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Assessment of a Biochar-Based Controlled Release Nitrogen Fertilizer Coated

with Polylactic Acid

Article in Journal of Soil Science and Plant Nutrition · May 2021

DOI: 10.1007/s42729-021-00497-x

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Journal of Soil Science and Plant Nutrition
https://doi.org/10.1007/s42729-021-00497-x

ORIGINAL PAPER

Assessment of a Biochar-Based Controlled Release Nitrogen Fertilizer

Coated with Polylactic Acid
Zhisheng Cen 1 & Lin Wei 1 & Kasiviswanathan Muthukumarappan 1 & Abdus Sobhan 1 & Rachel McDaniel 1

Received: 9 September 2020 / Accepted: 27 April 2021

# Sociedad Chilena de la Ciencia del Suelo 2021

Abstract
Conventional nitrogen (N) fertilizers used in crop production typically have use efficiencies of only 30 to 40%. While reduced
efficiency can be a result of multiple factors (rate, placement, source), mismatched timing between N availability and N crop
demand is a significant cause of reduced efficiency. This study aims to develop a biochar-based controlled release nitrogenous
fertilizer (BCRNF) from relatively low-cost renewable materials to improve N availability when needed by the corn crop thus
reducing N losses and improving nitrogen use efficiency. Ammonium sulfate was impregnated in biochar and then pelletized into
particles. Three concentrations (3%, 6%, and 10%) of polylactic acid (PLA) solutions were used to coat the particles to produce
BCRNF. The effects of different PLA concentrations on N release and physical properties of BCNRFs were investigated in both
water and soil conditions. Water absorption and retention, thermal stability, and microstructures of BCRNFs were also analyzed
to determine the N release mechanism of BCRNFs. The BCRNF coated by 10% and 6% of PLA both released 70% of N over
12 days in water and 25 days in soil. The biochar held 14% N that was not released into the water. However, coating with PLA,
increased N holding to 16% inside BCRNF particles. The thermal properties of BCRNFs were stable under 230 °C. The PLA
concentration of the coating layer significantly affected not only the N releasing time and rate but also the morphology and
thermal properties of BCRNFs. Higher PLA concentrations resulted in a longer releasing time at lower N release rates. This study
demonstrates that a biochar-based controlled-release nitrogen fertilizer (BCRNF) can enhance N release time and rate in both
water and soil environments through the integration of biochar absorption and a PLA coating. Further development could yield a
BCRNF that can optimally synchronize timing and amount of available N with crop N demand to increase N use efficiency.

Keywords Nitrogen . Fertilizer . Biochar . Polylactic acid . Controlled release fertilizer . Coating

Abbreviations 1 Introduction
BCRNF Biochar-based controlled release
nitrogenous fertilizer Annual consumption of nitrogen (N) fertilizer in the USA was
BNF Biochar-based nitrogenous fertilizer over 13 million tons in 2015 (USDA ERS 2019), but nitrogen
CRF Controlled release fertilizer use efficiency (NUE) is only 30 to 40% (Sun et al. 2020). A
N Nitrogen primary reason for the low NUE is a mismatch of the fertil-
NUE Nitrogen use efficiency izers’ N availability with N demand during crop growth (Raun
PLA Polylactic acid and Johnson 1999). The low NUE and associated N losses
TGA Thermogravimetric analyzer result in higher production costs and environmental problems
such as greenhouse gas (N2O) emissions, water quality im-
pairments, and soil degradation (Carpenter et al. 1998;
Erisman et al. 2018; Sharma and Bali 2018; Yao et al.
2018). To improve NUE in crop production and minimize
* Lin Wei nutrients loss, various types of controlled release fertilizer
Lin.Wei@sdstate.edu (CRF) have been developed to manipulate N release to match
crop N demand. Most existing CRFs are produced by two
1
Agricultural & Biosystems Engineering Department, South Dakota technologies: (1) fertilizers physically mixed with low-
State University, 1400 North Campus Drive, Brookings, SD 57007, solubility compounds (either organic or inorganic); (2)
USA

fertilizers coated with a physical barrier layer of chemicals,
either hydrophobic (e.g., olefin and rubber) or hydrophilic
(e.g., resins). In the latter case, the nutrient release is deter-
mined by the composition and microstructure of the coating
material (Azeem et al. 2014). These existing CRFs face sev-
eral challenges. First, they are significantly more expensive
than conventional fertilizers because of complicated, multi-
step production processes and costly coating materials. This
limits their application to high cash crops or specialties (e.g.,
professional turf, landscaping, and horticulture) with less than
1% of existing CRF products were used for large-scale crop
production (like corn) (Sempeho et al. 2014; Wang et al. 2015;
Pereira et al. 2017). Second, many of the coating materials
used in the existing CRFs are not biodegradable, which results
in unforeseen environmental concerns. The coating materials
like thermoplastic used in CRFs are very chemically stable
and minimally degraded in soil, which results in long-term
accumulation of microplastics and new pollution issues
(Pereira et al. 2017). Third, many commercially available con-
trol release fertilizers have stated claims of continual nutrient
release for up to 30 weeks, but because the coating materials
of sulfur-coated or bio-based polymers are susceptible to mi-
crobial or enzymatic degradation in soils, nutrient release is
unstable and inconsistent. There are very few successful prod-
ucts that can control nutrient release to match the timeline of
nutrient demand for a crop like corn growth reported in liter-
ature. There is a critical need to develop an effective, low-cost
CRF that does not cause unintended environmental
consequences.
Biochar, a mixture of solid residues resulting from various
biomass thermochemical processes, may help to address the
challenges of existing CRFs. Biochar has been applied in crop
production throughout human history to improve soil fertility
and crop productivity due to its characteristics of high carbon
content, porosity, pH value, stability, surface area, etc.
(Atkinson et al. 2010; Fryda and Visser 2015; Ding et al.
2016; Liu et al. 2018). It also has been proven a good soil
conditioner through increasing organic matter and improves
soil stabilization and retention of nutrients and water (Downie
et al. 2009; Atkinson et al. 2010; Gwenzi et al. 2018; Weber
and Quicker 2018). Moreover, biochar has a strong affinity to
inorganic ions (e.g., phosphate and nitrate). It can adsorb ni-
trogen (such as NH4+, NO3−, or NO2−), phosphorus (P, as
orthophosphate), potassium (K) from aqueous solutions to
be nutrient-enriched biochar to improve soil fertility (Clough
et al. 2013; Gwenzi et al. 2018; Zhang et al. 2018). Compared
to nutrient-unenriched biochar, nutrient-enriched biochar in-
creased soil organic matter 232 to 514% NPK soil macronu-
trients 110 to 230%, which resulted in 75 to 85% higher total
biomass production compared to conventional NPK fertilizers
(Kizito et al. 2019). The positive effects on soil
micronutrients, macronutrients, organic matter, and biomass
yield indicate that biochar may be a good carrier of nutrients
J Soil Sci Plant Nutr
for developing new CRF products (Cheng et al. 2008;
Ascough et al. 2011; Spokas et al. 2012; Milne et al. 2015;
Yang et al. 2020). The biochar produced from pyrolysis of
corn stove is one of the best nutrient carriers for CRF fabrica-
tion because of its excellent properties with over 70% of car-
bon content and very high porosity (Qu et al. 2012). There are
significant amounts of functional groups containing oxygen
(O), hydrogen (H), carbon (C), and N, such as hydroxyl (-
OH), carboxylic (COOH), carbonyl (C=O), amino (R-NH2),
distributed on the biochar surfaces, or trapped in micropores
and mesopores, which can absorb or bond with various nutri-
ents or ions (Qu et al. 2012; Lee et al. 2017). However, bio-
char is currently treated as waste and costs disposal fees in
bioenergy industries. If this wasted biochar could be used for
CRF fabrication, it not only benefits the bioenergy industries
but also can be continually supplied at a relatively low cost.
More importantly, the use of biochar makes economically
producing CRF products possible while minimizing the
waste’s impacts on environment.
Biomass-derived polylactic acid (PLA) is a biodegradable
and hydrophobic biopolymer. When N fertilizer particles coat-
ed by a PLA layer, N release is controlled by layer thickness
and surface morphology (Papangkorn et al. 2008;
Kampeerapappun and Phanomkate 2013). Calcagnile et al.
(2019) determined that a proper PLA-coating layer decreased
N release rates approximate 40% in water, compared to un-
coated fertilizer particles. Although PLA is relatively expen-
sive, PLA-coated CRFs can be produced at relatively low cost
if percentage of the PLA used is low.
Since nitrogen is considered to be the most important
nutrient in corn production, this study was focused to
develop a biochar-based controlled-release nitrogen fertil-
izer (BCRNF) that can control N release time and rate to
synchronize with the N demand of corn growth while
significantly reducing N loss to the environment. Our hy-
pothesis was that integration of biochar absorption and
biodegradable PLA coating layers in BCRNF fabrication
would improve N releasing time and rate in both water
and soil environments. The novelty of this BCRNF is the
integration of two existing CRF technologies: combining
biochar and coating with biodegradable PLA in one prod-
uct. This approach could address multiple challenges of
existing CRF products since it is a more consistent, bio-
degradable, CRF that can be produced inexpensively
through use of relative low-cost materials (biochar) and
only a small amount of a high-cost material, PLA. The
objectives of this study were to determine the effects of
different PLA coating layer concentrations on N release
time and rate under both water and soil conditions.
BCRNFs physical and thermal properties were also char-
acterized. The ultimate goal is to develop an affordable,
environmentally friendly, and effective BCRNF product
to improve NUE in corn production.
J Soil Sci Plant Nutr
2 Material and Methods
2.1 Material
Ammonium sulfate (21-0-0) was selected as the model con-
ventional N fertilizer and purchased from local markets. The
purity of this fertilizer is 90%. Methylcellulose was acquired
from The Candlemaker’s Store (Hamilton, OH, USA). Sandy
soil was purchased from Lowe’s (Brookings, SD, USA). PLA
pellets were purchased from the Solutions of Consequences
LLC (Grand Rapids, MI). All solutions were prepared with
distilled water. All chemical reagents were of analytical grade.
2.2 Preparation of Biochar
The biochar used in this study was produced from pyrol-
ysis of corn stover in the Bioprocessing Lab at South
Dakota State University (SDSU), Brookings, SD, USA.
To prepare the biochar, corn stover was collected from
the Agricultural Experiment Station farm at SDSU and
then air-dried to a moisture content less than 12%. The
stover was ground to achieve a diameter of less than
1 mm for 90% of particles. Finally, the powder was
pyrolyzed into three products (syngas, bio-oil, and
biochar) in a reactor (capacity of 3 kg per hour) at about
550 °C. During the pyrolysis process, many reactions
(e.g., dehydration, fragmentation/depolymization,
carbonazation, repolymization, oxidation) were taking
place to break down the long-chain large molecules of
lignin, celluloses, and hemicelluloses of corn stover into
short-chain smaller molecules of liquid bio-oil (mainly
containing aromatics and other hydrocarbons, phenols,
organic acids, water, etc.), syngas (a gas mixture of
CO 2 , H 2 , CO, CH 4 , steam, etc.), and solid biochar
(contained over 70% of carbon with rest of minerals
and ashes). The properties, compositions, and yield pro-
portions of these three products are heavily affected by
feedstock species, reactor type, and operating conditions.
Generally, the yield ratio of bio-oil:biochar:syngas in the
pyrolysis of corn stover at about 550 °C in our previous
studies was 42:25:33 in average (Qu et al. 2012). The
syngas and bio-oil are used to produce biofuel products,
but the biochar is currently treated as waste in biofuel
industries. More details of pyrolysis of corn stover were
described in our previous work (Qu et al. 2012). To
eliminate traces of harmful organics, the fresh biochar
was stored and aged in plastic bags over 2 years. The
biochar was ground and passed through the sieve of the
US Mesh number 80 with 90% of particle size less than
0.18 mm before being used to fabricate the BCRNF ma-
terial. The bulk density of this biochar was 0.095 g/cm3
with 3.44% of moisture content.
2.3 Preparation of Biochar-Based Nitrogen Fertilizers
Preliminary data indicated that the maximum adsorption ca-
pacity of biochar for ammonium sulfate 1:5 (biochar to am-
monium sulfate) at which point little to no ammonium sulfate
crystal particles appeared in the mixture. However, to ensure
complete absorption of ammonium sulfate into the biochar
micropores, a mass ratio of 1:1 (biochar to ammonium sulfate)
was used. To prepare the biochar-based nitrogen fertilizers
(BNF), 150 g of ammonium sulfate was dissolved in 200 ml
of deionized water in a 2000 mL beaker and stirred at room
temperature (25 °C) for 20 min. Then, 150 g of biochar was
slowly loaded to the ammonium sulfate solution and continu-
ally stirred for an additional 20 min to remove pore spaces
within the biochar powder. Next, 15.8 g of kaolin clay was
added into the biochar, ammonium sulfate solution and stirred
for an additional 20 min. Then, the mixture was dried for 5 h at
65 °C to impregnate ammonium sulfate into the micropore
space, mesopore space, or on the biochar surface. After
mixing and drying, the bulk volume of biochar, as well as
the bulk volume of the mixture, was significantly reduced to
less than 500 ml. Finally, the dried mixture was blended with
16.62 g methylcellulose and 10 mL deionized water and then
pelletized (Nesco FG-180) into particles with 3 mm diameter
and less than 5 mm length.
2.4 Preparation of Biochar-Based Control Released
Fertilizer
To prepare biochar-based control released fertilizer
(BCRNF) samples, PLA pellets were first dissolved in
chloroform solvent (99% purity) at three different concen-
trations (3%, 6%, 10%) of PLA by mass basis. The BNF
particles were submerged in each PLA solution for about
10 s and then quickly taken out and lay on a stainless-steel
tray to coat the surface of BNF particles. All coated
BCRNF samples were air-dried at room temperature (20
± 2 °C) for 8 h to remove the residues of chloroform sol-
vent. Based on the coating concentration of PLA solution,
these three different BCRNFs were named BCRNF-P3,
BCRNF-P6, and BCRNF-P10, for 3%, 6%, and 10% re-
spectively. To compare the color, particle size, and shape,
the ground biochar powder, conventional ammonium sul-
fate fertilizers, and the produced BCRNF particles were
shown as Fig. 1. The appearance of BCRNF-P3,
BCRNF-P6, and BCRNF-P10 particles was visually indis-
tinguishable. Coating BNF particles with PLA resulted in
less than 5% change in weight from uncoated particles.
While a higher concentration of PLA resulted in a gener-
ally thicker coating, there was less than a 1% difference in
weight among BCRNF-P3, BCRNF-P6, and BCRNF-P10
particles.

Fig. 1 The biochar powder and conventional ammonium sulfate fertilizer were used to prepare BCRNF particles. BCRNF is biochar-based controlled
release fertilizer
2.5 Experimental Design of N Release in Water
Figure 2a shows a schematic diagram of the N release in
water experiment. The experimental procedure for N re-
lease of BCRNF in water was previously described in Li
et al. (2018) and Jia et al. (2020). First, 1 g of each
sample of BCRNF-P3, BCRNF-P6, and BCRNF-P10, as
well as conventional ammonium sulfate and BNF, was
individually submerged into 100 mL deionized water in-
side an airtight bottle. After slightly shaking the bottle,
the NH4+ concentration of each sample solution inside
the bottle was measured and recorded daily by using an
ammonium Ion Specific (ISE) meter (Oakton) until the
NH4+ concentration had no change for at least 48 h. The
Fig. 2 Schematic diagrams of determining nitrogen releasing in water (a) and in the leachate of a soil column (b). BCRNF is biochar-based controlled
release fertilizer
J Soil Sci Plant Nutr
bottle was covered by a lid to minimize the influences of
possible evaporations. Each measurement was performed
in triplicate. The measured NH4+ concentration was used
to represent N release of each sample in this study. The
cumulative N release (%) of each sample was calculated
with Eq. 1:
C i *V i
Ni ¼  100% ð1Þ
N c *mt
where N i is the cumulative N release (%) in the water
on the i th day. Ci (g/L) is the NH 4+ concentration of the
solution on the i th day. V i (L) is the water volume; m t
(g) is the total mass of the BCRNF sample submerged
J Soil Sci Plant Nutr
in the water. Nc (%) is the percentage of NH 4+ in the
initial BCRNF sample before submerged in the water.
2.6 Experimental Design of N Release in Sandy Soil
An experiment of soil columns was designed to investigate the
N release of BCRNFs in sandy soil under a simulation of a
natural rainy environment. The transparent PVC columns
(7.5 cm diameter and 25.5 cm height) were used for this ex-
periment (Fig. 2b). To reduce the loss of soil during the ex-
periment, a filter paper was placed at the bottom of each col-
umn before loading the sandy soil. A mass of 1738 g of the
soil was slowly loaded into each column without compacting.
As shown in Fig. 2b, the average soil height was 23.3 cm. A
mass of 3 g of each sample (BCRNF-P3, BCRNF-P6, and
BCRNF-P10 as well as conventional ammonium sulfate and
BNF) was buried in the soil at a depth of 5 cm below the top
soil surface. Inflow parameters were selected to simulate nat-
ural rainfall patterns from the model established by Goodrich
et al. (1995). A storm was simulated by continuously adding
7000 ml of deionized water into the top of the column at a
constant flow rate of 20 ml/min and using a liquid peristaltic
pump (GP 1000, Fisher Scientific). Leachate effluent was col-
lected at the bottom of the column in a glass jar. The NH4+
concentration of the leachate from each sample was measured
and recorded using the ammonium Ion Specific (ISE) meter.
After the initial “storm,” the soil column was flushed with
1000 mL of deionized water at the same flow rate every 3
days to simulate regular raining conditions until the NH4+
concentration in the leachate had no change. The leachate
generated from the new water flushing was separately collect-
ed in new bottles. The purpose of the periodic flushing was to
simulate regular rain-washing-soil in the real environment
(Beven 2011). All treatments were tested in triplicate. Again,
the NH4+ concentration of leachate was used to represent the
N release (%) of the samples in the sand soil, which were
calculated with Eq.2:
0 0
CiV i
N i’ ¼ ∑i¼0  100% ð2Þ
N c  mt
where Ni′ is the total cumulative NH4+ release (%) in the
leachate on the ith day. Ci′ (g/L) is the NH4+ concentration of
the leachate on the ith day. Vi′ (L) is the volume of the leachate
on the ith day. mt (g) is the total mass of the BCRNF sample
applied into the column, and Nc (%) is the percentage of NH4+
in the initial BCRNF sample before applying in the columns.
2.7 Water Absorbance and Retention of BCRNFs
Water absorbance of BCRNFs was investigated by following
the steps established in previous research (Gwenzi et al.
2018). A mass of 0.5 g of each sample (BNF, BCRNF-P3,
BCRNF-P6, and BCRNF-P10) was oven dried at 60 °C for
48 h. The dried samples were then conditioned in an airtight
chamber with constant 75% relative humidity (RH). The
weight change of each sample was measured and recorded
daily during the conditioning until the sample weight became
stabilized. Water absorbance was calculated with Eq. 3:
ðM 2 −M 1 Þ
WA ¼  100% ð3Þ
M1
where WA (%) represents water absorbance, M2 (g) is the
sample weight after water absorption, and M1 (g) is the sample
weight before water absorption.
The water retention of BCRNF was investigated using the
same procedure as Gwenzi et al. (2018). After maximum ab-
sorbance was attained, the relative humidity inside the cham-
ber was conditioned to around 50%. The sample weights of
BCRNFs were again measured and recorded every 24 h until
the sample mass had no change. The water retention is pre-
sented by the rate of water lost over time. The lower water lost,
the higher the water retention. The water loss was calculated
with Eq. 4:
ðW 1 −W 2 Þ
Wl ¼  100% ð4Þ
W1
where Wl (%) is the water loss of a sample to represent
its water retention. W1 (g) represents the mass of the sam-
ple before losing water. W2 (g) represents the mass of the
sample after losing water. Each treatment was tested in
triplicate.
2.8 Scanning Electron Microscopy Analysis
The surface morphology of BCRNFs coated by different
concentrations of PLA (3%, 6%, and10%) was examined
using a scanning electron microscopy (SEM) (Hitachi-S-
3400, filament-based SEM, MO, USA). Before SEM ob-
servation, the BCRNF samples were first oven dried at
60 °C for 48 h. To evaluate the surface morphology of
BCRNFs, the samples were then dipped into liquid nitro-
gen and then fastened on the support. Then, they were
coated with Au using a sputter-coater (DC-150, sputtering
system, 10 nm of Au). Ultimately, the surfaces of BCRNF
particles were observed to get their morphology images
under an electric voltage of 10 kV at a working distance
of 10 mm with a 1500 × magnification.
2.9 Thermal Stability Analysis
To investigate the thermal stability of BCRNFs, samples
were analyzed using a Thermogravimetric analyzer (TGA)
(Q5000SA, TA instruments, New Castle, DE, USA). The
TGA analysis was conducted in accordance with the TGA

analyzer standard operational procedure. A mass of 3 mg
of each sample of BNF, BCRNF-P3, BCRNF-P6, and
BCRNF-P10 was individually put into different aluminum
pans. The samples were then placed in the TGA furnace
and heated from 20 to 450 °C under a nitrogen atmo-
sphere at a heating rate of 10 °C/min with a gas flow rate
of 20 mL/min. An empty aluminum pan was also tested as
a reference.
2.10 Statistical Analysis of Experimental Results
All the values of final results shown in the figures and tables
are the means of three replications. The data were subjected to
manually analyze via one-way ANOVA to identify the signif-
icances between different treatments at 95% of confidence
level.
3 Results
3.1 N Release of BCRNFs in Water
The cumulative N-releases of different BCRNFs and the BNF
and conventional ammonium sulfate fertilizers in water are
shown as Fig. 3a. N release from ammonium sulfate and
BNF followed an exponential pattern. Up to 90% N of ammo-
nium sulfate and 76% N of BNF were released at 1 day and no
additional N was released from ammonium sulfate and BNF
beyond 1 day. In contrast, only 1.82% N of BCRNF-P10,
3.22% N of BCRNF-P6, and 10.58% N of BCRNF-P3 re-
leased into the water at 1 day. N release from BCRNF-P3
samples also followed an exponential pattern on days 2 and
3 after which point it had released 74% of N and NH4+
remained stable. N release in BCRNF-P10 and BCRNF-P6
samples followed a linear pattern until day 12 when 70% of
N had been released and the concentration remained stable
after day 12. There was no significant difference in N release
Fig. 3 The cumulative nitrogen
releases of different biochar-
based control release nitrogen
fertilizers and ammonium sulfate
in water (a) and in the leachates of
soil columns (b). Ammonium
sulfate is the conventional nitro-
gen fertilizer as control; BNF is
biochar-based nitrogen fertilizer;
BCRNF is biochar-based con-
trolled release nitrogen fertilizer;
PLA is polylactic acid; BCRNF-
P3 is BCRNF coated by 3% of
PLA solution; BCRNF-P6 is
BCRNF coated by 6% of PLA
solution; and BCRNF-P10 is
BCRNF coated by 10% of PLA
solution
J Soil Sci Plant Nutr
between BCRNF-P6 and BCRNF-P10, but the N release of
these two samples was significantly different from that of the
other 3 samples: ammonium sulfate, BNF, and BCRNF-P3
(Fig. 3a). The measured results of BCRNF-P10 had very
low standard deviation (small error bars) indicating precise
results with high experimental repeatability. Therefore, the
error bars on the N release curve of BCRNF-P10 are too small
to be seen in Fig. 3a.
3.2 N Release of BCRNFs in Soil
Overall, a significantly higher percentage of N was released
initially from ammonium sulfate and BNF compared to the
three experimental treatments (Fig. 3b). On day 1, the test was
performed under simulating conditions of storm rain-wash-
ing-soil. After the initial 7000 ml water was flushed through
each column, 57% N of ammonium sulfate and 56% N of
BNF were leached and present in the effluent on day 1. In
contrast, about 53% N of BCRNF-P3, 15% N of BCRNF-
P6, and 6% N of BCRNF-P10 were released on day 1. After
the succeeding 1000 ml flushes, there was very little N release
detected in the column effluent of ammonium sulfate, BNF,
and BCRNF-P3 indicating that the maximum leachable N had
been reached. It was observed that about 15% N in the
BCRNF-P6 treatment effluent and 20% N in the BCRNF-
P10 treatment effluent were present on day 3. N release into
the column effluent continued to decrease with no N addition-
al release after 25 days. The BCRNF-P10 showed the longest
N-releasing time (25 days), followed by BCRNF-P6 (19 days),
BCRNF-P3 (4 days), BNF (1 day), and ammonium sulfate
(1 day). The measured results of BCRNF-P10 had very low
standard deviation (small, imperceptible error bars in Fig. 3b),
indicating very stable results with low variability and high
repeatability. The N release patterns for all treatments in the
soil leaching experiment were similar to patterns observed for
N release in water (Fig. 3a).
J Soil Sci Plant Nutr
Fig. 4 The total nitrogen releases of ammonium sulfate, biochar-based
nitrogen fertilizer, and different biochar-based control release nitrogen
fertilizers in the leachates of soil columns. Ammonium sulfate is the
conventional nitrogen fertilizer as control; BNF is biochar-based nitrogen
fertilizer; BCRNF is biochar-based controlled release nitrogen fertilizer;
PLA is polylactic acid; BCRNF-P3 is BCRNF coated by 3% of PLA
solution; BCRNF-P6 is BCRNF coated by 6% of PLA solution; and
BCRNF-P10 is BCRNF coated by 10% of PLA solution
In summary, the total cumulative N release of each
sample into leachate during the soil column experiment
is shown in Fig. 4. Compared to the total loss of 59% N
from ammonium sulfate, 58% N from BNF, and 56% N
from BCRNF-P3 that leached from the columns, BCRNF-
P10 had only 34% N released into leachate, and BCRNF-
P6 lost only 40% N. These results indicate that as a result
of multiple rain events, up to 66% N from BCRNF-P10
and 60% N from BCRNF-P6 remained in the soil avail-
able for crop uptake, but N remaining in the soil from
ammonium sulfate, BNF, and BCRNF-P3 was just 41%,
42%, and 44% N, respectively. These results indicate that
it is very difficult to have NUE more than 40% with
ammonium sulfate.
Fig. 5 The water absorption rates
(a) and water loss rates (b) of
biochar-based nitrogen fertilizer
and different biochar-based con-
trol release nitrogen fertilizers.
BNF is biochar-based nitrogen
fertilizer; BCRNF is biochar-
based controlled release fertilizer;
PLA is polylactic acid; BCRNF-
P3 is BCRNF coated by 3% of
PLA solution; BCRNF-P6 is
BCRNF coated by 6% of PLA
solution; and BCRNF-P10 is
BCRNF coated by 10% of PLA
solution
3.3 Water Absorbance and Retention of BCRNFs
Water absorbance on the first day was the highest for BNF and
decreased sequentially in the following order: BCRNF-P3,
BCRNF-P6, BCRNF-P10 (Fig. 5a). The absorbance of all
samples decreased after day 1. It was observed that BCRNF-
P10 had significantly higher water absorbance than that of
other samples after 6 days. The BCRNF-P10 showed the
highest water absorbance among the samples in the period
from the 7th to 10th day. After 10 days, BNF reached the
saturated water absorption of equilibrium state at the earliest
time among the samples, followed by BCRNF-P3 (13 days),
BCRNF-P6 (14 days), and BCRNF-P10 (15 days).
The water loss (%) of sample was used to represent its
water retention capacity in this study. The water loss of dif-
ferent BCRNFs and BNF is shown as Fig. 5b. Started from the
saturated state of water absorption, the water loss (%) of all
samples decreased sharply in the first day by following this
order: BNF, BCRNF-P3, BCRNF-P6, BCRNF-P10. It was
observed that BCRNF-P10 had significant lower water loss
than that of all other samples until day 3. After day 3, BCRNF-
P6 and BCRNF-P3 had lower water loss than that of BNF and
BCRNF-P10 until reached a new lowest saturated water equi-
librium on day 4. The BCRNF-P10 continually lost water
until reached the lowest water equilibrium state on day 5.
All BCRNFs and BNF samples can retain water for 4 days
or more. Especially, BCRNF-P10 can retain water in the lon-
gest time (5 days).
3.4 Surface Morphology of BCRNFs
The SEM images of BCRNFs and raw biochar are shown to
compare their surface morphology in Fig. 6. The image of Fig.
6a shows the initial surface morphology of raw biochar before
being used to fabricate BCRNF samples. Respectively, Fig.
 J Soil Sci Plant Nutr

Fig. 6 The morphology images

of biochar powder (a) and
different biochar-based control
release nitrogen fertilizers:
BCRNF-P3 (b), BCRNF-P6 (c),
and BCRNF-P10 (d) generated
by a scanning electron microsco-
py. SEM is scanning electron mi-
croscopy; BCRNF is biochar-
based controlled release fertilizer;
PLA is polylactic acid; BCRNF-
P3 is BCRNF coated by 3% of
PLA solution; BCRNF-P6 is
BCRNF coated by 6% of PLA
solution; and BCRNF-P10 is
BCRNF coated by 10% of PLA
solution

6b, c, and d show the surface morphologies of BCRNF-P3,
BCRNF-P6, and BCRNF-P10 after coated by different con-
centrations (3%, 6%, and 10%) of PLA solutions. When the
coating PLA concentration changed from 3%, 6%, and 10%,
the surfaces of the BCRNF particles were covered by PLA
coating layers, but the surface morphologies were visibly dif-
ferent from each other. The surface of BCRNF-P3 (Fig. 6b)
was rough with more small pores and cracks. There were
much less rough and less small pores and cracks on the surface
of BCRNF-P6 (Fig. 6c). The surface of BCRNF-P10 (Fig. 6d)
became smoother with very few small pores.
450 °C. Results clearly demonstrated two separate stages of
thermal degradations for these BCRNF and BNF samples in
the range of 20 to 450 °C with no obvious mass change be-
tween 20 and 160 °C and more than 80% mass loss through
thermal decomposition from 160 to 450 °C. The thermal de-
composition of BNF was significantly different from the 3
samples of BCRNS and completely decomposed without
any residue at 420 °C.
4 Discussion

3.5 Thermal Stability of BCRNFs
All samples were stable with no thermal degradation until
160 °C. BNF began degrading slowly at 170 °C with water
evaporation and release of volatiles. BNF then dramatically
lost mass between 250 °C and 340 °C as ammonium sulfate
evaporated. Mass loss continued, but more slowly at temper-
atures higher than 340 °C until complete decomposition and
residue depletion at 420 °C. In contrast, the thermal degrada-
tion of BCRNF-P3, BCRNF-P6, and BCRNF-P10 began at
230 °C. The degradation rates of BCRNFs varied depending
on PLA concentration in the range between 230 and 380 °C.
The order of degradation rates was BCRNF-P3 > BCRNF-
P6 > BCRNF-P10. However, the BCRNF-P10 quickly lost
mass and stopped degradation with about 18% of mass residue
at 380 °C. After 380 °C, if ignored possible measuring errors,
the order of degradation rates was reverted, becoming
BCRNF-P3 < BCRNF-P6 < BCRNF-P10 between 380 and
4.1 Effects of PLA Concentrations of Coating Layers on
the N Release of BCRNFs
There was no change in the NH4+ concentration after 90% N
released from the sample of ammonium sulfate into water
(Fig. 3a) since the purity of ammonium sulfate fertilizer pur-
chased from the local market is 90%. There was no residue
observed in the ammonium sulfate solution after completely
dissolved in water. Steps were taken to minimize measuring
errors during the experiment, and it is unlikely that there was
significant NH3 evaporation, so it is reasonable to assume that
this ammonium sulfate sample contained about 90% of solu-
ble N. Although there was no significant difference in the total
cumulative N release between BNF and BCRNF-P3,
BCRNF-P3 had a longer release time at a lower release rate
(74% N into water in 3 days) compared to BNF (76% N in
1 day). BCRNF-P6 and BCRNF-P10 released 70% in 12 days,
which was much longer than ammonium sulfate, BNF, and
J Soil Sci Plant Nutr

BCRNF-P3. Compared to the N release time of existing CRFs

developed by other researchers, for example, 6 h for Tang
et al. (2018), 8 h for Dubey and Mailapalli (2019), 3 days
for Ye et al. (2020), 5 days for Wei et al. (2019), 8 days for
Gwenzi et al. (2018), and 10 days for Li et al. (2018), the
BCRNF-P6 and PLA BCRNF-P10 have achieved a signifi-
cant improvement. While higher PLA concentrations (6% and
10%) both resulted in longer release times and lower N release
rates, there was no significant difference between 6 and 10%,
indicating that controlled release is achievable at a lower PLA
concentration. A lower PLA concentration will result in a
lower cost for BCRNF fabrication, which will improve the
economic survivability of BCRNF products.
Biochar can retain about 14% N of BNF particles and not
release into water (Fig. 3a). If the BNF particles were coated to
fabricated BCRNF particles by different concentrations (3% Fig. 7 Schematic diagram of controllable nitrogen releasing mechanism
of a biochar-based controlled release fertilizer particle (partially referred
6%, and 10%) of PLA coating layers, the biochar can even to Lee et al. 2017). BNF is biochar-based nitrogen fertilizer; BCRNF is
retain more N inside the BCRNF particles. As shown in Fig. biochar-based controlled release nitrogen fertilizer; PLA is
3a, BCRNF-P3 can retain 16% N. Both BCRNF-P6 and polylactic acid; BCRNF-P3 is BCRNF coated by 3% of PLA solution;
BCRNF-P10 can retain 20% of N. There is no significant BCRNF-P6 is BCRNF coated by 6% of PLA solution; BCRNF-P10 is
BCRNF coated by 10% of PLA solution
difference in retaining N between BCRNF-P6 and BCRNF-
P10. As mentioned in the 3.2 section of soil column experi-
ment, when the BNF, BCRNF-P3, BCRNF-P6, and BCRNF-
hydrophobic bonding, π-π electron donor-acceptor interac-
P10 particles were buried in the soil, N release from the par-
tions resulting from fused aromatic carbon structures, and
ticles was much less than that of N release under water con-
weak unconventional H-bonds (Fig. 7). After the solution
dition. At least 41% and 42% N of BNF and BCRNF-P3 can
was dried into powder, the biochar particles were impregnated
be retained while 44% and 60% N of BCRNF-P6 and
with NH4+, which are bound through ligand exchange, dis-
BCRNF-P10 are kept in the soil as shown in Fig. 3b.
solved multidentate ligand, C-π-cation interaction, acid-base
Logically, the biochar cores of BNF, BCRNF-P3, BCRNF-
reactions with COOH, C-OH, C-O, and C-N functional
P6, and BCRNF-P10 particles are able to retain at least 14% N
groups on the biochar surface, coordination of deprotonated
under both water and soil conditions because of the integration
OH or COOH functional groups, and reactions of O-
of biochar absorption and PLA coating layers. The remaining
containing groups (Lee et al. 2017) (Fig. 7a). The powder of
N and biochar can not only increase carbon sequestration but
biochar impregnated with NH4+was pelletized to small parti-
also provide more nutrients and energy to support microbe
cles and then coated with PLA layers to form granular
activities in soil, moderate soil degradation, and reduce N
BCRNF particles. When a BCRNF particle starts to absorb
leaching into groundwater. The results of soil column exper-
moisture and penetrate through the coating layer into the
iment also demonstrated that the PLA concentrations of coat-
BCRNF core due to swelling and cracking of the coating
ing layers had significant effects on the N releasing time and
layer, osmotic pressure builds up and water molecules pene-
rate of BCRNFs in soil environment (Fig. 3b). There was a
trate the surfaces into mesopores and micropores of biochar to
positive correlation between high PLA concentration and long
dissolve the impregnated solid N fertilizer to release NH4+
N release time, with BCRNF-P10 having both the highest
(Fig. 7b). Most irrigation water is absorbed by biochar and
PLA concentration and the highest release time (25 days),
part of the NH4+solution is stored inside the pores of biochar.
followed by BCRNF-P6 (19 days), BCRNF-P3 (4 days),
Then, the dissolved NH4+ ions are released to the interface
BNF (1 day), and ammonium sulfate (1 day). These results
between biochar and coating layer via diffusion, under con-
verified the initial experimental hypothesis: integration of bio-
centration or pressure gradient, or a combination of these as
char and a PLA coating layer would improve N release time
the driving force. When more water is absorbed into the
and rate in both water and soil environments.
BCRNF core, the stored NH4+ solution and water can diffuse
The controlled release mechanism of BCRNP utilizes the
to the interface following the dehydration of biochar (Fig. 7b).
physical and chemical properties of biochar and the PLA coat-
With changes in the osmotic pressures of both interfaces of
ing layer. When biochar mixed with the dissolving ammoni-
biochar and coating layer and the coating layer and water or
um sulfate, NH4+ ions were attached on surfaces and trapped
soil, the processes of absorption, swelling, diffusion, and de-
within mesopores and micropores of biochar due to chemi-
hydration of biochar and coating PLA take place in parallel
sorption of polar and nonpolar compounds, including

Fig. 8 The thermal degradation of different fertilizers. NH is ammonium ion; H O is water molecule; -OH is hydroxyl group;
group; is sulfonic acid group; is phenyl group
and series if water shortage occurs in the surrounding soil
(Chen et al. 2018; Li et al. 2018; Jia et al. 2020). In these
processes, the coating layer works as a controller: the diffu-
sion and penetration of water and NH4+ are controlled by
swelling and cracking of the coating layer. The permeability
of NH4+ gone through the coating layer will be decreased if
less cracks occur on thicker coating layer surfaces like 6
BCRNF-P6 and BCRNF-P10. This will result in longer N
releasing time and lower release rate. Conversely, the release
rate will become higher if more cracks occur on the coating
layer surfaces such as BCRNF-P3. If designed properly, the
coating layer would be able to control N release in the rate,
time, or pattern as desired. Moreover, the BCRNF complex of
ammonium sulfate, biochar, and PLA coating layer makes the
N release and degradation of BCRNF complex more stable
with either microbes or enzymes and resistant to higher tem-
peratures with greater moisture content to reduce N volatiliza-
tion, leaching, or runoff. Therefore, it is possible to develop a
good BCRNF product that can synchronize with the timeline
of N demand for corn growth while minimizing N lost into
environment, eventually, improving NUE of corn production.
4.2 Effects of PLA Concentrations of Coating Layers on
the Physical Properties and Thermal Properties of
BCRNFs
Biochar produced from corn stover pyrolysis had a good po-
rous structure with large surface area, which allowed it to
J Soil Sci Plant Nutr
is carboxylic
adsorb NH4+ as a N carrier for BCRNF fabrication (Gwenzi
et al. 2018) (Fig. 6a). It is possible to manipulate N release if a
particle of ammonium sulfate impregnated biochar was cov-
ered by a PLA coating layer (Fig. 7). The N release time and
rate might depend on the microstructure and surface morphol-
ogy of the coating layers. The SEM images (Fig. 6b, c, and d)
of BCRNFs demonstrated that the coating layer PLA concen-
tration significantly affected the surface morphology of the
coated particles. When PLA concentration increased from 3
to 6% and 10%, the surfaces of BCRNFs particles changed
from very rough with more small pores and cracks (Fig. 6b) to
less rough with less small pores and cracks (Fig. 6c), eventu-
ally, becoming denser and smoother surface with very few
small pores (Fig. 6d). These changes not only altered the N
release of BCRNFs to be controllable in both water and soil
environments as explained in the earlier discussing section but
also modified the physical properties and thermal properties of
BCRNFs.
In addition to the hydrophobic property of PLA, the
concentrations of PLA coating layers significantly affected
the water absorbance and retention of BCRNF particles
through formation of different microstructure and surface
morphology on their surfaces (Fig. 6) As shown in Fig. 7b,
upon the concentration gradient, water continually diffuses
into the biochar core to dissolve ammonium sulfate and
release the N ions, and then dehydration from the core in
parallel moving forward to the coating layer, where the
concentration N ions are lower, while water absorption
J Soil Sci Plant Nutr
occurs on the interface of coating layer between inside and
outside of BCRNF particles as water become available.
Driven by the gradient difference of osmotic pressure and
vapor pressure, water may penetrate the coating layers to
be stored inside of the particles more than the water dif-
fuses or dehydrates to outside of the particles. Therefore,
BCRNF particles would be continually absorbing more
water until an equilibrium of water movement occurs be-
tween inside and outside of the particles, the so-called sat-
urated water absorption. The water movement is signifi-
cantly affected by the resistance caused by the coating
layer. The BNF sample showed the highest water absor-
bance at 22% on day 1 since the water was directly
absorbed into BNF particles without any resistance of coat-
ing layer (Fig. 5a). Followed by 19% of BCRNF-P3 under
little resistance due to its very rough surface with more
small pores and cracks (Fig. 6b), 17% of BCRNF-P6 with
more resistance because of less rough surface with less
small pores and cracks (Fig. 6c), and 12% of BCRNF-
P10 having the highest resistance due to its dense and
smooth surface with very few small pores (Fig. 6d).
Similarly, after water was absorbed inside the particles, it
was more difficult to be diffused or released from inside to
outside, depending on the resistance caused by the coating
layer. This is the reason why the BCRNF-P10 particles
(Fig. 5a) had higher water absorbance than other samples
after 6 or 7 days until 15 days and the longest water reten-
tion time (6 days) shown in Fig. 5b. This “theory” of coat-
ing layer resistance can also explain why the BCRNF-P10
(25 days) and BCRNF-P6 (19 days) had longer N release
time at lower rates than that of BCRNF-P3 (4 days), BNF
(1 day), and ammonium sulfate (1 day) since the N release
depended on the water movement.
It was also verified that PLA concentrations of coating
layers significantly affected the thermal stability of
BCRNF particles (Fig. 8). Different PLA concentrations
of coating layers resulted in different thermal stability of
BCRNF particles. Compared to the thermal degradation of
BNF starting at 170 °C, there was no any thermal degra-
dation for all BCRNF samples until 230 °C. This is be-
cause higher PLA concentrations can form dense and
smooth coating layers on the surfaces of BCRNF particles
with very few micropores and cracks. These coating
layers can slow down the evaporation of water, volatile
organics, and ammonium sulfate. The higher PLA con-
centrations, the lower degradation rate in the heating
range of between 230 and 380 °C. However, at tempera-
tures higher than 380 °C, higher PLA concentrations cor-
related with higher degradation rate between 380 and to
480 °C due to final degradations of PLA and biochar and
resulted in 18% of the total mass remaining as
undegradable residues. More importantly, the TGA anal-
ysis identified that all of the BCRNF samples were
thermally stable under 230 °C, which means these
BCRNF products are stable and safe for applying not only
in soil but also under the conditions of existing packag-
ing, transportation, and storage technologies.
5 Conclusions
This study firstly investigated the effects of combination of
biochar absorption and polylactic acid coating on controlling
the releasing time and rate of ammonium (NH4+) released
from a novel biochar-based controlled release nitrogenous fer-
tilizer in water and soil. The results indicated that the releasing
time and rate were significantly affected by the concentration
of coating polylactic acid solution. When the concentration of
polylactic acid solution increased, the releasing time of am-
monium also increased in both water and soil while its releas-
ing rate decreased, but the influence of polylactic acid concen-
tration was not significant when the concentration was higher
than 6%. Biochar was found capable of retaining up to 20% of
ammonium in water and 60% in soil. Although further re-
search is necessary to optimize the combination of biochar
absorption and polylactic acid coating to effectively control
the releasing time and rate of ammonium, it is feasible to
develop an environmentally friendly biochar-based controlled
release nitrogenous fertilizer to improve nitrogen use efficien-
cy by integrating renewable and relatively low-cost biochar
and biodegradable polylactic acid.
Funding This research was supported by the South Dakota Governor’s
Office of Economic Development (grant #:POC2020-04), North Central
Regional Sun Grant Center (Grant #: 3FG386), and the USDA NIFA
program through the Hatch Project (No. 3AR676 and 3AH658) of the
South Dakota Agricultural Experimental Station.
Data Availability The datasets generated and analyzed during the current
study are available from the corresponding author upon request.
Declarations
Competing Interests The authors declare no competing interests.
Disclaimer Only the authors are responsible for the opinions expressed
in this paper.
References
Ascough PL, Bird MI, Francis SM, Thornton B, Midwood AJ, Scott AC,
Apperley D (2011) Variability in oxidative degradation of charcoal:
influence of production conditions and environmental exposure.
Geochim Cosmochim Acta 75:2361–2378. https://doi.org/10.
1016/j.gca.2011.02.002
Atkinson CJ, Fitzgerald JD, Hipps NA (2010) Potential mechanisms for
achieving agricultural benefits from biochar application to temperate

soils: a review. Plant Soil 337:1–8. https://doi.org/10.1007/s11104-
010-0464-5
Azeem B, KuShaari K, Man ZB, Basit A, Thanh TH (2014) Review on
materials & methods to produce controlled release coated urea fer-
tilizer. J Control Release 181:11–21. https://doi.org/10.1016/j.
jconrel.2014.02.020
Beven KJ (2011) Rainfall-runoff modelling: the primer. John Wiley &
Sons
Calcagnile P, Sibillano T, Giannini C, Sannino A, Demitri C (2019)
Biodegradable poly (lactic acid)/cellulose-based superabsorbent hy-
drogel composite material as water and fertilizer reservoir in agri-
cultural applications. J Appl Polym Sci 136:47546. https://doi.org/
10.1002/app.47546
Carpenter SR, Caraco NF, Correll DL, Howarth RW, Sharpley AN,
Smith VH (1998) Nonpoint pollution of surface waters with phos-
phorus and nitrogen. Ecol Appl 8:559–568. https://doi.org/10.1890/
1051-0761(1998)008[0559:NPOSWW]2.0.CO;2
Chen S, Yang M, Ba C, Yu S, Jiang Y, Zou H, Zhang Y (2018)
Preparation and characterization of slow-release fertilizer encapsu-
lated by biochar-based waterborne copolymers. Sci Total Environ
615:431–437. https://doi.org/10.1016/j.scitotenv.2017.09.209
Cheng CH, Lehmann J, Engelhard MH (2008) Natural oxidation of black
carbon in soils: changes in molecular for-m and surface charge along
a climosequence. Geochim Cosmochim Acta 72:1598–1610.
https://doi.org/10.1016/j.gca.2008.01.010
Clough TJ, Condron LM, Kammann C, Müller C (2013) A review of
biochar and soil nitrogen dynamics. Agronom-y 3:275–293. https://
doi.org/10.3390/agronomy3020275
Ding Y, Liu Y, Liu S, Li Z, Tan X, Huang X, Zeng G, Zhou L, Zheng B
(2016) Biochar to improve soil fertility. A review. Agronomy for
Sustainable Development 36:1–18. https://doi.org/10.1007/s13593-
016-0372-z
Downie A, Crosky A, Munroe P (2009) Physical properties of biochar
Dubey A, Mailapalli DR (2019) Zeolite coated urea fertilizer using dif-
ferent binders: fabrication, material properties and nitrogen release
studies. Environmental Technology & Innovation 16:100452.
https://doi.org/10.1016/j.eti.2019.100452
Erisman JW, Leach A, Bleeker A, Atwell B, Cattaneo L, Galloway J
(2018) An integrated approach to a nitrogen us-e efficiency (NUE)
indicator for the food production–consumption chain. Sustainability
10:925. https://doi.org/10.3390/su10040925
Fryda L, Visser R (2015) Biochar for soil improvement: evaluation of
biochar from gasification and slow pyrolysis. Agriculture 5:1076–
1115. https://doi.org/10.3390/agriculture5041076
Goodrich DC, Faurès JM, Woolhiser DA, Lane LJ, Sorooshian S (1995)
Measurement and analysis of small-scale convective storm rainfall
variability. J Hydrol 173:283–308. https://doi.org/10.1016/0022-
1694(95)02703-R
Gwenzi W, Nyambishi T, Chaukura N, Mapope N (2018) Synthesis and
nutrient release patterns of a biochar-based N–P–K slow-release
fertilizer. Int J Environ Sci Technol 15:405–414. https://doi.org/10.
1007/s13762-017-1399-7
Jia C, Zhang M, Lu P (2020) Preparation and characterization of poly-
urethane-/MMT nanocomposite-coated urea as controlled-release
fertilizers. Polymer-Plastics Technology and Materials 59:975–
984. https://doi.org/10.1080/25740881.2020.1719136
Kampeerapappun P, Phanomkate N (2013) Slow release fertilizer from
core-shell electrospun fibers. Chiang Mai J Sci 40:775–782
Kizito S, Luo H, Lu J, Bah H, Dong R, Wu S (2019) Role of nutrient-
enriched biochar as a soil amendment during maize growth: explor-
ing practical alternatives to recycle agricultural residuals and to
J Soil Sci Plant Nutr
reduce chemical fertilizer demand. Sustainability 11:3211. https://
doi.org/10.3390/su11113211
Lee J, Kim KH, Kwon EE (2017) Biochar as a catalyst. Renew Sust
Energ Rev 77:70–79. https://doi.org/10.1016/j.rser.2017.04.002
Li Y, Jia C, Zhang X, Jiang Y, Zhang M, Lu P, Chen H (2018) Synthesis
and performance of bio-based epoxy coate-d urea as controlled re-
lease fertilizer. Progress in Organic Coatings 119:50–56. https://doi.
org/10.1016/j.porgcoat.2018.02.013
Liu L, Tan Z, Gong H, Huang Q (2018) Migration and transformation
mechanisms of nutrient elements (N, P, K) w-ithin biochar in straw–
biochar–soil–plant systems: a review. ACS Sustain Chem Eng 7:
22–32. https://doi.org/10.1021/acssuschemeng.8b04253
Milne E et al (2015) Soil carbon, multiple benefits environmental.
Development 13:33–38
Papangkorn J, Isaraphan C, Phinhongthong S, Opaprakasit M,
Opaprakasit P (2008) Controlled-release material for urea fertilizer
from polylactic acid. Adv Mater Res 55-57:897–900. https://doi.org/
10.4028/www.scientific.net/AMR.55-57.897
Pereira EI, Nogueira AAR, Cruz CC, Guimarães GG, Foschini MM,
ACC B, Ribeiro C (2017) Controlled urea release employing nano-
composites increases the efficiency of nitrogen use by forage. ACS
Sustain Chem Eng 5:9993–10001. https://doi.org/10.1021/
acssuschemeng.7b01919
Qu W, Wei L, Ma Z, Julson J (2012) Fast pyrolysis of corn stover and
sawdust in a novel reactor. In 2012 Dallas, T-exas, July 29-August
1, 2012 (p. 1). American Society of Agricultural and Biological
Engineers. https://doi.org/10.13031/2013.41833
Raun WR, Johnson GV (1999) Improving nitrogen use efficiency for
cereal production. Agron J 91:357–363. https://doi.org/10.2134/
agronj1999.00021962009100030001x
Sempeho SI, Kim HT, Mubofu E, Hilonga A (2014) Meticulous over-
view on the controlled release fertilizers. Ad-vances in Chemistry
2014:1–16. https://doi.org/10.1155/2014/363071
Sharma LK, Bali SK (2018) A review of methods to improve nitrogen use
efficiency in agriculture. Sustainability 10:51. https://doi.org/10.
3390/su10010051
Spokas KA, Novak JM, Venterea RT (2012) Biochar’s role as an alter-
native N-fertilizer: ammonia capture. Plant Soil 350:35–42. https://
doi.org/10.1007/s11104-011-0930-8
Sun C, Chen L, Zhai L, Liu H, Wang K, Jiao C, Shen Z (2020) National
assessment of nitrogen fertilizers fate and r-elated environmental
impacts of multiple pathways in China. J Clean Prod 227:123519.
https://doi.org/10.1016/j.jclepro.2020.123519
Tang J, Hong J, Liu Y, Wang B, Hua Q, Liu L, Ying D (2018) Urea
controlled-release fertilizer based on gelatin mi-crospheres. J Polym
Environ 26:1930–1939. https://doi.org/10.1007/s10924-017-1074-
6
USDA Economic Research Service (2019) Using data from Tennessee
Valley Authority (TVA), Association of A- merican Plant Food
Control Officials (AAPFCO), and The Fertilizer Institute (TFI).
https://www.ers.usda.gov/data-products/fertilizer-use-and-price.
aspx
Wang SL, Heisey P, Schimmelpfennig D, Ball VE (2015) Agricultural
productivity growth in the United States: measurement, trends, and
drivers. Economic Research Service Paper No.Err-189. Available at
SSRN: https://ssrn.com/abstract=2692612
Weber K, Quicker P (2018) Properties of biochar. Fuel 217:240–261.
https://doi.org/10.1016/j.fuel.2017.12.054
Wei H, Wang H, Chu H, Li J (2019) Preparation and characterization of
slow-release and water-retention fertilizer based on starch and
halloysite. Int J Biol Macromol 133:1210–1218. https://doi.org/10.
1016/j.ijbiomac.2019.04.183
J Soil Sci Plant Nutr

Yang X, Kang K, Qiu L, Zhao L, Sun R (2020) Effects of carbonization performance and mechanism. Chem Eng J 381:122704. https://doi.
conditions on the yield and fixed carbon co-ntent of biochar from org/10.1016/j.cej.2019.122704
pruned apple tree branches. Renew Energy 146:1691–1699. https:// Zhang C, Liu L, Zhao M, Rong H, Xu Y (2018) The environmental
doi.org/10.1016/j.renene.2019.07.148 characteristics and applications of biochar. Environ Sci Pollut Res
Yao Y, Zhang M, Tian Y, Zhao M, Zeng K, Zhang B, Zhao M, Yin B 25:21525–21534. https://doi.org/10.1007/s11356-018-2521-1
(2018) Azolla biofertilizer for improving low nitrogen use efficiency
in an intensive rice cropping system. Field Crop Res 216:158–164
Publisher’s note Springer Nature remains neutral with regard to jurisdic-
Ye HM, Li HF, Wang CS, Yang J, Huang G, Meng X, Zhou Q (2020)
tional claims in published maps and institutional affiliations.
Degradable polyester/urea inclusion complex applied as a facile and
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