%), and
Sslow-release fertilizers swelling ratio (3.64 g g
1) than biochar, which is advantageous for preserving soil water levels. The salt
index values (0.087mmhos/cc) of the created nanocomposite performed better when compared to the
conventional fertilizers due to their safer application. Long-term availability of all doped minerals to
the plants, during experimental cycle, was revealed by slow-release nutrient studies in water and soil,
which is ideal for promoting germination and growth. The findings of this research revealed that pre-
pared BNF showed improved germination parameters i.e., time for 50% germination (3.4, 3.3, 4.4 days),
germination index (3.1, 3.5, 2.4), final germination percentage (91.7, 100, 83.3%), mean germination time
(4.0, 3.9, 4.9 days), for cucumber, broccoli and okra, respectively. In addition to that the prepared BNF
facilitated enhanced shoot and root length in all the three vegetables as compared to conventional fertil-
izers. The dose optimization studies depicted that best results of germination as well as plant growth
parameters are facilitated by BNF (37.5 kg/ha) owing to enhancement in soil quality by supplying addi-
tional organic matter in addition to provision of nutrients on slow-release.
Ó 2023 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an
open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction Yada 2011). These problems can further lead to compounding

and sprouting of additional issues concerned with urbanization,
Agriculture is the backbone of Pakistan’s economy but the sec- reliability, and environmental effects (such as nutrient seepage,
tor is facing daunting challenges not only in the country but all global warming, and pesticide and fertilizer buildup) (Ditta
over the world owing to food security, climate change and inten- 2012). In spite of all of these obstacles, suitable agricultural meth-
sive agro-farming practices that have put enormous burden on this ods and much-needed innovative crop-producing methods are
sector (Yaqoob et al., 2022). With the passage of time this pressure constantly being developed in order to ensure a stable and safe
is mounting as escalating increase in world’s population is food supply. These include cutting-edge technologies, irrigation
recorded that is expected to reach 7.75 billion in 2025(Chen and advancements, superior hybrid seeds, and controlled use of chem-
ical fertilizers, herbicides, and pesticides in order to address the
needs of such a big population (Liu et al., 2014, Bucci et al., 2018,
⇑ Corresponding author. Serebrennikov et al., 2020, Fahad et al., 2021, Montazar 2021).
E-mail address: rabiapcsir@yahoo.com (R. Nazir).

https://doi.org/10.1016/j.jssas.2023.06.002
1658-077X/Ó 2023 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
O.F. Tarar, A. Asghar, S.A. Qayyum et al. Journal of the Saudi Society of Agricultural Sciences 22 (2023) 535–545

Over the years, field of fertilizers have also taken many roads in Enhancement in crop growth parameters by use of developed
essence to improvise the product and create balance between its nanofertilizer in comparison to the conventional fertilizers and 4)
positive and negative impacts. Fertilizers can significantly increase optimization of nanofertilizer dosage for attaining best yield.
crop yield, but their improper and unbalanced use has become a
serious issue since it not only reduces output but also stresses 2. Materials and methods
the economy. Efforts are underway to optimize the dose to yield
ratio for producing crops with better quality while mitigating their 2.1. Chemicals
environmental impacts. When standard fertilizers, such as urea,
NPK, and di-ammonium phosphate (DAP), which contain 40–70% The experiments only employed analytical-grade chemicals.
of nitrogen, 80–90% of phosphorus, and 50%–90% of potassium, Sodium phosphate monobasic dihydrate (NaH2PO42H2O) was pur-
are applied to soil, very little of it is absorbed into the plants while chased from Merck. Potassium sulphate (K2SO4), sodium nitrate
the remainder of nutrients are lost and spread into the environ- (NaNO3) and sodium chloride (NaCl) were procured from Sigma-
ment due to numerous physicochemical processes (Solanki et al., Aldrich. Urea (NH2CONH2) was supplied by local fertilizer com-
2015, Lubkowski 2016). This drives these minerals and their pany while hydrochloric acid (HCl) was prepared by Pakistan
byproducts to spread all across the environment, harming the Council of Scientific and Industrial Research Laboratories Complex,
quality of soil and water as well as accelerating global warming Lahore, Pakistan. Distilled water was used throughout the study.
(Six et al., 2004).
In addition to that crop rotation is another practice that is fre-
2.2. Synthesis of biochar nano-fertilizer (BNF)
quently adopted by the farmers to address the supply and demand
imbalance. This has not only resulted in nutrient deprived soil as
Two-step approach was adopted for the synthesis of BNF, in
well as nutritionally weak crops. To make up for nutritional inad-
first step the biochar was prepared and in second step the prepared
equacies, extensive chemical fertilizers are used, which appears
biochar was doped with macronutrients.
to be a curse in disguise (Mura et al., 2013). Globally, the use of fer-
tilizers is fast rising in order to enhance agricultural productivity
which starting in 2014, the world’s fertilizer usage is growing at 2.2.1. Synthesis of banana peel biochar (BPBC)
a rate of 1.8 percent annually (Lubkowski 2016). Hence, there is A conventional approach was utilized to synthesize biochar.
a need to design practices that not only helps in enhancing crop Banana peels were washed with tap water to get rid of any dust
yield but also promote reduced used of these fertilizers. and impurities followed by their slicing into small pieces and air
In this regard, biochar use is considered beneficial by many drying under sunshade. The dried peels were grinded using home
researchers which prove that addition of biochar to soils can blender and resulting powder was pyrolyzed at 600⁰C for 6 h under
improve soil condition and boost nutrient retention which conse- inert atmosphere. After carbonization, the contents were allowed
quently leads to enhanced nutrient usage efficiency (Güereña to cool down to room temperature while keeping the nitrogen sup-
et al., 2013). Following heavy rainfall or irrigation, soil frequently ply intact. The resulting powder was sieved through 100 mesh
loses nitrogen to groundwater in the forms of ammonium (NH+4) sieve and then treated with 1 N HCl for 3–4 h while maintaining
and nitrate (NO–3). This nitrogen shedding mechanism taints the temperature of reaction vessel at 60-70⁰C. The contents of
groundwater and other bodies of water, which leads to eutrophica- flasks were filtered and resulting residue was washed with distilled
tion. According to reports, applying biochar decreased nitrogen water till washings are neutral to pH paper. The material was again
leaching by 23.1% to 32.4%. However, there are conflicting reports grinded after oven drying at 105 °C. The biochar (BPBC) yield was
regarding how adding biochar to soil impacts the drainage of inor- calculated using Eq. (1) (Table 1).
ganic nitrogen (Sun et al., 2018). Higher biochar treatment rates
without fertilizer result in higher NH+4 loss, but controlled biochar 2.2.2. Synthesis of biochar-based nano-fertilizer (BNF)
application with regulated fertilizer resulted to reduced NH+4 loss, Simple impregnation approach was adopted to prepare biochar
as per studies (Teutscherova et al., 2018). Moreover, modified bio- nano-fertilizer (Lateef et al., 2019). For the purpose, 5% solution of
char that are loaded with nutrients can further facilitate reduction salts of macro-nutrients (NH2CONH2, NaH2PO42H2O, and K2SO4)
in nutrient losses and volatilization by linking nutrient delivery to as source of N, P and K were prepared in distilled water followed
time,environmental factors and coordinating the nutrient release by their addition into the suspension of biochar in distilled water
with crop uptake. In addition to that nano-fertilizers improve (50 g/L). The mixture was agitated for three hours followed by
nutrient consumption effectiveness and yield while minimizing overnight stay. The resulting nanocomposite was then vacuum fil-
fertilizer application rates and minimizing soil pollution (Naderi tered, dried in oven at 105 °C, finely powdered using homogenizer
and Danesh-Shahraki 2013). In this context, different loadings of and stored in air-tight jar till used.
nutrients of choice were done on biochar matrix derived from var-
ious sources like corncob (Lateef et al., 2019), sugarcane residues 2.3. Characterization
(Borges et al., 2020), animal waste (Chen et al., 2018), poultry
waste (Lustosa Filho et al., 2020), wheat residues (Sun et al., The proximate and physical parameters of BPBC and BNF were
2021), grape marc (Ferjani et al., 2020), saw dust (Gwenzi et al., determined using standard methods i.e. moisture (ASTM E871-
2018) etc. targeted to slowly provide nutrients to the plant for 82), Ash (ASTM D1102-84), Volatile organic matter (ASTM E872-
ensuring their enhanced growth. In addition to slow-release, these 82), fixed carbon calculated by difference, pH (ASTM D4959-00),
slow release nanofertilizers improve soil health and fertility, conductivity (ASTM D1125-14), bulk and tap densities (ASTM
sequester carbon and reduce greenhouse gas emissions. Further D2854-70), Methylene blue (MB) value (ASTM C1777-15) and
the utilization of these waste materials and their conversion into ash content (ASTM D2866-70).
value added materials helps in resolving the problems of waste The prepared materials were characterized by using different
management and environmental impacts (Gwenzi et al., 2018). techniques. ATR-FTIR was performed on Thermo Nicolet spectrom-
The objective of current study is focused on 1) Exploration of eter over a range of 600–4000 cm
1 to determine the functional
banana peel biochar, a potential agro-waste, as potentially eco- groups present in the prepared NC. SEM images were obtained
nomically feasible alternative fertilizer; 2) effectiveness of sources using Nova NanoSEM 450 to evaluate surface characteristics, parti-
of N, P, K when used in slow-release setup based on biochar, 3) cle size and particle distribution. Elemental composition was
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Table 1
Formula and description of parameters used for calculating nano-fertilizer characteristics and its impact on plant germination and growth.

Eq. Parameter Formula Symbols description Ref

No.
1. Biochar Yield (Y) M
M Mc = weight of biochar after pyrolysis (kg) (Ronsse
Y ¼ Mdry;b
c

M ash;b  100
ash;c

Mdry,b = weight of oven-dried raw biomass (kg) et al.,

Mash,c = ash content in biochar 2013)
Mash,b = ash content in raw materials
2. Salt Index (SI) SI ¼ rrNC
SN
rSN = NaNO3 conductivity (He et al.,
rNC = BNF conductivity 2007)
3. Swelling ratio (SR) SR ¼ WsW
W
d
d Ws = Wet sample weight (He et al.,
Wd = Dry sample weight 2007)

Wd
4, Equilibrium water EWC ¼ WsWs
X 100 Ws = Wet sample weight (He et al.,
content (EWC) Wd = Dry sample weight 2007)
5. Water absorption WAR ð%Þ ¼ ðW3W
W
1
2Þ
X100 W1 = Sample Weight (Hamid
rate (WAR) W2 = Sample + Petri dish Weight et al.,
W3 = Weight of sample + petri dish after 5 days 2013)
6. Time for 50 % ðN2
niÞðtj
ti Þ N = Final number of seeds sprouted (Farooq
T50 ¼ ti þ ðnj
ni Þ
Germination, T50 nj and ni = reflects the total number of seeds that have successfully sprouted by et al.,
equivalent counts of times i.e., tj and ti, respectively, when ni < N/2 < nj. 2005)
7. Germination GI ¼ GS
Days of first count
þ    þ Days of final
GS
count
GS = No. of germinated seeds (Farooq
index, GI et al.,
2005)
8. Final germination FGP ð%Þ ¼ GS
TS X 100
GS = No. of germinated seeds (Farooq
percentage, FGP TS = Total no. of seeds et al.,
2005)
P Dn
9. Mean MGT ¼ D = Number of days counted from the start of germination (Farooq
n
Germination time n = no. of seeds germinated on day D et al.,
(MGT) 2005)

determined using EDX (Nova) by spreading powdered samples on 2.8.1. Slow-release studies in water
carbon tape and subsequently positioning them on aluminum One week of column experiments were conducted to assess the
studs. pattern of nutrient release of BNF in water. In order to avoid col-
umn fracture, the test was conducted in a glass column (3000 x
2.4. Salt index (SI) 0.500 ) carefully filled with tap water followed by addition of 5.0 g
of BNF. The system was allowed to stay for 24 h, after which
Sodium nitrate (NaNO3) and BNF were weighed out (1.0 g) sep- 25 mL of water was collected and volume of the column was recon-
arately in two beakers which were then filled with 200 mL of dis- stituted to 50 mL with tap water. The similar protocol was adop-
tilled water. After 24 h, the conductivities of the solutions (rSN and ted over the span of seven days and collected effluent was
rNC) were measured using a conductivity meter (Hanna 5211). Salt evaluated for the presence of nitrogen, potassium, and phosphorus
index was calculated by using Eq. (2) (Table 1) (He et al., 2007). in order to determine the delivery of nutrients from the BNF
(Jamnongkan and Kaewpirom 2010).
2.5. Swelling ratio (SR)
2.8.2. Slow-release studies in soil
During the 2-week column investigation, 400 g of well homog-
SR (Eq. (3), Table 1) was determined by suspending BPBC (1.0 g)
enized sieved soil and 10 g of BNF were placed inside a glass col-
and BNF (1.0 g) in distilled water (200 mL) for a period of 24 h at
umn (6200 x 500 ). The soil in the column was saturated with
room temperature. The mixture was filtered employing pre-
180 mL of tap water. For the period of trial, 50 mL of water was ta-
weighted sintered crucible (He et al., 2007).
ken from the column after every 24 h. To maintain a consistent
moisture level, the column was refilled with 100 mL of water.
2.6. Equilibrium water content (EWC) The sampled water was evaluated for nutrients contents to deter-
mine their release behavior from prepared BNF in the soil. A very
EWC was calculated by using Eq. (4) (Table 1) by performing the similar approach was used for the 400 g soil sample used as exper-
same protocol as mentioned in section 2.2 (He et al., 2007). imental blank (Kottegoda et al., 2011).
The samples collected in the aforementioned studies were eval-
2.7. Water absorbance rate (WAR) uated for K1+, NO1- 3-
3 , and PO4 contents using the Flame Photometer
Tenway PSP7, Holand, and Ion Selective Electrode 930,
For investigations on water absorption, BPBC and BNF (1.0 g respectively.
each, labelled as W1) were placed in pre-weighted Petri plates
(W2). The samples’ capacity to absorb water was determined using 2.8.3. Kinetic studies on slow-release studies
Eq. (3) by placing these petri dishes in a desiccator for five days in a Four kinetic models i.e., zero-order (Eq. (10), first-order (Eq.
moist environment, then weighing them (W3) (Hamid et al., 2013). (11), Higuchi (Eq. (12) and Korsmeyer-Peppas (KP) (Eq. (13) were
The results are calculated by employing Eq. (5) (Table 1). applied to the slow-release data in both water and soil (Kareem
et al., 2021, Mohamed et al., 2022).
2.8. Slow-release studies Q t ¼ K0t ð10Þ

To ascertain the trend of nutrient leaching, two different slow- Q t ¼ Q o e k1 t ð11Þ

release investigations were carried out i.e., in soil and water. The
tap water used in the study was previously analyzed for N, P and pffiffi
Q t ¼ KH t ð12Þ
K contents and these values were used as blank.
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M 3. Results and discussion

¼ K KP t n ð13Þ
M1
3.1. Synthesis of BNF
where, Qt and Q0 are nutrient released at time t and available in the
matrix initially, respectively. K0, K1, KH and KKP are the constants for Pyrolysis technique was employed to synthesize BPBC, which
zero-order, first-order, Higuchi and KP, respectively. was then used to make BNF via simple nutrient impregnation (N,
P and K). Considering the fact that biochar is characterized by
highly porous network (Atinafu et al., 2021), simple adsorption of
the nutrients into its porous channels can lead to their loading
2.9. Germination studies and involving simple physical or chemical forces to bind these
nutrients into the matrix (Ding et al., 2016). Additionally, biochar
The experiment was conducted to evaluate and compare the is proven to be candid materials for improving soil properties
effects of BNF with those of conventional fertilizer. Cucumber, (Ding et al., 2016, Igalavithana et al., 2016) and their long network
broccoli and red okra seeds were chosen for evaluating the impact channels can facilitate slow release of nutrients into the soil, hence
of prepared BNF. Fully randomized procedures were used to the current studies have chosen the agro-waste biochar to act as
administer the six different treatments, which are as follows: support of nutrients. Depending on the porosity, adsorption rate,
T1 = Blank (only soil); T2 = Control (Urea (10 kg/acre = 24.71 kg/ and binding capacity or impregnation level, these nutrients will
ha)); T3 = Biochar (10 kg/acre = = 24.71 kg/ha); T4 = Nanocomposite be released from BNF. The BPBC was pyrolyzed at 600⁰C as higher
(10 kg/acre = 24.71 kg/ha); T5 = Nanocomposite (15 kg/acre = 37. temperature facilitates complete carbonization (Mopoung 2008) as
515 kg/ha); T6 = Nanocomposite (20 kg/acre = 49.42 kg/ha). well as uptake of more nutrients as also confirmed by previous
Two sets of experiments were performed in green-house set- studies (Yao et al., 2012).
tings to check the effect of various treatments applied on the The biochar yield obtained in this case is around 13%, which is
sprouting and germination of selected vegetables (Cucumber, broc- in line with previous studies that state that higher pyrolysis tem-
coli, red okra) with controlled conditions of temperature (⁰C), perature results in reduced biochar yield (Ronsse et al., 2013)
humidity (%rh) and day and night hours (12/12). The experimental which in turn impacts the ratio of volatile to fixed carbons and
unit (plastic trays and petri dishes) used in the experiment were total carbon content present in the biochar.
washed with distilled water to remove any contaminants and soil Biochar based fertilizers have the ability to retain the nutrients
was sterilized at 102⁰C in autoclave prior to use in experiments. in the soil and hence impacting their leaching and enhanced avail-
ability to the plants. This indirect nutrient value of the biochar
facilitates the plants’ growth and can also improve the soil quality
2.9.1. Petri dish experiments by removal of various soil constraints that limit the plant growth.
Each petri dish (94 mm) was prepared by placing two Whatman The high N content of these biochar based nanofertilizers helps in
filter paper in it. The filter papers were wetted with approx. 5 mL of improving the soil organic carbon content (Chan and Xu 2012).
distilled water followed by sprinkling of fertilizer homogenously
dispersed /mixed in 5 mL distilled water. The seeds (10/ petri dish) 3.2. Physical and proximate parameters
were placed in petri dish in well dispersed manner and covered
with lid. The seeds were considered sprouted when radicle pro- The physical and proximate parameters i.e., moisture, ash, vola-
truded is 2 mm. The measurements of root length were done on tile organic carbon, fixed carbon, bulk density, tap density, pH, and
daily basis for a period of 14 days and results are reported as aver- conductivity of BPBC and BNF were evaluated and resulted are
age of three replicates. summarized in Table 2.
As observed from the data tabulated in Table 2, there is slight
decrease in the pH of BNF as compared to BPBC owing to doping
2.9.2. Seedling trays experiments of salts. Introduction of the ions into biochar porous structure
50 holes seedling trays were utilized in this experiment. Each has slightly increased its conductivity from 518.23 to 566.27lS
hole was filled with approximately 14 g soil followed by sowing cm
1. Small increase in the moisture value of BNF was also noticed
of seeds (1 in each hole) and filling of top 2-inches with 1.0 g soil resulting from the retention of some moisture owing to presence of
mixed with known weight of the fertilizer (applied based on treat- salts introduced as well as increase in hydrophobicity of the char-
ments i.e., urea, BPBC, BNF). The holes were daily irrigated with 1– coal. Volatile organic carbon and fixed carbon are basically depen-
2 mL water or as per requirement. To determine germination dent on the pyrolysis temperature, usually higher temperatures
indices, seed sprouting was monitored daily and shoot lengths yield biochar with enhanced amount of fixed carbon and less vola-
were recorded for a period of 14 days. The data was collected in tile content (Enders et al., 2012, Ronsse et al., 2013). There is a
replicates and reported as average. small increase in volatile organic carbon and decrease in fixed car-
Following parameters were calculated from the germination
data: Time for 50 % Germination, T50 (Eq. (6), Table 1), Germination Table 2
index, GI (Eq. (7), Table 1), Final germination percentage, FGP (Eq. Proximate and Physical Analysis of BPBC and BNF.
(8), Table 1), Mean germination time, MGT (Eq. (9), Table 1)
Parameters BPBC BNF
(Zinzolker et al., 1985, Farooq et al., 2005, He et al., 2007, Hamid
Biochar yield (%) 13.3 –
et al., 2013).
Moisture Content (%) 2.62 4.60
Ash (%) 3.42 4.37
Volatile Organic Carbon (%) 8.44 9.28
Fixed Carbon (%) 83.79 80.41
2.10. Statistical analysis Bulk density (g m
3) 3.2e-4 3.6e-4
Tap density (g m
3) 1.93e-3 2.34e-3
The replicate measurements were taken and data is presented pH 7.96 6.24
as mean ± S.D (standard deviation) using MS Excel and Origin- Conductivity at 25 ℃ (lS cm
1) 518.23 566.27
MB value 61 66
Pro 8.
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bon after doping of biochar, which again is linked with increased dispersed all over the biochar surface indicating homogeneous
content of dopants in BNF. Availability of the high fixed carbon doping of the ions onto the biochar surface.
(80% in current case, Table 2) is termed as ‘‘major currency of soil Fig. 2 provides the details of EDX spectra and analysis for BPBC
system” as it governs the microbial activity in the soil (Kibblewhite and BNF. The BPBC is majorly composed of C with some traces of Si
et al., 2008), hence such a trait is deemed as a positive aspect of the and S. The presence of Si is typical of the banana peel charcoal as
developed biochar. Bulk density, tap density and ash content of the also confirmed by previous studies (Mopoung 2008). EDX analysis
BNF all show slightly higher value than the BPBC which can be of BNF (Fig. 2d) affirmed the doping of N, P and K in BNF. The wt%
attributed to doping of nutrients into the biochar. MB value, an of P doping is less than that of the N and K which is in line with the
indication of porosity or adsorption capacity of the biochar, is previous studies that states that binding capacity of biochar is high
noticed to increase slightly surprisingly, as doping of BPBC should for nitrate and low with phosphorus (Ding et al., 2016).
decrease the uptake capacity of biochar (Lateef et al., 2019) hence,
it is deduced that the incorporation of the nutrients facilitates
development of more adsorption sites into the biochar porous 3.5. Salt index
structure resulting in high MB value.
Fertilizer burn is a common condition resulting in huge losses to
the farmers owing to seedling and germination injury. SI is a mea-
3.3. FT-IR sure of osmotic pressure induced by fertilizer when compared with
sodium nitrate. It is an indication of ions released into the soil upon
FTIR spectra of BPBC and BNF are contrasted in Fig. 1.Hydroxyl fertilizer application and hence enhancing the probability of the
ion bridging, or moisture incorporated into the porous structure of damage to crop (Laboski 2008, Gowariker et al., 2009); conse-
biochar are two main factors that contribute to the peak at quently higher the SI potential higher the chances of crop damage.
3353 cm
1 in biochar (BPBC) spectra, which is in line with the find- In terms of electrical conductivity, the allowable range for SI
ings of physical parameters (section 3.1.1). Peaks at 2920 and is<2 mmhos/cc (2000lS/cm), which in current case comes around
1703 cm
1, respectively, indicate the stretching of CAH ring owing 0.087 mmhos/cc (87lS/cm) indicating that the prepared fertilizer
and carbonyl group (C@O). Small intensity peaks also appear (BNF) is safe for crops and can promote better yield of crops
around 1521, 1442, 1204 and 1160 which are attributed to cellu- (Gowariker et al., 2009).
lose CAH bending as well as C@N. The peaks 1026 and 659 cm
1
are assigned to hydrogen bonds in cellulose and CAH bonds in aro-
matic ring in lignin (Yousaf, 2015, Mopoung and Udeye 2017). 3.6. WAR, SR and EWC
Almost similar trend is observed for BNF which showed minor shift
in in peaks (3344, 2921, 1725, 1520, 1447, 1370, 1234, 1159, 1025, Another important aspects of fertilizer are WAR (Wu et al.,
890 and 656 cm
1) or changes in their intensity which can be 2008), SR (Bortolin et al., 2013), and EWC (He et al., 2007) which
attributed to interaction of biochar with the doped ions. are all necessary for the slow release fertilizer to perform well.
The experimental values for BPBC and BNF for WAR, SR and EWC
are 53%, 3.32 g g
1, 78.81% and 68%, 3.64 g g
1, 78.97% respectively.
3.4. Sem/edx All the three values showed improvement in the case of BNF as
compared to BPBC. This increase in water holding capacity is a pos-
The micrographs of BPBC and BNF (Fig. 2) were acquired to get itive planting potential attribute of the fertilizer as it helps in pro-
insight into the morphology of synthesized samples. SEM of bio- viding moisture to plants on slow-release basis thereby reducing
char showed a typical structure with some grooves and channels the need for excessive irrigation. In addition to that such qualities
(Sial et al., 2019) that promote high uptake and incorporation of also pose added advantage of being useful especially in areas
ions into the structure. Pulverization and higher pyrolysis temper- where there is water shortage. In some aspects the water absorp-
ature impacted the main channel structure promoting appearance tion in the fertilizer is related to nutrient release pattern of the
of rough structure with more sites to facilitate cation and anion slow release fertilizers by facilitating their dissolution and leading
exchange. Similar pattern is observed in case of BNF (Fig. 2b), with to their release from pores and channels of the biochar (Trinh and
some white dots or pattern (average particle size 59.8 nm) seen KuShaari 2016). Additionally, the presence of moisture makes it

Fig. 1. FTIR spectra of banana peel biochar (BPBC-orange) and biochar-based nano-fertilizer (BNF-blue).

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O.F. Tarar, A. Asghar, S.A. Qayyum et al. Journal of the Saudi Society of Agricultural Sciences 22 (2023) 535–545

Fig. 2. SEM micrographs (a & b) and EDX analysis (c& d) with elemental composition in the inset of BPBC and BNF, respectively.

easier for crops to have consistent access to nutrients (Wu et al., the soil (Atinafu et al., 2021). Furthermore, early seed sprouting,
2008). and plant germination were aided by the availability of high nutri-
tional content from the outset, allowing for the establishment of
3.7. Slow-release studies healthy plants. The delivery of nutrients from a porous fertilizer
is influenced by the porosity and chemical composition of the
Slow release of nutrients is a very important expect of fertiliz- nutrients (Khan et al., 2008, Lateef et al., 2019).
ers, as it determines the release behavior of the nutrients and Hence, when compared to traditional fertilizers, the observed
hence their availability to plants. The data acquired from indepen- patterns can help in maintaining the supply of nutrients to plants
dent studies performed in tap water and soil is presented in Fig. 3. as needed and reducing nutrient leaching. Due to its large surface
According to the literature, these kinds of investigations are a kind area, porosity, and physiochemical binding, biochar is able to
of approved method for establishing fertilizer compatibility for a absorb nutrients, resulting in reduced nutrient leaching and
crop (Pereira et al., 2012, Costa et al., 2013). The data obtained con- improved plant development (Hunt et al., 2010, Steiner and
firms regular provision of specific nutrients to plants and their pre- Harttung 2014). These and other factors support the use of biochar
cise release from fertilizer on incremental basis in water as well as to improve soil fertility and spur plant growth. Thus, the BNF’s ini-
soil. The release of nutrients in case of tap water studies showed a tial delivery can promote seed germination, which in turn
regular pattern leading to fast release of the three nutrients in the enhances the right number of plants per unit area, plant develop-
water system which afterwards slows down over time (Fig. 3). This ment, and eventually yield.
kind of trend favors plant growing potential of the prepared fertil- The mechanism of slow-release of nutrients can be explained in
izer since soil enriched with nutrients facilitates germination fol- context with voids, pores and channels of the charcoal. The water
lowed by growth of the plant. Among the three nutrients, release in the soil system penetrates the BNF leading to its absorption by
of all the nutrients though starts in 24 h but release pattern the biochar (as affirmed by water absorbency studies) followed
showed the release % of nitrate is more than that of phosphate by establishment of dynamic exchange between water in BNF
which in turn is greater than potassium which again favors the and in soil. Water enters the biochar pore structure followed by
prepared fertilizer as high concentration of N promotes start of channels inside it leading to release of nutrients firstly from the
germination (Zhang et al., 2020). exposed points available on the surface and then inside the chan-
The same pattern was observed in 14-day nutrient release stud- nels that occur deep down the pore. Water available in the biochar
ies in soil (Fig. 3) with the exception that proportion of nutrients is now equipped with soluble nutrients released from the biochar
released in soil is less than that in water owing to higher solubility surface which then release into the soil by dynamic exchange
of nutrients in 100% water media as compared to soil–water sys- (Wu et al., 2008, Lateef et al., 2019).
tem. These results are consistent with earlier research, and the The application of kinetic models to the slow-release data of
observed pattern guarantees continuous nitrogen delivery to water and soil (Fig. 4) and the fitting parameters obtained in this
plants, preventing leaching losses that are typical of conventional regard are presented in Table 3. It is evident from the R2 value that
fertilizers (Costa et al., 2013). Earlier studies have shown that the best fit model in the case of water slow-release studies for N
water-soluble NPK compound fertilizer (conventional) is fast to comes out to be zero-order while for P and K KP model hold good.
enter into soil system due to its high solubility in the water, hence For soil release studies, the KP model is suggested to be the best fit
it becomes easily exhausted from the soil as soon as it is added to model for all the three nutrients. The zero-order model indicates

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O.F. Tarar, A. Asghar, S.A. Qayyum et al. Journal of the Saudi Society of Agricultural Sciences 22 (2023) 535–545

Fig. 3. Slow-release studies performed for BNF nutrient (P2O5, NO-1

3 , K2O) release behavior in water (a, b, c) and soil (d, e, f).

towards mass transport of nutrients occurring due to diffusion of tively indicating the higher potential of prepared fertilizer to grow
water and bioactive species. The applicability also suggests that vegetables. Among BNF treatments (T4-T6), the highest GI was
the stability of matrix that release nutrient from the matrix with- recorded for T5 in all the three vegetables, while among the veg-
out degrade (Ibahati et al., 2014). KP model is explained on basis of etables highest GI was recorded for broccoli as compared to
‘n’ value which is when below 0.45 refers to Fickian nutrient cucumber and red okra.
release model, when ‘n’ is between 0.45 and 0.89 the model refers In case of FGP (Fig. 5b), significant effect was observed in all the
to non-Fickian mechanism and when ‘n’ is>0.89 the model indi- three vegetables of the treatments applied. Compared to the blank,
cates nutrient release by following the non-Fickian release or Type FGP was enhanced 16.61, 33.27 and 50.02% in case of T2, T3 and T4
II mechanism (Hermida and Agustian 2019, Ahmad et al., 2023). for studies carried out on cucumber. For broccoli and red okra, the
increase recorded for these treatments (T2, T3 and T4) is 14.28,
3.8. Germination studies 28.58.42.86% and 20.02, 40.01, 60.01%, respectively. The highest
impact of application of BNF wasobserved for red okra followed
3.8.1. Germination indices by cucumber. As observed that there is quiet an increase in FGP
The influence of urea, a conventional fertilizer, BPBC and BNF on for simple biochar employed, which showed that application of
germination traits (T50, FGP, GI and MGT) of cucumber, broccoli biochar promoted soil health as well as provision of nutrients to
and red okra seeds are contrasted in Fig. 5. As evidenced from the plant that are already available in the soil (Ding et al., 2016).
the bar graph, in all the three cases germination indices of BNF The provision of additional nutrients by use of BNF further facili-
treatment (T4-T6) recorded improvement as compared to T1, T2 tated growth and promoted sprouting and germination. When
and T3. compared among different BNF treatments (T4-T6), the highest
GI (Fig. 5a) depicts the percentage and speed of germination, positive impact was recorded for the T5 after that there is a small
hence higher value defines better germination rate of the fertilizers decrease in FGP hence the optimized dose of BNF is considered to
under study (Zinzolker et al., 1985). For control (T2) and equivalent be the one used in this treatment.
dose of BNF (T4), the values recorded for GI are 3.42, 4.24, 2.84 and For remining two parameters i.e. T50, MGT (Fig. 5c&d), lower the
5.53, 5.77 and 4.24% for cucumber, broccoli, and red okra, respec- time required better is the impact of fertilizer on germination

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O.F. Tarar, A. Asghar, S.A. Qayyum et al. Journal of the Saudi Society of Agricultural Sciences 22 (2023) 535–545

Fig. 4. Kinetic models application to the nutrient slow-release study in water and soil.

Table 3
Fitting parameters of the slow-release study of nutrients in water and soil.

Kinetic model Parameter Water Soil

N P K N P K
Zero-order R2 0.8949 0.9441 0.5782 0.9512 0.8877 0.9787
K0 0.0065 0.0035 0.0022 2.7e-4 1.5e-4 0.0019
Higuchi R2 0.7084 0.7885 0.9642 0.7589 0.9544 0.7420
KH 0.0687 0.0377 0.0251 0.0041 0.0023 0.0287
KP R2 0.8991 0.9450 0.9946 0.9661 0.9788 0.9979
N 1.2645 1.1858 0.3541 1.2550 0.6519 1.239
KKP 0.0018 0.0014 0.0496 6.7127 0.0010 5.2e-4

(Zinzolker et al., 1985). In current case the time acquired to reach N contents that in some cases have reported to reduce the germi-
germination for BNF (for both parameters) is comparatively less nation (Zhang et al., 2020) or may be due to higher ratio of biochar
than that of T2 which recorded delay. For T50, time required by to soil that can lead to sequestering of nutrients from the soil–wa-
BNF (T4) to germinate 50% seeds is almost 16, 2 and 10% less than ter system rather than leaching (Ding et al., 2016).
that of T2 for cucumber, broccoli and red okra. Even simple biochar Germination indices demonstrated highly significant variation
(BPBC) took smaller number of days to grow 50% of the seeds. Sim- of FGP at p < 0.001, GI at p < 0.001and MGT at p < 0.001 for three
ilar findings were recorded for MGT or Emergence time (Zinzolker vegetable crops (Table 4). Except for T50 (p > 0.05) revealed non-
et al., 1985), for which there was a lapse of 2–3 days to result in significant variation among three vegetable crops. While overall
germination of seeds leading to reduction in time for cucumber, impact of conventional and BNF fertilizer treatments showed sig-
broccoli and red okra by approximately 10.23, 4.48 and 9.36% for nificant variation for all germination indices. As FGP, GI showed
BNC (T4). Among the BNF treatments, there is decrease in T50 as high significant variation at p < 0.001, while MGT demonstrated
well as MGT as the applied dose increase from 10 to 15 kg/acre the significant variation at p < 0.01 and T50 indicated the signifi-
but with further enhancement in dose, decrease is recorded in both cant variation at p < 0.05 for all six fertilizer treatments.
the parameters, posing that higher concentrations can lead to 3.8.2. SOV = source of variation; DF = degree of freedom; *** = highly
reduction in germination rate probably owing to release of higher significant at p < 0.001; ** = significant at p < 0.01; * = significant at

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Fig. 5. Germination indices observed after application of different treatments T1-T6 among the three vegetable crops (Cucumber, Broccoli, Red Okra).

Table 4
Analysis of variance (ANOVA) for root, shoot length and germination indices among
treatment (T4-T6) indicated significant longer root and shoot
three vegetable crops grown under six treatments.
length compared to T1-T3. T5 was observed to have highest root-
SOV Crops Treatments shoot lengths while the shortest lengths were observed for blank
DF 2 5 and biochar (Fig. 6).
Root length 7.13*** 2.47*** In case of cucumber, as per average data collected from all the
Shoot length 112.11*** 4.81*** seeds employed, there is almost 200–300 % increase in root length
T50 0.32ns 0.83*
FGP 416.4*** 729.2***
of the seeds for BNF (T4-T6) as compared to that of T2 on day 4
GI 2.83*** 5.79*** when all the applicable treatments showed sprouting of roots. In
MGT 0.53*** 0.82** case of BNF treatments, the highest growth was recorded for T5
as compared to T4 and T6. Similar results were recorded for root
heights of broccoli and red okra which showed increase of 122–
p < 0.05; ns = non-significant at p > 0.05.Growth parameters (Root- 155% and 34–85% as compared to urea with longest roots obtained
shoot length). in case of T5.
Three vegetables including: Red okra, cucumber, and broccoli For shoot lengths, the trend analysis of data (Fig. 7) depicted
were used to study the impact of BNF application on root-shoot similar results, showing increase of 9–27, 18–36 and 8–16% for
lengths of the plants. Analysis of variance were performed to esti- cucumber, broccoli and red okra on day 4 when compared to T2.
mate the variation of root and shoot length among three vegetable The recorded lengths on Day 14 for T5 (optimized dose) for the
crops (Table 4). Shoot and root length demonstrated highly signif- three vegetables are 12, 28 and 23% in comparison to T2. For sim-
icant variation at p < 0.001 for three vegetable crops. While overall ple biochar (T3), there was indeed increase in germination param-
impact of conventional and BNF fertilizer treatments also showed eters, but growth of both root and shoot length was little
significant variation at p < 0.001 for all growth traits. These results hampered as compared to treatment T2 showing that supply of
suggest the significant impact of conventional and BNF fertilizer NPK promotes growth of plant and constant supply as in case of
treatment on plant growth. prepared slow-release fertilizer (BNF) the plant growth is facili-
The control medium (T2) demonstrated better shoot and root tated as the nutrients remain available to the plant rather than
growth than blank (T1) and biochar medium (T3). Overall BNF being lost through leaching as in case of conventional treatments.

Fig. 6. Effect of treatments (T1-T6) on root and shoot length among the three vegetable crops i.e., Broccoli, Cucumber, Red Okra.

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Fig. 7. The impact of treatments on root and shoot length of different vegetables used in the study.

4. Conclusion Acknowledgment

The banana peel biochar-based nano-composite is introduced The authors (OF and AA) like to acknowledge the efforts of all the
as a potential environmentally friendly slow-release fertilizer hav- technical staff of Pakistan Council of Scientific and Industrial Research
ing doping of N, P and K. The prepared material as characterized by who facilitated in successful completion of the research work.
FTIR, SEM and EDX is observed to contain various functional groups
and have typical structure of biochar with grooves and channels
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