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Deashed biochar as N-carrier extended the N-release by inhibiting N-losses

in calcareous soils

Article in Biomass Conversion and Biorefinery · April 2023

DOI: 10.1007/s13399-023-04250-5

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Biomass Conversion and Biorefinery
https://doi.org/10.1007/s13399-023-04250-5

ORIGINAL ARTICLE

Deashed biochar as N‑carrier extended the N‑release by inhibiting

N‑losses in calcareous soils
Muhammad Rashid1,2 · Qaiser Hussain1 · Rifat Hayat1 · Mukhtar Ahmad3 · Muhammad Azeem1 · Sarosh Alvi2 ·
Arshad Nawaz Chaudhry1 · Sajid Masood4 · Rabia Khalid1 · Sarvet Jehan1 · Obaid ur Rehman2

Received: 17 January 2023 / Revised: 17 April 2023 / Accepted: 19 April 2023

© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2023

Abstract
Recently, biochar has been tested as a nutrient carrier for synthesizing slow-release fertilizers. But, such slow-release fertilizer
exists which is designed specifically for alkaline calcareous soils. Biochar adsorbs/complex large quantities of nutrient ions
due to extensive surface area, porosity, and surface functional groups. In addition, the indigenous properties of biochar can
be tailored for specific use. Therefore, in this study, the emphasis was given to formulate a designer slow-release nitrogen
fertilizer by modifying biochar by deashing to suit the alkaline calcareous soils since such soils are prone to heavy nitrogen
losses. The acacia wood (Acacia Arabica L.) biochar was made and deashed with 0.1 M HCl. Then, raw and deashed biochar
was characterized to evaluate the changes in pH, CEC, ash contents, volatile matter, fixed-C, surface area, pore volume,
surface morphology, mineral structure, and surface functional groups after deashing. Biochar-based slow-release nitrogen
fertilizer (BSRNF) was synthesized by impregnating the urea onto biochar while starch and polyvinyl alcohol were used
as binders. The effect of BSRNF on N release, N ­ H3-volatilization, ­NO3-leaching, and ­N2O emission was examined in two
different soils compared to conventional urea. It was found that deashing significantly modified the properties of biochar
which favored urea sorption onto biochar which was confirmed by SEM images, XRD patterns, and FTIR spectra of raw and
deashed biochar. The evaluation of BSRNF in two different alkaline calcareous soils showed that N release was extended
up to ≥ 60 days. Consequently, BSRNF, compared to conventional urea, significantly decreased the N ­ H3-volatilization up to
38.09%, ­NO3-leaching up to 49.66%, and N ­ 2O-emission up to 52.39% of applied N. The BSRNF significantly delayed the
nitrogen release in soil, resulting in decreased nitrogen losses compared to conventional urea. The mechanism behind this
was the sorption of nitrogen onto biochar which was further enhanced by deashing. The deashing also made biochar suitable
for alkaline calcareous soils. In addition, the application rate of biochar has also economized.

Keywords Slow-release fertilizer · Biochar · Deashing · Ammonia volatilization · Nitrate leaching · Nitrous-oxide
emission · N release · Alkaline calcareous soils

1 Introduction

Nitrogen (N) is the most limiting nutrient in the soil–plant

system mostly because of the rapid hydrolysis of N fertiliz-
* Qaiser Hussain ers. The crop plants are, therefore, unable to absorb a sig-
abuxeneb@gmail.com
nificant portion of applied N. Consequently, excess N from
1
Institute of Soil and Environmental Sciences, PMAS-Arid the root zone is lost into the environment in the forms of
Agriculture University, Rawalpindi, Pakistan ­NH3-volatilization, ­NO3-leaching, and N ­ 2O emissions [1].
2
Soil and Water Testing Laboratory for Research, Rawalpindi, The alkaline calcareous soils which occupy one-third of
Pakistan total cultivated lands are more prone to these losses [2]. The
3
Department of Agronomy, PMAS-Arid Agriculture mechanisms behind higher losses of N fertilizers in alkaline
University, Rawalpindi, Pakistan calcareous soils are low cation-exchange-capacity (CEC)
4
Department of Soil Science, Faculty of Agricultural Sciences and soil organic matter (SOM), and high soil pH and tem-
and Technology, Multan, Pakistan perature [3]. Unfortunately, limited research work has been

13
Vol.:(0123456789)

reported to combat the N losses under alkaline calcareous
soils. Nevertheless, nitrogen use efficiency (NUE) in such
soils is declining and reported as low as 15–23% compared
to non-calcareous soils [4]. Slow-release fertilizers (SRFs)
have marked their significance to improve NUE considerably
[5]. But, the use of SRFs is limited only to high-value crops
because of higher costs since SRFs involve the use of costly
carriers. Therefore, an appropriate carrier for the synthesis
of SRFs needs further exploration to find an affordable and
efficient carrier [6].
The findings of some previous research studies have
advocated that the incorporation of organic amendments to
soil has the ability to counter N losses, viz., ­NO3 leach-
ing [7], ­NH3 volatilization [8], ­N2O emission [9], and also
have tremendous potential to enhance the N retention in soil
[10]. Biochar has become a subject of significant interest
over the past two decades due to its ability to store carbon
(C) for centuries, making it a promising option for long-
term atmospheric carbon removal compared to other tech-
nologies mentioned in the literature [11]. Biochar is con-
sidered the most promising option due to its technological
feasibility, scalability possibilities, cost-effectiveness for C
removal, stability and perpetuity of C storage, verification,
and monitoring methods, as well as the benefits associated
with the various possible C sink applications [12]. A meta-
analysis of 24 studies confirmed the stability of biochar in
soil. It was found that the labile C pool of various biochars
has a mean residence time of 108 days, while the stable
C pool has a mean residence time of 556 years, with each
pool accounting for 3% and 97% of the total C, respectively.
This indicates that only a small percentage of biochar is
bioavailable, while a significant portion contributes to long-
term C sequestration [13]. These findings advocate that a
small quantity of biochar can be used as a nutrient carrier
to formulate SRFs to enhance the benefits of biochar. In
addition, biochar has been used successfully as an N carrier
to formulate SRFs in recent times [14, 15]. But, no such
SRF has been designed for alkaline calcareous soils while
NUE in alkaline calcareous soils is much lower than in non-
calcareous soils and could be enhanced effectively by the
maintenance of soil organic carbon (SOC) [16]. Biochar is
a recalcitrant carbon-based amendment that can stabilize
the SOC otherwise added SOM is mineralized rapidly in
such soils. However, biochar is a costly amendment, and
its heavy recommended doses (10–50 t h­ a−1) are costly for
farmers to apply on a large scale [17]. Secondly, biochar
is mostly an alkaline material and not suitable for alkaline
calcareous soils. However, the properties of biochar can be
tailored for specific use [18]. The beneficial effects of bio-
char are mostly tested in acid tropical soils [19]. The impacts
of biochar may differ in acidic and alkaline soils [20]. There
are many reports that biochar is a potential liming material
for acid soils [21], so biochar can increase soil pH [22],
13
Biomass Conversion and Biorefinery
and increasing the soil pH in calcareous alkaline soils may
reduce the availability of nutrients. Chemical modification
of biochar, therefore, with acids may enhance its adsorption
efficiency and increase surface area [23, 24] and also reduce
the liming effect. Therefore, it was hypothesized that the
deashing of biochar will not only increase the adsorption of
N by enhancing microporosity and surface area [25] but will
reduce the pH of biochar [26] making it suitable for alkaline
calcareous soils. In addition, as an N carrier, the recom-
mended rates of biochar will also be reduced. Previously,
some scientists used biochar as an N carrier [27-29], but no
one used deashed biochar as an N carrier, and no specific
SRF has developed for alkaline calcareous soils yet.
Keeping in view this background it was hypothesized
that the impregnation of urea on acidified (deashed) bio-
char as an N carrier will slow down the urea mineralization
which will reduce the N losses including ­NH3-volatilization,
­NO3-leaching, and ­N2O-emissions.
2 Materials and methods
2.1 Preparation of biochar‑based slow‑release
nitrogen fertilizer (BSRNF)
Acacia wood (Acacia Arabica L.) pieces (4–5 cm) were
used as feedstock for biochar production. After air drying
for two weeks, the feedstock was carbonized in the MRC
Lab Furnace (Model GSM 11–8, UK) at the Institute of
Soil and Environmental Science, PMAS-Arid Agriculture
University, Rawalpindi, Pakistan. The pyrolysis conditions
[30] were set at slow pyrolysis heating steps of 10 °C per
minute, following the Biochar standard of the International
Biochar Initiative [31] until reaching 350 °C of setting tem-
perature with 2 h. After carbonization, the biochar samples
were allowed to cool in the furnace until room temperature
before being stored in a desiccator for further investigation.
For modification of biochar by deashing, the biochar was
ground (≤ 0.50 mm) and soaked in 0.1 M HCl for 24 h under
agitation at a ratio of 1:9 to remove the indigenous minerals
[32]. Following deashing, biochar was leached with DI water
till stable pH. The urea was impregnated onto biochar at a
weight ratio of 1:1 (biochar: urea) by agitating it for 24 h at
200 rpm after preparing the urea solution at a weight ratio
of 1:5 (urea: DI water). After drying the mixture at 65 °C, a
50:50 blend of starch and polyvinyl alcohol (PVA) was pre-
pared. PVA was first dissolved in water overnight at 90 °C
for this purpose. The starch was then gelatinized for 10 min
at 100 °C with constant stirring. The gelatinized starch was
added to the PVA solution and stirred continuously at 70 °C
for 30 min. The solution was then poured onto the urea-
impregnated biochar mixture and homogenized for 30 min
[33]. The mixture was then passed through a granulator fitted
Biomass Conversion and Biorefinery

Table 1  Characteristics of N fertilizers N fertilizers. Experiment 2 measured the changes in soil

Fertilizers N contents (%) pH
Conventional urea 46.0 7.22
Commercial-SRF 26.0 6.90
BSRNF 21.0 6.47
with a 2-mm die extruder. BSRNF granules were air-dried at
room temperature and stored in tightly closed glass bottles
until further analysis [27]. The characteristics of BSRNF are
shown in Table 1.
2.2 Characterization of raw and deashed biochar
The pH and EC of raw and deashed biochar were deter-
mined in a mixture (1:25, w/v) in deionized water [34] while
the CEC of raw and deashed biochar was described by the
method of Takaya et al. [35]. Further, the volatile matter
(VM), ash (A), and fixed carbon (FC) of raw and deashed
biochar were determined according to the ASTM D1762-84
method [36]. The mineral structure of raw biochar, deashed
biochar, and urea-impregnated biochar were determined by
X-ray diffractometer (XRD). The Brunauer–Emmett–Teller
(BET) surface area and pore volume were determined by
the ASAP-2020 surface area and pore volume analyzer
(Micromeritics, Norcross, GA, USA). The surface morphol-
ogy of raw biochar, deashed biochar, and urea-impregnated
biochar was determined on the inspect-S-50 scanning elec-
tron microscope (SEM).
2.3 Experiments setup
The present study comprised three sections. Experiment 1
investigated the N release after the application of different
C (%)
­NH3 volatilization. Experiment 3 estimated the ­NO3 leach-
ing. Experiment 4 determined the changes in ­N2O emissions
- from soils after conventional urea, commercial slow-release
- fertilizer (C-SRF), or BSRNF application. All the experi-
31 ments were conducted in two different textured alkaline
calcareous soils (Table 2) to evaluate the BSRNF under
variable soils.
2.4 Experiment 1: N release
An incubation experiment was conducted at 25 ± 2 °C to
assess the N release behavior of N fertilizers in different
soils. For this purpose, three different BSRNF blends with
varying urea and biochar ratios were developed: BSRNF
(1:1), BSRNF (1:2), and BSRNF (2:1). The experimental
treatments were as follows: i) conventional urea (CU); ii)
commercial slow-release N fertilizer (CSRF); iii) BSRF
(1:1); iv) BSRF (1:2); and v) BSRF (2:1). All fertilizer treat-
ments on the basis of N contents equivalent to 1 g of urea
were embedded into a polypropylene mesh bag (5 × 5 cm)
tied with a label showing the name fertilizer. These mesh
bags were buried beneath the 2–3 cm of soil surface into
plastic containers filled with 150 g soil. The soil moisture
contents were maintained at 60% of field capacity by weigh-
ing and adding distilled water if necessary. The experiment
was laid in a completely randomized design (CRD) hav-
ing 3 replications in two different textured alkaline calcare-
ous soils (coarse and fine texture). After 1, 3, 5, 10, 20,
30, 40, 50, 60, and 70 days of the incubation period, one
mesh bag from each treatment was retrieved and the total
N was determined after being dried at room temperature to
a constant weight. The loss in total N was subtracted from
the initial contraction to assess the N release. This method
was adopted by Liu et al. [1] with some modifications. The

Table 2  Physicochemical Soil parameter Unit Values

characteristics of soils before
start of experiments Coarse-textured Fine textured

Soil particle size distribution % Sand Silt Clay Sand Silt Clay
53 30 17 19 54 27
Textural class - Sandy loam Silty clay loam
pH - 7.7 7.6
EC d ­Sm-1 1.02 1.11
OC % 0.34 0.41
NO3-N mg ­kg-1 7.4 8.1
NH4-N mg ­kg-1 6.3 7.4
Available P mg ­kg-1 4.7 5.4
Extractable K mg ­kg-1 92 94
CaCO3 % 7.2 10.9
CEC cmol+kg-1 11.3 13.1

13

best-performing BSRNF was selected and evaluated for fur-
ther estimations.
2.5 Experiment 2: ­NH3‑volatilization
The enclosure technique was adopted to trap and quantify
the ­NH3 volatilization as reported earlier by Liu et al. [37].
The experiment was conducted with treatments including,
i) Control ii) conventional urea iii) C-SRF, and vi) BSRNF,
respectively, with 3 replications arranged in CRD layout.
The application rates of different N fertilizers were 200 kg
N ­ha−1. Briefly, screw-lid plastic jars were filled with 500 g
of soil. The treatments were mixed at the top 5 cm layer of
each jar. About one-half of the space in the jars was left
vacant for the production of N­ H3. Distilled water was slowly
sprinkled on the surface of the soil to bring the soil mois-
ture level up to 60% of WHC and a vial containing 10 mL
of 4% boric acid, mixed with methyl red and bromocresol
green indicators was placed in every jar as ­NH3-trap and
lids were screwed and airtight. All jars were incubated at 25
ºC. The experiment was repeated on two different textured
alkaline calcareous soils. The experiment was executed soon
after wetting the soil. The boric acid vials were removed and
replaced daily until the color of the mixed indicator did not
change, and the trapped N ­ H3 was measured by titrating with
0.01 M ­H2SO4.
2.6 Experiment 3: ­NO3‑leaching
An incubation experiment was conducted at 25 °C to
evaluate the impact of BSRNF on ­NO 3-leaching in two
different alkaline calcareous soils. The experiment was
conducted with treatments including, i) Control ii) conven-
tional urea iii) CSRF, and vi) BSRNF with 3 replications
arranged in CRD layout. The application rates of different
N fertilizers were 200 kg N ­ha−1. The PVC columns 34 cm
in height and 5 cm in diameter were fixed with polypro-
pylene meshed cloth at the bottom and then columns were
fixed on the plastic funnel having gravel in it. A layer of
3.0 cm of coarse sand was laid into every column to facili-
tate leachate movement. The columns were packed with
soil and a bulk density of 1.4 g ­cm−3 was maintained by
gently tapping. A 4.0 cm from the top of every column was
left open for ponding of distilled water. The apparatus was
clipped on a wooden stand and 500 mL leachate receiv-
ing bottles were placed under each column to receive lea-
chate. The columns were saturated with distilled water and
a 5-pore volume of distilled water was leached for proper
conditioning. Then the treatments were mixed on top of
every column and one pore volume was leached on days
1, 7, 14, 21, 28, 35, and 42. Leachate was collected until
it had totally leached out and then the leachate volume
was recorded. The N ­ O3 concentration in the leachate was
13
Biomass Conversion and Biorefinery
measured and the columns were covered with a polythene
sheet to reduce evaporation and the outlet was plugged
till the next event of leaching. The method used in this
experiment was adopted by Kanthlea et al. [38] with some
modifications.
2.7 Experiment 4: ­N2O‑emission
An incubation experiment was conducted at 25 °C to evalu-
ate the impact of BSRNF on ­N2O emission in two different
alkaline calcareous soils. The experiment was conducted
with treatments including, i) control ii) conventional urea
iii) C-SRF, and vi) BSRNF, respectively, with 3 replications
arranged in CRD layout. The application rates of different
N fertilizers were 200 kg N h­ a−1. Plastic jars having 7.5 cm
diameter, and 13 cm height, providing 250 mL headspace
to a depth of 7 cm were filled with 500 g soil. Soil moisture
was kept at 60% of field capacity for 30 days. The jars were
capped during the sampling and remained open the rest of
the time. All the treatments were mixed into the surface of
the soil (2–3 cm deep). The ­N2O measurements were made
on 1, 4, 7, 10, 13, 16, 19, 25, and 30 days, at 0 h and 2 h
for the initial and final time, after incubation using air-tight
10 mL syringes. Gas samples were immediately analyzed
for ­N2O concentration using a gas chromatograph equipped
with an electron capture detector. Total ­N2O–N emission
during 30 days was calculated by integration of actual ­N2O
emissions on sampling days. The method used in this exper-
iment was adopted from Majumdar et al. [39] with some
modifications.
2.8 Soil analyses
The analysis of soils used in experiments was conducted
following soil pH and soil EC (1:2 soil–water ratio) [40],
organic carbon [41], total nitrogen (TN) [42], ­CaCO3 [43],
particle size distribution [44], available-P [45], and ­NH4 and
­NO3 [46].
2.9 Statistical analysis
For the properties of biochar samples, the means and stand-
ard deviations (± SD) were computed. Moreover, to com-
pare the effects of BSRNF on N-release, N­ H3-volatilization,
­NO3-leaching, and ­N2O emission, the differences of means
were analyzed statistically by a two-way analysis of vari-
ance (ANOVA) using Statistics 8.1 software. In addition,
the obtained data were evaluated using the least significant
difference (LSD) test for post hoc comparisons (at the 0.05
level of significance).
Biomass Conversion and Biorefinery

Table 3  Characteristics of raw biochar and deashed biochar deashed biochar confirming the demineralization/ leaching
Property Raw Biochar Deashed Biochar
of mineral contents. However, some new sharp and small
peaks emerged in the urea-impregnated biochar pattern. The
pH 7.59 ± 0.07 6.69 ± 0.05 matching of XRD intensities confirmed that a sharp peak at
EC (d ­Sm−1) 0.47 ± 0.01 0.42 ± 0.01 2θ angle 22.01° is recognized as urea along with other peaks
CEC ­(cmol+kg−1) 24.67 ± 0.23 28.41 ± 0.19 of urea at 2θ angle 19.84° 24.41°, 29.14°, 31.54°, 35.46°,
Volatile matter (%) 33.86 ± 1.13 34.16 ± 0.98 and 42.14°, respectively (Fig. 1).
Ash (%) 6.24 ± 0.17 0.97 ± 0.07 The FTIR spectrums (Fig. 2) showed a carboxylic (C = O)
Fixed carbon (%) 59.91 ± 1.27 64.87 ± 1.03 stretching vibration at 1677 ­cm−1, at 1592 ­cm−1 deforma-
Surface area ­(m2 ­g−1) 13.97 ± 0.05 104.57 ± 0.16 tion vibration of amide II band (C–N), and at 1460 ­cm−1
Pore volume ­(cm3 ­g−1) 0.013 ± 0.00 0.097 ± 0.001 symmetric stretching vibration of carboxylic (C = O) group
were observed in raw biochar. The FTIR spectra showed that
these vibrations were kept constant with a slight shift after
3 Results the deashing of biochar. However, in the urea-impregnated
biochar, some new stretching vibrations were seen. A broad
3.1 Characterization of raw biochar, deashed stretching vibration of the hydroxyl (O–H) functional group
biochar, and BSRNF was seen at 3431 ­cm−1, increased intensity of aminoacidic
­(NH2) at 3321 ­cm−1, carboxyl functional group (C = O)
The modification of biochar by deashing significantly at 1635 ­cm−1, amide II band (C-N) at 1592 ­cm−1, sym-
decreased the pH, and EC of raw biochar by 11.86%, and metric stretching vibration of carboxylic (C = O) group at
10.64%, while the CEC was increased by 13.16%. The 1460 ­cm−1, carbohydrate (C–O–C) vibration at 1153 ­cm−1,
deashing significantly decreased the VM and A by 0.88% and aromatic (C-H) stretching at 785 ­cm−1 were diagnosed.
and 84.45%, respectively, while the FC increased by 7.64%. The structure of raw biochar is presented in Fig. 3a show-
Similarly, after deashing surface area and pore volume of ing a honeycomb-like structure exhibiting numerous hollow
raw biochar increased by 86.64% and 86.59%, respectively channels of various diameters. This network of channels is
(Table 3). classified into three groups, depending on the cross-sectional
The XRD characterization (Fig. 1) showed that the peaks area: large, medium, and small-sized channels. The raw bio-
of calcite (at 2θ angle 39.46°), halite (at 2θ angle 44.04° char unveiled a porous structure with a smooth, tight, and
and 64.42°), pyrite (at 2θ angle 57.54°), quartz (at 2θ angle micro-tube bundle morphology. Further, some free particles
68.86°), and graphite (at 2θ angle 77.56°) were common in are seen throughout the structure which is attributed to the
raw biochar, deashed biochar, and urea-impregnated bio- ash contents. The deashing of raw biochar greatly influenced
char. The peak intensities of these minerals decreased in the composition of the biochar (Fig. 3b). The removal of

Fig. 1  XRD patterns of raw

biochar, deashed biochar, and
urea-impregnated biochar

13

Fig. 2  FTIR patterns of raw
biochar, deashed biochar, and
urea-impregnated biochar
minerals/ash from raw biochar as a result of deashing was
noticed which consequently exposed the porosity of bio-
char which is presumably obstructed by indigenous ash.
Urea impregnation filled the pores and covered the surface
of biochar (Fig. 3c).
3.2 N release
The BSRNF significantly delayed the N hydrolysis com-
pared to conventional urea and CSRF (Fig. 4). The con-
ventional urea showed the fastest release and 100% of N
was hydrolyzed and released from the mesh bag within 24 h
in both soils. The commercial SRF, however, restricted N
hydrolysis, but the N contents from commercial SRF last
only up to 20 days in different soils. On the other hand, the
N-release from BSRNFs was delayed significantly compared
to conventional urea and CSRF. In fine texture soil, BSRNF
Fig. 3  SEM-images of; (a) raw lignite, (b) deashed lignite, (c) urea-impregnated biochar, and granules of BSRNF
13
Biomass Conversion and Biorefinery
(1:1) released all N in 70 days, BSRNF (1:2) released all N
in 30 days, while BSRNF (2:1) released 81% of N in 70 days
of the incubation period. In coarse texture soil, the N release
pattern remained the same by BSRNF (1:1) and BSRNF
(1:2) but BSRNF released 92% of N during 70 days of the
incubation period. On the basis of N release behavior in
different soils and crops uptake patterns, BSRNF (1:1) was
selected for further evaluations.
3.3 NH3‑volatilization
NH 3-volatilization and cumulative ­N H 3-volatilization
from the applied N following the application of various
N-fertilizers is presented in Figs. 5(a, b) and 6. The results
showed that on all sampling days in fine texture soil,
­NH3-volatilization from control (untreated), urea, CSRF,
and BSRF ranged from 0.0–0.0, 0.41–7.92, 0.51–3.69, and
Biomass Conversion and Biorefinery
Fig. 4  Cumulative N release (%) (a) fine texture soil, (b) coarse texture soil after application of different N-fertilizers. Error bars show standard
error of the mean of three replicates
0.66–2.54 mg ­kg−1, respectively. At any point through-
out the incubation period, no ­N H 3 -volatilization was
detected in the control. It was observed that there was
a significant increase in N ­ H 3 -volatilization from the
­3 rd to ­7 th day in all treatments regardless of N fertiliz-
ers and then there was a decreasing trend. On the ­3rd day
of incubation, conventional urea emitted the maximum
­NH3-volatilization (7.92 mg ­kg−1), followed by the CSRF
emitted 3.69 mg ­kg−1 ­NH3-volatilization on the 4­ th day.
However, BSRNF emitted the highest ­NH3 (2.54 mg ­kg−1)
on the ­7th day of incubation. It was further noticed that
conventional urea and CSRF showed a sharp decline
in ­NH 3-volatilization after attaining the peak, whereas,
BSRF demonstrated a slow and consistent decrease in
­NH3 volatilization after attaining the peak. The cumulative
­NH3-volatilization of applied N from conventional urea,
Fig. 5  NH3-volatilization (mg ­kg−1) (a) fine texture soil, (b) coarse texture soil after application of different N-fertilizers. Error bars show the
standard error of the mean of three replicates
CSRF, and BSRNF was 23.02%, 20.38%, and 14.25%,
respectively. These results showed a decrease of 11.47%,
and respectively in N ­ H3-volatilization following the appli-
cation of CSRF, and BSRF, respectively, compared to urea.
Similarly, in coarse texture alkaline calcareous soil,
­N H 3-volatilization from urea and CSRF ranged from
0.56–7.81 mg ­kg−1 and 0.43–5.83 mg ­kg−1, respectively. The
­NH3 volatilization, on the other hand, from BSRNF ranged
from 0.0.53–3.09 mg ­kg−1. The pattern of NH3-volatilization
remained almost the same as it was seen in fine texture soil.
The results further showed that cumulative N
­ H3-volatilization
of applied N from conventional urea, CSRF, and BSRNF was
25.61%, 22.18%, and 17.19%, respectively. It means that the
application of CSRF, and BSRNF decreased the cumulative
­NH3-volatilization by 13.39%, and 32.87%, respectively com-
pared to conventional urea.
13
 Biomass Conversion and Biorefinery

Fig. 6  Effect of different N fer-

tilizers and soil types on cumu-
lative ­NH3 volatilization. Error
bars indicate standard error of
the mean of three replicates.
Different lowercase letters show
significant (p < 0.05) difference
among N fertilizers treatments
at same soil and uppercase let-
ters show significant difference
between soils at same N fertiliz-
ers treatments

3.4 NO3‑leaching ­NO3-leaching followed by CSRF in both soils compared to

The results shown in Figs. 7(a, b) and 8 revealed that
the application of BSRNF significantly decreased the
­N O 3-leaching compared to conventional urea in both
soils. It was also noticed that N­ O 3 leaching was higher
at the start of the incubation period from all N fertilizers
with the highest ­NO3 leaching in the first four leaching
events followed by a declining trend. It was further noticed
that ­NO 3 leaching was higher in conventional urea and
CSRF compared to BSRNF in the first four leaching events
while in the last four leaching events, ­NO3 leaching was
higher in BSRNF in both soils. However, among all N
fertilizers, conventional urea showed the maximum total
BSRNF. This trend clearly indicates a slow mineralization
of N by BSRNF.
The results showed that after 8 leaching events, total
­NO3-leaching from control, urea, CSRF, and BSRF was
7.64, 43.03, 35.85, and 26.17 mg ­kg −1, respectively, in
fine texture soil. Additionally, cumulative N
­ O3-leaching of
applied N in fine texture soil from urea, CSRF, and BSRF
was 35.39%, 28.21%, and 18.53%, respectively. It was
noted that the application of BSRF significantly decreased
the cumulative N ­ O 3-leaching by 47.64%, compared to
conventional urea. Similarly, the total ­NO 3-leaching in
coarse texture soil from control, urea, CSRF, and BSRF
was 8.89, 51.86, 40.41, and 30.52 mg ­kg−1, respectively. It

Fig. 7  NO3 leaching (mg k­ g−1) (a) fine texture soil, (b) coarse texture soil after application of different N-fertilizers. Error bars show the stand-
ard error of the mean of three replicates

13
Biomass Conversion and Biorefinery

Fig. 8  Effect of different N

fertilizers at different soils on
cumulative ­NO3 leaching. Error
bars indicate standard error of
the mean of three replicates.
Different lowercase letters show
significant (p < 0.05) difference
among N fertilizers treatments
at same soil and uppercase let-
ters show significant difference
between soils at same N fertiliz-
ers treatments

was also noticed that cumulative N

­ O3-leaching of applied
N decreased by 26.65%, and 49.66 by CSRF and BSRNF,
compared to conventional urea.
3.5 N2O emission
Application of all N fertilizers significantly increased the
­N2O emission (Figs. 9a, b, and 10) in both soils compared
to the control. But, it was observed that BSRNF significantly
decreased the ­N2O- emission compared to conventional urea
and CSRF in both soils. In fine texture soil, the maximum
­N2O flux (296 and 209 µg ­kg–1 soil d­ ay–1) was measured on
the ­4th day in conventional urea and CSRF which declined
sharply after the 4­ th day. However, in BSRNF, the maximum
­N2O flux (65 µg ­kg–1 soil d­ ay–1) was recorded on the 7­ th
day which declined slowly and gradually afterward instead
of a fast decline as it occurred in conventional urea and
CSRF. The conventional urea had the highest ­N2O emission
(757 µg ­kg–1), which was about 9 times greater than the con-
trol and significantly higher than the cumulative N
­ 2O emis-
sion from all other treatments. The cumulative ­N2O emission
of applied N from conventional urea, CSRF, and BSRF was
0.67%, 0.57%, and 0.32%, respectively. The results showed
that CSRF and BSRF significantly decreased the cumulative
­N2O emission by 14.52%, and 52.40%, respectively, com-
pared to conventional urea.

Fig. 9  N2O-emission (µg ­kg–1) (a) fine texture soil, (b) coarse texture soil after application of different N-fertilizers. Error bars show the standard
error of the mean of three replicates

13

Fig. 10  Effect of different N
fertilizers at different soils on
cumulative ­N2O emission. Error
bars indicate standard error of
the mean of three replicates.
Different lowercase letters show
significant (p < 0.05) difference
among N fertilizers treatments
at same soil and uppercase let-
ters show significant difference
between soils at same N fertiliz-
ers treatments
In coarse texture soil, conventional urea had the highest
­N2O flux (179 µg ­kg–1 ­day–1), followed by 119 µg ­kg–1 ­day–1
in CSRF occurred on the 4­ th day. These values were 11 and 7
times greater than the control. ­N2O flux in these treatments
declined sharply after attaining this peak while in control,
­N2O- flux was quite low, never exceeded 16 µg ­kg–1 soil
­day–1. The highest ­N2O emission (504 µg ­kg–1) was recorded
in conventional urea following 423 µg k­ g–1 in CSRF. How-
ever, in BSRNF, the maximum ­N2O flux (89 µg ­kg–1 ­day–1)
was recorded on ­7th day. These results clearly indicated that
BSRNF significantly decreased the daily ­N2O flux compared
to urea and CSRF. It was also observed that BSRNF showed
a moderate drop in ­N2O flux after attaining the peak. The
cumulative ­N2O emission of applied N from urea, CSRF,
and BSRNF was 0.47%, 0.39%, and 0.33%, respectively.
The results showed that CSRF and BSRNF significantly
decreased the cumulative ­N2O emission by 17.30% and
29.91%, respectively, compared to conventional urea.
4 Discussion
4.1 Characterization of raw biochar, deashed
biochar, and BSRNF
The physicochemical properties of biochar produced in
this study are consistent with previous work [47] but differ
slightly from those found by Fawzy et al. [48]. However,
it was observed that modification of biochar by deashing
significantly changed the characteristics of biochar. Deash-
ing decreased the pH and EC of biochar, while increased
the CEC of biochar. Several studies have found that
13
Biomass Conversion and Biorefinery
acid-washing biochar can reduce electrical conductivity
and increase C stability by removing contaminants from the
exterior and interior surfaces of the biochar particles [49-
51]. We know that biochar is generally alkaline in nature,
therefore, it is mostly not recommended for alkaline calcare-
ous soils. The high ash contents/alkaline minerals in biochar
are responsible for the high pH and EC. However, chemical
treatment of biochar like deashing with dilute acids leaches
down the alkalinity and converts the biochar to acidic which
is suitable for alkaline calcareous soils [18]. The acidic pH
and low EC, are attributed to the abundance of weak acidic
oxygen-containing carboxylic and phenolic functional
groups [52]. The decrease in biochar pH is consistent with
the understanding that biochar deashing with acid created
the carboxylic acid groups on biochar surfaces [53, 54] as
demonstrated by FTIR of deashed biochar. Biochar CEC is
a key property that helps in retaining nutrients, reduces ferti-
lizer runoff, and improves soil water retention. In this study,
it was noted that the deashing enhanced the CEC of biochar
due to the insertion of new binding sites, development of
new pores, and widening of original pores [55]. The SEM
images of deashed biochar confirmed these changes in the
structure of biochar. The characteristics of deashed biochar
like reduction in pH and EC, and high CEC can make it suit-
able for alkaline calcareous soils [56].
The deashing also decreased the VM and A contents of
biochar. In this way, the FC of biochar was enhanced in this
study. Biochar having high ash contents results in lower FC
contents [57]. It was also reported earlier that the deashing
of biochar with acids decreased the VM and A from bio-
char [25]. The ash contents had blocked the pores of biochar
as well which were removed by deashing (SEM images of
Biomass Conversion and Biorefinery
deashed biochar). Due to the removal of A, and VM trapped
in the biochar by the process of deashing, the porosity of
biochar was enhanced [58].
The deashing significantly changed the structural proper-
ties including surface area and pore volume of biochar [48]
which created more sites for N adsorption [59]. The increase
in the surface might be attributed to the widening of exist-
ing pores or the creation of new pores [60]. The deashing
loosened the structure so that the volatiles removal opened
the microspores present in the structure by diffusing the ash
out from the inner zones [61]. The mechanism was clari-
fied in SEM images of deashed biochar during this study.
It has been discovered that biochar produced at pyrolysis
temperatures (400–500 °C) contains the highest levels of
organic contaminants, including volatile organic compounds
(VOCs) and polyaromatic hydrocarbons (PAHs), making its
use for agronomic purposes risky. However, deashing and
washing of biochar not only remove such contaminants but
also improve biochar properties such as porosity, surface
area, CEC, and C stability [62].
The XRD diffractograms of deashed biochar showed that
the intensities of some minerals peaks either disappeared
or were reduced due to the loss of minerals. These findings
are in line with the results of a previous study [63]. Further,
XRD confirmed the presence of urea without shifting any
peak. These findings advocate the infusion of urea into the
biochar without disrupting the urea structure. The results,
therefore, directed the formation of the complex with bio-
char and binders. Almost similar results have been reported
by Bakshi et al. [29]. Liu et al. [1] investigated that urea
reflection appeared at 2θ = 22.61°, 24.95°, 29.65°, 31.85°,
35.91°, 37.33°, 45.73°, 49.84°, and 55.24° in the XRD pat-
terns of BNF-2 and BNF-4 indicating that biochar was effec-
tively filled and loaded with urea.
The FTIR spectra of both raw and deashed biochar exhib-
ited almost the same peaks. However, it was noticed that
some of the functional groups either disappeared or shifted
their position. It was found that urea loading increased the
intensity at both higher and lower wavenumbers. At the
high-wavenumber region 4000–1600 ­cm−1 BSRNF had
higher intensity of peaks stretches O–H and N–H. Further,
the high intensity of carbonyl stretching (C = O) in the range
of 1642–1652 ­cm−1 was attributed to amide groups. This
suggested the reaction of C = O in adsorbents with ­NH2 from
urea. Barbosa et al. [64] investigated that after loading urea
to biochar, absorption bands characteristic of urea at 3428.7
to 3253.3 ­cm−1 and the characteristics of primary amides in
the ­NH2 group. The band at 1675.8 ­cm−1 was characteristic
of amide carbonyl; the band at 1675.8 ­cm−1 was characteris-
tic of amyl carbonyl. The peak at 1625.7 ­cm−1 was evidence
of another common fold in primary amides, which is asso-
ciated with the C = O bond of the urea molecule, and the
bands at 1457.9 and 1149 ­cm−1 were related to C–N axial
deformation. Similarly, Liu et al. [1] found similar urea peaks
associated with N–H stretching (3450 ­cm−1, 1462 ­cm−1) and
C = O stretching of the acyl bond (1611 ­cm−1), indicating
that urea loaded to biochar. The FTIR spectra from 4000 to
500 ­cm−1 relate to the findings of previous research work
[65] which indicated that the broadband at 3311–3494 ­cm−1
is attributed mainly to H-bonded hydroxyl groups and amino
groups. The band at 1700–1740 ­cm−1 is attributed to C = O
of carboxyl, aldehyde, ketone, and ester groups. The bands
at 1500–1620 ­cm−1 are attributed to C = C in aromatic rings.
The bands at 2931, 2854, 1458, and 1370 ­cm−1 are attributed
to aliphatic C-H. The bands at 745–881 ­cm−1 are attributed
to aromatic C-H. Therefore, the sorption of urea to biochar
could be mainly caused by the hydroxyl and carboxyl groups
on the biochar surface, which could form coordination bonds
with the N atom. It has been found that the presence of a
wide range of oxygen-containing functional groups (FTIR
results) like carboxyl and hydroxyl increases the adsorption
ability after deashing which further enhanced their abun-
dance [66].
The SEM image of raw biochar showed relatively lesser
porosity due to blockage by ash. We know that the pres-
ence of the macropores are the connecting channels that
facilitates the urea entry into biochar [1]. But, deashing
increased the porosity of biochar which increased its surface
area as well. The significant increase in the surface area due
to deashing may result in an increase in the surface area-
mediated adsorption capacity of biochar by the formation
of an organo-mineral layer [67]. Deashing resulted in the
removal of the inorganic constituents and reduction of min-
eral matter of the raw material [68]. In previous research, it
was investigated that acid washing can import oxygen‐con-
taining functional groups to biochar, thereby increasing the
percentage of H/C and O/C which promote nutrient sorption
[56]. A partial collapse of macro-pores during deashing cre-
ated numerous micropores and mesopores in biochar [24].
The abundance of meso and micro-pores created after the
deashing of biochar allowed favorably to transport and store
urea and water. Some urea particles filled into the pores and
exposed cavities resulted due to deashing while some urea
crystallized on the surface of biochar unevenly which is seen
as fissures and cracks in SEM images.
4.2 N release
It was confirmed that BSRNFs significantly delayed the
N release in different soils compared to conventional urea
and CSRF. This extended N release was due to the network
structure of starch and PVA with biochar. In addition, bio-
char also adsorbed the N which slowed down the N release
rate from BSRNFs. The synergetic effects between bio-
char and binders (PVA and starch) further strengthen the
adsorption of N. This phenomenon could be the result of
13

N adsorption on the surface of biochar which was firstly
dissolved in the soil solution and then released through
dynamic water exchange after the application BSRNFs
in soil. The urea was adsorbed onto biochar via hydrogen
bonding and surface complexation with oxygen-containing
functional groups would gradually dissolve and then slowly
released with water molecules [69]. Liu et al. [1] indicated
that urea reacted with acidic functional groups of biochar or
bound to specific sites on the surface. Moreover, the FTIR
indicated that the N retention by biochar is attributed to the
chemisorption, such as hydrophobic bonding [70], π-π elec-
tron donor–acceptor interactions [71], and unconventional
hydrogen bonding [72]. The granules of BSRNFs absorbed
moisture which results in swelling of PVA and starch mix-
ture and upon condensation of BSRNF the partial nutri-
ent dissolution by osmotic pressure. However, most of the
nutrient solution remains stored in biochar pores that release
slowly via diffusion under a concentration or pressure gradi-
ent called the “diffusion mechanism.”
Among the three different composites of BSRNFs, it was
observed that N release from BSRNF (1:2) was relatively
faster which may not synchronize the needs of N by the
crop plants. On the other hand, N release from BSRNF (2:1)
was appreciably slower which may restrict the growth of
crop plants at early growth stages by inducing a deficiency
of N. But, the N release pattern of BSRNF (1:1) was more
appropriate for most of the crops. Therefore, BSRNF (1:1)
was selected for further evaluation based on this experiment.
However, it is recommended that further formulations and
combinations can be tested in the future since most N uptake
in crops occurs during a short period of maximum growth.
In particular, rapid N uptake in corn grown in North Caro-
lina begins approximately 30 days after planting [73]. There-
fore, the timing and extent of its release from controlled-
release fertilizers are of interest in agronomic management
decisions. Mahfuza et al. [74] studied that an ample supply
of N is necessary up to the 8­ th week of maize cultivation to
obtain the best yield and FUE.
4.3 NH3‑volatilization
According to the findings of this study, the introduction
of BSRNF, as opposed to conventional urea, significantly
reduced ­NH3-volatilization in alkaline calcareous soils. It
was due to the complexation of N onto the surface of bio-
char. The adsorption of urea was confirmed by SEM, XRD,
and FTIR characterization BSRNF during this study. These
results support the findings of other researchers who found
that the application of biochar in combination with urea
reduced ­NH3-volatilization by 23.1% in calcareous sandy
loam soil [26]. However, there are some discrepancies
between the responses of ­NH3 volatilization and N trans-
formation when biochar produced at high temperatures was
13
Biomass Conversion and Biorefinery
used [75]. Therefore, the unsatisfactory performance of
coated biochar fertilizers, made with non-acidified biochar,
can be attributed to the high pH of the granules. Esfandbod
et al. [76] found that alkaline biochar volatilized more than
75% of the applied N, whereas acidified biochar volatilized
only 24% of applied N. In the present study, deashed bio-
char having a slightly acidic pH was used as a carrier which
caused the reduction in ­NH3-volatilization by BSRNF in two
different alkaline calcareous soils. In addition, acidity (low
pH), high CEC, and high hydrogen ion buffering capacity of
biochar could have reduced the ­NH3-volatilization in alka-
line calcareous soils [77]. The restricted mineralization of
N from BSRNF in this study could also have inhibited the
­NH3-volatilization.
4.4 NO3‑leaching
Acidified biochar (deashed) as an N carrier significantly in
the form of BSRNF reduced the ­NO3-leaching compared
to conventional urea. The reduction in N ­ O3-leaching by
BSRNF was more noticeable in coarse texture soil than fine-
textured soil. Joseph et al. [78] reported that N ­ O3 capture
followed by biochar application could be due to a series of
complex reactions involving migration into biochar pores,
surface adsorption, and integration into an organo-mineral
layer. A recent meta-analysis also found that chemical N fer-
tilizer and manure-treated fields reduced ­N2O emissions and
­NO3 leaching by 44 and 47%, respectively [79]. The impact
of biochar on N ­ O3 leaching is influenced by a variety of
physical, chemical, and biological processes. The potential
of biochar to retain N
­ O3 and N
­ H4 or the suppression of nitri-
fication by clay particles has been postulated as a factor in
soil ­NO3 leaching [37, 80]. Depending on fertilizer type, soil
type, and leaching conditions, some biochar studies found
a decrease in N­ O3 leaching, whereas other studies showed
inconsistent effects of biochar on leaching [81, 82]. Van-Es
et al. [83] observed that more N leaching occurred in sandy
loam soils than in clay loam soils because coarse texture
soils cannot retain as much water as fine soils, and more
water is lost to leaching. Biochar has the ability to retain
water which is why BSRNF retained water and restricted
the ­NO3 leaching.
4.5 N2O‑emission
The ­N 2O emission was also significantly decreased by
BSRNF. The decrease in ­N2O-emission could be due to
slower N release and lower ­NO3 availability during the
incubation period after the application of BSRNF. This is
consistent with previous work, which found that biochar
significantly decreased N­ 2O emissions from soil [84]. It
was also observed that cumulative N ­ 2O emissions were
lower in coarse-texture soil compared to fine-texture soil.
Biomass Conversion and Biorefinery
Biochar added to arable soils can minimize ­N2O emissions
from soils by controlling N dynamics [76, 85]. Cayuela
et al. [86] conducted a meta-analysis, which found a 54%
reduction in ­N2O emissions in laboratory and field studies.
The mechanisms explaining the observed reduction of N ­ 2O
emissions following biochar application are still uncertain.
5 Conclusion
The losses of urea from the soil in the form of
­NH3-volatilization, ­NO3-leaching, and ­N2O emission are
very high attributing to low N retention. These losses
aggravate further in alkaline calcareous soils. It was inves-
tigated in this study that complexation of urea with deashed
biochar extended the N retention in soil which inhibited the
N losses without contributing any additional alkalinity to
alkaline calcareous soils. The XRD, FTIR, and SEM char-
acterization of BSRNF confirmed that urea was effectively
sorbed into the biochar. It was also studied that the deash-
ing of biochar as an N carrier for the synthesis of BSRNF
enhanced the capacity of biochar to sorb urea compared to
pristine biochar. Deashing also alters the biochar surface
chemistry to suit the alkaline calcareous soils. It is, there-
fore, recommended that modification of biochar not only
reduce the recommended rates of biochar but also serve as
an efficient N carrier for the formulation of SRFs. Further
research is necessary to improve the formulation of BSRNF
using a variety of feedstocks, pyrolysis temperatures, and
biochar modification techniques. Moreover, field trials of
BSRNF in diverse agroecological zones would assess nitro-
gen use efficiency (NUE) and determine the potential mul-
tiple benefits of BSRNF in terms of long-term economic
and environmental impacts on soil and plant health.
Authors’ contributions Muhammad Rashid conceived the research idea
and wrote the manuscript, Qaiser Hussain, Rifat Hayat, and Mukhtar
Ahmad supervised the overall research, Muhammad Azeem, Sarosh
Alvi, and Arshad Nawaz helped in analytical work, Sajid Masood,
and Rabia Khalid conducted the statistical analysis, Sarvet Jehan, and
Obaid ur Rehman performed the editing and improved the draft.
Funding This research didn’t receive any external funding.
Data availability The data will be available on reasonable request.
Declarations
Ethical approval This manuscript is authors' own research and has not
been submitted for publication elsewhere.
Competing interests The authors declare that there are no competing
interests.
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