pubs.acs.

org/acsagscitech Article

Engineered Urea-Doped Hydroxyapatite Nanomaterials as Nitrogen

and Phosphorus Fertilizers for Rice
Chwadaka Pohshna and Damodhara Rao Mailapalli*

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ABSTRACT: The application of nanomaterials as nanofertilizers is one of the advanced solutions to overcome the excessive use of
conventional fertilizers without compromising the yield. In this study, the synthesized urea-doped hydroxyapatite nanomaterials
(UHN) at recommended (UHN_RD) and half-recommended (UHN_HRD) doses were compared with a recommended dose of
commercial bulk urea fertilizer (BUF) and control (CNT) treatment for nutrient availability in soil and yield of rice crops. Rice was
grown in 12 field columns (four treatments × three replications) by applying the fertilizer treatments at four growth stages and
Downloaded via 165.93.7.103 on June 5, 2023 at 06:51:11 (UTC).

irrigating the columns conventionally. The crop growth parameters such as plant height, biomass, and yield were measured for all
columns. The depths of ponding water and drainage were measured daily, and the water samples collected from ponding water and
drainage were analyzed for ammonium (NH4-N), nitrate (NO3-N), and ortho phosphorus (PO4-P) concentrations. The grain yield
was increased by 61, 60, and 65% in BUF, UHN_HRD, and UHN_RD, respectively, compared to the CNT treatment, which
indicates that the UHN can result in a yield at par with commercial fertilizers. The concentrations of NH4-N, NO3-N, and PO4-P in
the leachate were reduced by 69.11, 16.3, and 87%, respectively, under UHN_HRD and by 60, 10.6, and 66.3%, respectively, under
UHN_RD compared to BUF. The nutrient use efficiency was the highest in UHN_HRD for nitrogen (76.5%) and phosphorus
(14.27%) nutrients. The application of UHN as nitrogen and phosphorus sources revealed yield improvement and reduced leaching
of nutrients. Therefore, UHN could be used both as a nitrogen and phosphorus supplement to rice crops at a reduced application
rate.
KEYWORDS: nanofertilizer, rice, nitrogen, hydroxyapatite, phosphorous

■ INTRODUCTION
Agriculture is becoming a challenging task day-by-day due to
the growing population and increasing food demand caused by
low production rate, low nutrient use efficiency of crops,
unfavorable climatic conditions, and diminishing resources
(cultivable land, water, etc.). Food production needs to be
increased by 25−70% from 2014 levels by 2050 to meet the
growing population’s demand.1 Rice is the staple food for more
than half of the world’s population; it is cultivated in most
Asian countries, and to maintain its productivity, the
application of conventional fertilizers has been increased to
more than the recommended dose.2−4 In India, the optimal
nitrogen (N), phosphorus (P), and potassium (K) ratio (N/P/
K ratio) is suggested as 4:2:1, yet it is exercised as 10:2.7:1.2 In
China, fertilizer application has tripled in the last three
decades.3 Any kind of fertilizer used in farmlands cannot all be
absorbed by plants. The general fertilizer efficiency of nitrogen
is 30−60%, phosphorus is 2−25%, and potassium is 30−60%.5
This has led to environmental pollution such as elevated
leaching, volatilization and eutrophication, persistent organic
pollutants, soil acidification, and air pollution.6−8 As of 2019,
India was the top country for urea production and accounted
for 33.77% of the world’s urea production.9 The other top five
countries in urea production are the Russian Federation,
Indonesia, Pakistan, and the United States of America.9
The aggregate world fertilizer consumption increased by
33% between 2000−01 and 2013−14, with China, India, and
the United States being major global consumers.10 Hence, it is
necessary to supply the required nutrients in correct
proportions to fulfill the plant’s needs while minimizing the
environmental risk and maximizing outputs. To overcome the
excessive use of fertilizers, discovering new and advanced
solutions is encouraged without compromising the yield loss.
Fertilizer management can be engineered by introducing the
concept of nanotechnology in agriculture. Nanoparticles have
unique and different material properties compared with bulk
materials due to their smaller size,11,12 which can be more
advantageous than their bulk counterparts.13
Numerous reviews14−21 have reported the advantages of
using nanomaterials as nanofertilizers in agriculture. Some
studies observed that the water absorption and germination of
tomato seeds,22 mustard seeds,23 and gram seeds24 were
increased with the application of carbon nanotubes (CNTs).
The crop yield, root length, plant height, biomass, and
Received: July 27, 2021
Revised: December 8, 2021
Accepted: December 8, 2021
Published: December 17, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acsagscitech.1c00191

100 ACS Agric. Sci. Technol. 2022, 2, 100−112
ACS Agricultural Science & Technology
Figure 1. Synthesis process of HN and UHN using the sol−gel method.
chlorophyll content of peanuts25,26 and mung27 improved with
the application of zinc oxide nanoparticles and iron oxide
nanoparticles. An increase in the photosynthesis rate and
chlorophyll content of spinach crop,28 plant height, number of
leaves, fresh and dry weight as well as stem thickness of
tomato, pepper, and eggplants29 in the presence of titanium
dioxide and zinc oxide nanomaterials was observed compared
to control treatment. Also, the percentage of disease incidence
of soft rot bacteria significantly decreased in sugar beet plants
using silver nanoparticles and biological treatment.30 Labo-
ratory-scale studies are more prevalent since the overall effect
of nanoparticles on the environment and humans is yet to be
fully ascertained. Thus, there is a need to study the impacts of
different nanoparticles on food crops.
Hydroxyapatite (HN), Ca10(PO4)6(OH)2, is a mineral
containing calcium and phosphorus (Ca/P ratio, 1.67)
elements. It is the dominant inorganic phase in natural bone.
HN is used extensively in various biomedical applications,31,32
like fluorescent lamps, material for fuel cells, or an adsorption
and stabilization matrix for radioactive waste and harmful
metals.33 Dutta et al.34 observed a 21−41% reduction of sugar
levels in rice straw and rice husk with HN application as a
fertilizer. Liu and Lal35 also observed an increase in the growth
rate, seed yield, and biomass of soybean crops. The porous
nature of HN36,37 aids in the doping of the material with other
nutrients. Kottegoda et al.38,39 and Pradhan et al.40 synthesized
urea-doped hydroxyapatite (UHN) and tested the UHN on
rice crops. Kottegoda et al.39 investigated the effect of UHN on
rice yield but not on the leaching of N and P from the UHN-
treated rice fields. Pradhan et al.40 characterized the
synthesized UHN and tested it only for the germination of
rice seed (IR-36). Similarly, Madusanka et al.41 synthesized
nanocomposite UHN by encapsulating it with nanolayers of
montmorillonite and conducted a release study from the soil in
glass columns and pot trial experiments on rice crops. A
significantly slower release of N from the nanocomposite UHN
101
pubs.acs.org/acsagscitech Article
along with a significant enhancement in grain yield was
observed. The movement of nutrients in the soil−water−plant
system using a conventional fertilizer is understood well;
however, limited studies are available on the application of
nanofertilizers in agriculture and especially on HN-treated rice
fields. In this study, the aim is to investigate the movement of
N and P from the UHN in rice fields along with the effect on
crop yield. The movement of N and P nutrients in the soil−
water−plant system is important to understand, especially for
rice crops, which are grown in flooded conditions, and to be
able to determine the transport mechanism of the N and P
through UHN. This will help in understanding the transport of
N and P nutrients and planning better nutrient management
using nanofertilizers.
■ MATERIALS AND METHODS
Urea-Doped Nano-Hydroxyapatite. Nano-hydroxyapatite
(HN) was synthesized in the Nonpoint source pollution laboratory,
Indian Institute of Technology (IIT), Kharagpur, using the sol−gel
method after Pradhan et al.40,42 Figure 1 shows the flowchart for the
synthesis process of HN and the loading of urea into HN. The
following reagents of analytical purity grade from Merck/Sigma-
Aldrich were used for the synthesis of HN: calcium nitrate
tetrahydrate (Ca(NO3)2·4H2O), tri-ethanol amine, and dihydrogen
phosphate (NH4H2PO4). The reaction between these chemicals is
presented in eq 1. Water used in the synthesis procedures was distilled
and deionized. The synthesis protocol includes constant rate addition
of a 1.67 M solution of Ca(NO3)2·4H2O and ethanol in a 1 M
solution of ammonium dihydrogen phosphate (NH4H2PO4) while
maintaining the pH at 10 with the addition of ammonia. The mixture
was vigorously stirred at ambient conditions, and the resulting
solution was allowed to age for 48 h at room temperature. The final
solution was centrifuged with ethanol and deionized double distilled
water to remove ammonium and nitrate ions. The filtrate was dried at
80 °C for 24 h in a hot-air oven to obtain white powdered HN and
then characterized to determine its properties. For the loading of urea,
the procedure reported by Pradhan et al.40 was followed, with a urea/
HN ratio of 5:1 by weight. A saturated urea solution (0.5 M) was
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Figure 2. FESEM characterization of (a) HN and (b) UHN. EDX characterization of (c) HN and (d) UHN.

added to a solution of HN dispersed in distilled water (2 mg/mL) Table 1. Elemental Composition of HN and UHN
under ultrasonic mixing (30 kHz for 45 min) and stirred for 24 h.
After 24 h, the mixture was allowed to settle, the excess liquid was HN UHN
decanted, and the product was centrifuged with distilled water and material element weight % atomic % weight % atomic %
ethanol to remove excess urea and dried at 70 °C for 24−48 h to
C 16.00 28.05 18.40 28.70
obtain urea-doped hydroxyapatite nanoparticles (UHN), which were
then sent to Central Research Facility of IIT Kharagpur for O 31.29 41.19 36.79 43.08
characterization. P 19.81 13.47 14.13 8.55
Ca 32.91 17.29 24.54 11.47
10 Ca(NO3)2 ·4H 2O + NH4H 2PO4 + NH4 + + OH− N 6.13 8.20
total 100.00 100.00 100.00 100.00
→ Ca10(PO4 )6 (OH)2 + NH4 + + NO3− + H 2O (1)

Characterization of HN and UHN. The surface morphologies of

both HN and UHN were studied using a field emission scanning
electron microscope (FESEM: JSM-7610F, JEOL). The elemental
compositions of HN and UHN were measured by energy-dispersive
spectrophotometric (EDX) analysis. The shape and structure of HN
and UHN were determined with a FESEM (Figure 2).
Figure 2a indicates the FESEM images of the HN material, which
has a rod-shaped structure, although they were packed all together
due to agglomeration. As seen in Figure 2b, the rod-shaped structure
(similar to HN) in UHN indicates that doping does not affect the
morphology of the HN, and the size was less than 100 nm, as was also
observed by Pradhan et al.40 The EDX analysis (Table 1) indicated
the presence of Ca, P, C, and O as the major elements in HN (Figure
2c). The presence of N in UHN (Figure 2d) indicated that urea was
doped at 6.13% (by weight).
Field Column Experiments. Field columns were installed at the
Research farm of IIT Kharagpur. The experiments were conducted on
rice cultivar IR-36 during the Rabi season (Feb 6 to May 6, 2018).
The study site receives an average annual rainfall of 156.4 cm, a
minimum and maximum average annual temperatures of 12 and 40
°C, respectively, and a humidity of 12−99%. The average annual solar
radiation and wind speeds were 197.7 W/m2 and 2.78 km/h,
respectively.
Packing of Field Columns. The experiments were carried out in
an open field located at the Research farm of IIT Kharagpur using 12 Figure 3. Schematic representation of the soil column.
PVC columns, each having a diameter of 30.5 cm and a length of 37
cm (Figure 3). The bottom of the column was closed and had a drain

102 https://doi.org/10.1021/acsagscitech.1c00191
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hole at the center to allow leaching to a leachate collector (500 mL

available K (mg/g)
bottle). The columns were kept on a platform to facilitate free

0.041 (0.34)
drainage into the collection bottles.
The bottom of each column was lined with PVC mesh (to avoid
soil loss) and filled with pea gravel to a depth of 2 cm from the
bottom, followed by coarse sand of 1 cm depth on top of the pea
gravel. Then, the columns were filled with puddled soil up to 25 cm
depth using the field soil collected from the top 25 cm of the

total P (mg/g)
surrounding paddy fields. The columns were left undisturbed for a few

0.406 (0.3)
days for the soil to settle properly. Table 2 presents the physical and
chemical properties of the field soil. The top 12 cm of each column

Values in the brackets are standard deviation; K, potassium; P, phosphorus; N, nitrogen; BD, bulk density; EC, electrical conductivity; CEC, cation exchange capacity.
was kept free from soil to facilitate water ponding and fertilizer
application. The soil columns were initially saturated with water for 72

total N (mg/g)
h before the commencement of the experiments and allowed water to

0.1 (0.2)
drain from the columns to establish the same initial conditions (bulk
density, porosity, and soil nutrient content) in all columns.
Treatments. Four levels of N treatment, including control
(CNT), commercially available urea (BUF), UHN at the recom-
mended dose of nitrogen (UHN_RD), and UHN at half-

CEC (meq/100 g)
recommended dose of nitrogen (UHN_HRD), were considered.

8.40 (2.15)
Each treatment was replicated three times. The UHN was initially
sonicated with DI water for 1 h and then mixed with the ponding
water of the column. The recommended dose of nitrogen was taken as
120 Kg N/ha for all BUF and UHN_RD treatments, while it was 60
kg/ha for UHN_HRD. In the BUF treatment, the recommended dose
of P fertilizer was applied through SSP (60 kg/ha), while in UHN

1502.17 (21.3)
treatments, the P present as per the N application amounts to 350 Kg-

EC (μS/cm)
P/ha in UHN_RD and 175 Kg-P/ha in UHN_HRD. The potassium
(K) application rate was 50 Kg K/ha for all fertilizer treatments. Four
33-day-old seedlings were transplanted in each field column. The
fertilizer treatments were applied four times during the experiment:
once as the basal dose and then at 20-day (typical duration for a
growth stage) intervals. The depth of ponding maintained in the
5.601 (0.23)

columns varied from 1 to 5 cm during the growing period. The

pH

columns were irrigated to 5 cm depth when the depth of water in the

columns was 1 cm.
Data Collection. The rainfall data were collected from the
weather station located at the research farm. The ponding water depth
BD (g/cm3)
1.71 (0.01)

and leachate volume were measured daily at 9.00 AM. Water samples
were collected from the ponding water and the drainage point before
application of the fertilizer, after 4, 8, 12, and 24 h and daily for the
first week, every 48 h for the second week, every 72 h for the third
Table 2. Selected Physical and Chemical Properties of the Field Soila

week, and one sample per week thereafter. The number of tillers and
organic carbon (%)

plant height were also measured at every 20−23-day interval. The rice
0.18 (0.02)

crop was harvested from each column at the maturity stage (87 DAT)
to measure the grain yield and biomass. The soil (the surface and 15
cm and 25 cm depths) and plant samples were collected from the
columns after harvesting the crop to determine the nutrient content.
The field data collected during 0−54 DAT were considered for the
analysis as in the later stages of the experiment (after 54 DAT), the
16.08 (3.26)

columns experienced clogging. After harvesting the crop, the soil was
clay (%)

removed from the columns, and the bottom layers accumulated with
finer particles around the drain point were observed, which may cause
the clogging. The clogging of soil columns could possibly be due to
the constant hydraulic head maintained on top of the puddled soil.43
A reciprocating pump was used to pump water carefully from the
17.25 (2.84)
silt (%)

bottom drain without causing much disturbance to the soil to clear

the leachate collection point. The daily depths of ponding were
analyzed to see whether there was any significant difference in the
water levels among the treatments. The leachate samples were
analyzed in the NPS laboratory for NH4+, NO3−, and PO4− using the
66.67 (3.84)

Easychem 300 analyzer (AMS and Systea SPA, Italy). The collected
sand (%)

plant and soil samples were digested by following the standard

protocol and then analyzed for total N and P using the Easychem 300.
The nutrient use efficiency (NUE) was calculated using44 eq 2
depth (cm)

N or Puptake(fertilizer treatment) − N or Puptake(CNT treatment)

NUE% =
0−25

Total fertilizer applied

× 100 (2)
a

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Figure 4. Variation in the leachate volume, ETc, and ponding water levels in soil columns under (a) CNT, (b) BUF, (c) UHN_HRD, and (d)
UHN_RD treatments.

Balancing N and P is important to understand how efficiently crops
utilize the fertilizer, how much is lost in the process, and the nutrient
cycling of UHN. The inputs involve the total Kjeldahl nitrogen
(TKN) and total phosphorus (TP) present in the soil, the N and P
applied through the fertilizer, and the N (NH4-N, NO3-N) and P
(PO4-P) content in irrigation water. The output includes the TKN
and TP uptake by the plants, N (NH4-N, NO3-N) and P (PO4-P)
leaching through the column and ponding water, and the TKN and
TP, which remain in the soil. The N and P balance was calculated
using eq 3.
{N or Pfertilizer + TN or TPsoil before transplanting
+ N and Pirrigation water } − {TN and TPcrop uptake
physiological growth compared to the CNT treatment. Jha et
al.45 observed that the ETc from the flooded rice crop in pot
experiments was 0.4 cm/day, and Shekhar et al.46,47 in flooded
rice field experiment observed 0.3 to 0.6 cm/day ETc. The
ANOVA test shows that the effect of fertilizer treatments on
ETc was not significantly different (Table 3) as all treatments
Table 3. Average Depth of Irrigation, Drainage, and Crop
Evapotranspiration for Different Treatments in the
Columnsa
total irrigation depth
treatment (cm) drainage (cm) ETc (cm)

+ N and Pponding water + leachate + TN and TPsoil after harvesting } CNT 133.67 (3.7)a 58.63 (13.15)b 73.38 (3.72)c
BUF 135.76 (5.43)a 62.12 (20.16)b 74.41 (1.2)c
= N or Pother components (3) UHN_HRD 135.04 (1.3)a 52.72 (3.27)b 74.72 (2.8)c
UHN_RD 132.26 (2.52)a 45.10 (7.37)b 74.23 (1.3)c
Statistical Analysis. Statistical analysis was performed using
P-value 0.142NS 0.428NS 0.920NS
Minitab for analysis of variance (ANOVA) test at a 5% level of a
significance along with a Tukey post hoc test for pairwise comparison Shown are the means (±standard deviation) of three replications.
to specify the significant difference among the treatments for leachate Within each column, means designated with the same letter are not
volume, ponding water depth, NH4-N, NO3-N, and PO4-P significantly different. NSindicates nonsignificant difference, and
S
concentrations, agronomical parameters, and yield. indicates significant difference.

■ RESULTS
Crop Evapotranspiration. The crop evapotranspiration
(ETc) gradually increased with time during the growing season
for all fertilizer treatments (Figure 4). Overall, the seasonal
crop ET varied from 69.22 to 75.98 cm for CNT, 73.5 to 75.75
cm for BUF, 71.7 to 77.14 cm for UHN_HRD, and 72.8 to
75.4 cm for UHN_RD, with an average of 0.91, 0.93, 0.934,
and 0.927 cm/day, respectively. The nanofertilizer treatments
have slightly higher ETc, which may be due to the better
104
received adequate irrigation, and the seasonal water uptake
could be the same for all treatments. Regarding ETc, no
significant difference was seen among the treatments as
analyzed by Tukey’s test.
Drainage Depth. The depth of drainage collected from the
fertilizer treatments gradually decreased with time during the
season, possibly due to the gradual increase in ETc as the
depth of irrigation supplied to all fertilizer treatments was the
same (Figure 4a−d). The seasonal drainage depth under CNT,
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Figure 5. Rice crop growth dynamics: (a) plant height, (b) tiller count, (c) biomass, and (d) grain yield for different fertilizer treatments.

Table 4. Average Agronomical Parameters of Rice Crop for Different Treatmentsa

treatment plant height (cm) number of tillers (per hill) above-ground biomass (g/hill) below-ground biomass (g/hill) grain yield (g/hill)
CNT 53.3 (1.5)a 32.0 (8)c 32.230 (2.02)d 19.92 (2.18)f 23.41 (7.8)h
BUF 57.8 (5.1)ab 41.5 (1.5)c 40.450 (5.25)de 25.07 (1.25)g 60.22 (1.01)i
UHN_HRD 60.3 (0.6)ab 40.5 (0.5)c 39.895 (1.73)de 25.11 (1.83)g 57.78 (1.01)i
UHN_RD 61.3 (1.2)b 41.5 (0.5)c 41.485 (2.5)e 26.02 (1.22)g 67.17 (2)i
P-value 0.028S 0.058NS 0.027S 0.008S 0.000S
a
Shown are the means (±standard deviation) of three replications. Within each column, means designated with the same letter are not significantly
different. NSindicates nonsignificant difference, and Sindicates significant difference.

BUF, UHN_HRD, and UHN_RD treatments varied from 48.3
to 73.4, 43.2 to 83.3, 49.4 to 56, and 37 to 51 cm with an
average of 0.483, 0.77, 0.66, and 0.56 cm/day, respectively.
Relatively lower drainage depths were observed for nano-
fertilizer treatments, indicating that more soil water is available
for plant uptake. Furthermore, the irrigation frequency
increased with the growing period, possibly due to an increase
in ETc resulting from increased biomass. However, in Table 3,
the ANOVA test indicated that the effect of fertilizer
treatments on the drainage depth was not significantly different
(Tukey test, P <0.05).
Agronomic Parameters. As expected, the tiller count
(Figure 5a) and plant height (Figure 5b) increased until the
flowering stage and then decreased in all fertilizer treatments.
The effect of different fertilizer treatments on the number of
tillers was not significantly different. However, the effect of
fertilizer treatments on plant height, above-ground biomass
(Figure 5c), and grain yield (Figure 5d) was significantly
different. The plant height, above-ground biomass, and grain
yield were observed to be 10.3, 22.3, and 65% higher in
UHN_RD and 8, 19.2, and 60% higher in UHN_HRD than
those in CNT. However, they were 6.5, 2, and 11% higher in
UHN_RD, and 5, 1, and 4% less in UHN_HRD when
compared to the BUF treatment. The ANOVA test indicated
105
that the plant height, above-ground and below-ground
biomass, and grain yield were significantly different, while
the numbers of tillers were not significantly different. The
Tukey test results indicated that the plant height and above-
ground biomass under CNT and UHN_RD treatments were
significantly different among each other (Table 4); however,
BUF and UHN_HRD treatments were not significantly
different. The Tukey test also indicated that the below-ground
biomass and grain yield results were significantly different for
the CNT treatment and fertilizer treatments (UHN_RD,
UHN_RD, and BUF), but there was no significant difference
among fertilizer treatments (UHN_RD, UHN_RD, and BUF).
Leachate Quality. NH4-N Concentration. The NH4-N
concentration in ponding water was 2.6, 47.2, and 49.7%
higher than those in the leachate for BUF, UHN_HRD, and
UHN_RD treatments, respectively; this could be due to the
lower drainage volume of the columns and the presence of a
puddled layer at about 10 cm soil depth, which may restrict the
leaching of NH4-N from the surface to the bottom. The other
reason could be that the plant uptake and cationic NH4-N
concentration generally bond with the anionic clay particles
(9.1%) of the soil in the top layer, restricting the movement of
the NH4-N ions to the lower layers/drainage.48 However, in
the CNT treatment, the NH4-N concentration in ponding
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Figure 6. NH4-N concentration in ponding water and leachate under (a) CNT, (b) BUF, (c) UHN_HRD, and (d) UHN_RD treatments.

Table 5. Average NH4-N, NO3-N, and PO4-P Concentrations in Ponding Water and Drainage Water for Different Treatmentsa
ponding water concentration drainage water concentration
fertilizer treatment NH4-N NO3-N PO4-P NH4-N NO3-N PO4-P
CNT 35.9 (4.2)a 26.67 (0.2)d 0 (0)h 37.4 (6.9)k 25.44 (1.92)o 0.5 (0.46)q
BUF 140.0 (5.3)b 54.12 (1.5)e 94.4 (13)i 151.2 (11.8)l 34.44 (4.0) p 9.6 (4)r
UHN_HRD 73.16 (2.4)c 29.62 (0.2)f 63 (10)j 46.7 (7.7)km 28.81 (3.2)op 1.26 (0.4)q
UHN_RD 106.9 (3.2)d 37.23 (0.95)g 75.5 (12)j 60.5 (7.6)m 30.79 (0.6)op 3.23 (0.83)q
P-value 0S 0S 0S 0S 0.048S 0.002S
a
Shown are the means (±standard deviation) of three replications. Within each column, means designated with the same letter are not significantly
different. NSindicates nonsignificant difference, and Sindicates significant difference.

water and leachate was the lowest compared to all fertilizer
treatments, but the leachate concentration was 32% higher
than that in the ponding water. The concentration of NH4-N
in the CNT treatment may be due to irrigation water and
mineralization of organic N from organic matter, crop residues
present in the soil, and CEC of soil (Table 2). The NH4-N
concentration has four pronounced peaks in the ponding water
for all treatments, which could be attributed to the application
of fertilizer four times during the rice-growing seasons (Figure
6b−d). But, under the CNT treatment, the time series curve
was observed to be flat because the fertilizer was not applied.
Therefore, the NH4-N concentration gradually decreased
under the CNT treatment in both ponding and drainage
waters (Figure 6a).
The NH4-N concentration in ponding water for the BUF
treatment (Figure 6b) showed a sudden increase on the day of
fertilizer application and attained a peak of 5−8.9 ppm after 4−
106
6 days of fertilizer application due to urea hydrolysis. The
magnitude of the NH4-N peak varied positively with the
amount of N fertilizer applied during the season. The gradual
fall in the concentration may be due to the N uptake by rice
crop, N loss through drainage, and frequent irrigation
application in later DATs. The NH4-N concentration attained
a peak of 5−5.8 ppm under UHN_RD and 2−3.9 under
UHN_HRD within 6−7 days after fertilizer application. The
lower NH4-N concentration in the case of UHN_HRD was
due to the lower application rate. The high difference in peak
between the UHN and the BUF treatment may be due to the
doping effect of urea with HN, causing a delay in the
volatilization of urea in the nanofertilizer treatment and thus
warranting the effective slow nitrogen releasing property of
UHN.40 The NH4-N concentration in the ponding water for
UHN_HRD and UHN_RD treatments was reduced by 49 and
21.2%, respectively, while the leachate concentration decreased
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Figure 7. NO3-N concentration in ponding water and leachate under (a) CNT, (b) BUF, (c) UHN_HRD, and (d) UHN_RD treatments.
by 72.4 and 59.3% for UHN_HRD and UHN_RD compared
to the BUF treatment. The NH4-N concentration in the
drainage was lower due to the constant and very slow release
rate in the UHN nanomaterial.
Considering the peaks before the clogging of the column,
the travel velocity of NH4-N ranges from 4.2 to 6.3 cm/day,
2.8 to 2.5 cm/day, and 2.1 to 3.1 cm/day for BUF,
UHN_HRD, and UHN_RD treatments, respectively. Hence,
UHN treatments show slow-releasing properties since they had
a lower travel velocity than the BUF treatments. In later DATs,
both ponding and leachate peaks were almost similar due to
frequent irrigation application and rainfall. The effect of
fertilizer treatments on NH4-N concentration was significantly
different (Table 5) in ponding water and leachate; however,
the NH4-N concentration in CNT and UHN_HRD leachate
was almost similar. The ANOVA test confirms the significant
difference in NH4-N concentration among all treatments in
ponding and drainage water. The Tukey test shows that the
NH4-N concentration in ponding and drainage water are
significantly different among all treatments. The test also
indicates that the highest mean NH4-N concentration in both
ponding and drainage water was in the BUF treatment,
followed by UHN_RD, UHN_HRD, and then CNT treat-
ments.
NO3-N Concentration. Similar to NH4-N, the NO3-N
concentration responded positively with the N-fertilizer
application (Figure 7). The effect of fertilizer treatments on
NO3-N concentration was significantly different for ponding
water and drainage (Table 5). The NO3-N concentrations
were much lower in the CNT treatment than those in fertilizer
treatments, but the concentration was almost constant for
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ponding water and leachate. In the BUF treatment, the NO3-N
concentration increased steadily and hit a peak, and after that,
it declined due to the drainage and plant uptake. For
UHN_HRD and UHN_RD treatments, the NO3-N concen-
tration in ponding water was reduced by 45.2 and 31.2%,
respectively, compared to the BUF treatment. The highest
peak in ponding water was observed in the BUF treatment
ranging from 2 to 3.5 ppm, while much lower peaks were
observed in nanofertilizer treatments, with 0.8−1.4 ppm for
UHN_HRD and 1.2−2.5 ppm for UHN_RD.
The NO3-N concentration in the drainage had a peak within
3−5 days after ponding water, and the NO3-N concentration
in the drainage was reduced by 10.6% in the UHN_RD
treatment and by 16.3% in the UHN_HRD treatment
compared to the BUF treatment. It can also be seen from
Figures 6 and 7 that the NH4-N leaching was more than that of
NO3-N. Considering the anionic nature of the NO3-N,
leaching was lower due to the sandy loam soil in the column,
and the ponding of the columns makes the soil anaerobic and
reduces the nitrification rate. Tan et al.49 also observed higher
NH4-N concentrations at 33 and 58 cm depth than that of
NO3-N. The travel velocity of NO3-N ranges from 3.5 to 8.3
and 2.5 to 5 cm/day for BUF and UHN_RD treatments,
respectively, but the peaks were not very prominent in the case
of the UHN_HRD treatment. The ANOVA test confirms the
significant difference in NO3-N concentration among all
treatments in ponding and drainage water (Table 5). The
Tukey test shows that NO3-N concentrations in ponding water
among all treatments were significantly different, but in
drainage water, NO3-N concentrations under CNT and BUF
treatments were significantly different among each other
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Figure 8. Ortho P concentration in columns: (a) CNT, (b) BUF, (c) UHN_HRD, and (d) UHN_RD treatments.

Table 6. Mean Values of the Nitrogen and Phosphorus Balance Components (in mg/column) Observed for Different
Treatmentsa
nitrogen phosphorus
balance components CNT BUF UHN_HRD UHN_RD CNT BUF UHN_HRD UHN_RD
soil before 1041.3 (15.04) 2364.7 (27.7)
transplanting
fertilizer 0.0 800.4 400.8 800.4 0.0 332.1 918.2 1837.0
irrigation water 8.32 (1.11) 8.58 (1.8) 8.42 (0.9) 8.1 (1.24) 3.0 (0.12) 3.7 (0.15) 2.2 (0.15) 2.1 (0.2)
plant uptake 102.0 (10.11) 495 (24.5) 408.7 (5.6) 520.0 (21.22) 53.0 (6.74) 90.0 (7.7) 184.0 (12.55) 215.2 (3.84)
soil after harvesting 917.9 (50.2) 1215.9 (73.6) 1002.6 (62.5) 1295.4 (105.2) 2315.9 (85.7) 2488.9 (50.58) 3016.1 (83.58) 3875.5 (76.52)
ponding water 1.8 (0.68) 6.0 (2.11) 2.8 (0.56) 3.2 (1.4) 0.3 (0.11) 94.4 (8.14) 63.0 (1.8) 75.5 (5.9)
drainage 3.9 (0.6) 67.6 (2.3) 48.7 (6.73) 55.4 (4) 0.5 (0.05) 9.6 (0.8) 1.3 (0.22) 3.2 (0.15)
other losses 23.7 65.4 −12.6 −24.2 −2.0 17.5 20.8 34.3
a
The values shown in the brackets are standard deviations of three replications.

(Table 3); however, NO3-N concentrations under UHN_RD
and UHN_HRD treatments were not significantly different.
The test also indicates that the highest mean NO3-N
concentration in both ponding and drainage water was
observed in the BUF treatment, followed by UHN_RD,
UHN_HRD, and CNT treatments.
P Concentration. The ortho-P concentration in ponding
water attained a peak 2 days after fertilizer application (Figure
8), but the magnitude under different fertilizers was
significantly different (Table 5). In the CNT treatment, the
concentration of ortho-P was very low compared to other
fertilizer treatments; there were mild peaks at 0.07 and 0.352
ppm in ponding water and leachate, respectively. The effect of
fertilizer treatments on P concentrations in ponding water and
leachate was significantly different (Table 5). In ponding water
108
for all treatments, high concentrations of P were observed on
the first day of fertilization, which indicates the availability of
ortho-P; after that, the concentration gradually declined due to
plant uptake, P leaching, and irrigation application. The highest
peak was observed under the BUF (SSP fertilizer) treatment in
ponding water with 4.13−7.23 ppm. These high ortho-P
concentrations increase P availability possibly due to urea
hydrolysis, which inhibits the precipitation of insoluble
phosphates.50
In comparison, the peak in nanofertilizer treatments ranges
from 4−4.7 ppm in UHN_HRD and 3.6 to 6.19 ppm in
UHN_RD. There was a sudden decline in ortho-P
concentrations for all fertilizer treatments, but an extended-
release rate was observed in UHN_RD and UHN_HRD even
after irrigation, which may be due to the nanoparticle
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ACS Agricultural Science & Technology
properties of the HN material or due to the higher application
rate of P through N. Even though the application rate was
much higher in UHN treatments, the concentration of ortho-P
was higher in the BUF treatment in ponding water and
drainage. It was observed in the UHN treatment that there was
a 25% increase in ortho-P concentrations in UHN_RD
compared to UHN_HRD. The decrease of concentration in
ponding water does not increase the P concentrations in
leachate samples. The low P concentrations in leachate might
be due to the plant uptake and HN addition (nanofertilizer).
The bottom drainage shows an ortho-P concentration lower
than that in the ponding water in all fertilizer treatments. It was
observed that after 24 h of fertilizer application, leaching of
ortho-P occurs in the BUF treatment. However, in nano-
fertilizer treatments, the ortho-P leaching was highly
diminished and occurred at a very low peak of 0.07−0.59
ppm. The ortho-P concentrations in leachate were significantly
different; however, the total concentration among
UHN_HRD, UHN_RD, and CNT treatments was not
significantly different (Table 5). The ANOVA test confirms
the significant difference in ortho-P concentrations among all
treatments in ponding and drainage water. The Tukey test
shows that ortho-P concentrations in ponding and drainage
water were significantly different for CNT, BUF, and UHN
treatments; however, nanofertilizer treatments (UHN_HRD
and UHN_RD) were not significantly different. The test also
indicates that the highest mean ortho-P concentration in both
ponding and drainage water was observed in the BUF
treatment, followed by UHN_RD, UHN_HRD, and then
CNT treatments.
Nutrient Balance. N-balance. Table 6 presents the
nitrogen and phosphorus balance for all treatments. The
total N uptake of the rice crop from the fertilizer was 61.8, 102,
and 65% of the applied N for BUF, UHN_HRD, and
UHN_RD treatments. Li et al.51 and Shekhar et al.47 also
observed an average N plant uptake of 68−72 and 53%,
respectively, with the BUF treatment. The lowest plant uptake
was observed in the CNT treatment, with 9.8% uptake. In
CNT and UHN_HRD treatments, the uptake was taken
possibly from the soil reserve. The UHN_HRD indicates the
highest NUE for N among fertilizer treatments (76.5%),
followed by UHN_RD (52.2%) and BUF (49.5%). This
indicates a 3.1 and 27% increase in NUE with UHN_RD and
UHN_HRD treatments. Among the treatments, the N loss
through leaching was observed to be higher in BUF (67.57
mg/L), followed by UHN_RD (55.53 mg/L), UHN_HRD
(48 mg/L), and CNT (3.94 mg/L) treatments. Most of the N
nutrients were retained in the soil after harvesting the crop.
The change in soil N storage was −11.85, 16.7, −3.72, and
24.4% for CNT, BUF, UHN_HRD, and UHN_RD.
P-balance. The total P utilized by rice crop was 27.1, 20,
and 11.7% for BUF, UHN_HRD, and UHN_RD treatments,
respectively, of the applied P fertilizer. Nagumo et al.52
observed a P uptake of about 27% of applied P in rice crops,
and Beegle53 and Bhattacharyya et al.54 also documented that
the plant uptake of phosphorus is usually about 22−28%. The
percolation of water mainly drives the leaching of P with the
highest ortho-P leaching in the BUF treatment, while the
leaching was reduced by about 86.8 and 66.3% in UHN_HRD
and UHN_RD treatments, respectively. The rest of the applied
P was mostly retained in the soil, especially for nanofertilizer
treatments, where an increase in P concentration was observed
in the soil after harvesting the crop. The UHN_HRD
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treatment exhibited the highest NUE among fertilizer treat-
ments (14.27%), followed by BUF (11.14%) and then
UHN_RD (8.83%) treatments. The change in soil P storage
was −2.1, 5.3, 27.5, and 63.9% for CNT, BUF, UHN_HRD,
and UHN_RD. This can be attributed to a large amount of P
being held in soil because of the immobilization of P, or it can
be due to the change in soil pH creating rapid fixation
reactions with soil and other elements, which in turn limit
phosphorus availability.54 However, in the case of the UHN
treatment, it can also be due to the higher P concentration
applied. Other losses in the case of both N and P may be
attributed to the uptake by algae formed on the ponding water
of the column, the transformation of nutrients from one form
to another, the presence of small microbes and insects, or
consumption of water by birds. These are small factors that can
be prominent in the case of the column experiment due to the
smaller surface area of the column.
■ DISCUSSION
In this study, UHN has been used as a N and P source for rice
crops. The agronomical parameters such as tiller count, plant
height, and biomass responded positively toward conventional
and nanofertilizer treatments. Although statistically there was
no significant difference in the grain yield among fertilizer
treatments, the highest and lowest dry biomass and yield were
obtained from UHN_RD and CNT treatments, respectively
(Table 4). Since the grain yield among fertilizer treatments was
not significantly different, it indicates that UHN applied at half
of the recommended dose can yield other agronomical
parameters at par with the recommended dose of fertilizer
treatments. Kottegoda et al. investigated the effect of UHN on
rice crops and observed that the application of UHN at half the
recommended dose of N enhanced the yield by 6.9%
compared to urea applied to rice crops at recommended
levels.39 Their findings indicate that the application of N can
be reduced by 50% while maintaining N plant uptake and also
increasing the grain yield.39 Similarly, for the tea plant, 10−
17% increment in yield was observed when UHN was applied
at half the recommended dose of N.55 Furthermore, the
application of UHN at a recommended dose does not
significantly impact the yield and other agronomical parame-
ters, which were also observed in broad bean crops where
higher yields were obtained at a lower concentration (75 mg/
L) of UHN as compared to higher application rate (225 mg/
L).56
The NUE uptake is higher under UHN compared to the
BUF treatment in the case of N (Table 6), which can be
attributed to the bioavailability of the nanofertilizer due to the
slow release rate of urea from the HN, leading to a reduction in
the rate of urea decomposition in soil.39 Similarly, UHN-
treated rice seeds exhibited increased germination and a
significant amount of α-amylase activity compared to the CNT
and BUF counterparts.40 Correspondingly, the P uptake
increased significantly under UHN_HRD and UHN_RD
compared to BUF (Table 6) owing to the small size and
higher surface-to-volume ratio57 properties of the UHN and
also a higher concentration of P present in the UHN applied.
The increase in P uptake from HN was observed in lettuce57
and maize,58 while P uptake in rice crops from UHN was not
reported in the literature.
The leaching losses of N (NH4-N and NO3-N) and PO4-P
from the applied fertilizer were higher under the BUF
treatment as compared to UHN_HRD and UHN_RD
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ACS Agric. Sci. Technol. 2022, 2, 100−112
ACS Agricultural Science & Technology
treatments (Table 6), indicating that nanofertilizer treatments
in rice crops reduced the leaching of NH4-N, NO3-N, and
PO4-P. These lower concentrations of NH4-N, NO3-N, and
PO4-P indicated the slow-releasing properties of urea from
HN, which was also observed in soil plot trials.39 A significant
decline of ortho-P concentration in leachate was observed
despite a higher application rate in UHN treatments than in
the BUF treatment, which may be due to the adsorption/
fixation of P to the soil constituents as observed in soil column
studies,40 hybrid nanofertilizer for lady’s finger,59 and pot
studies of rice crop for urea−hydroxyapatite−montmorillonite
nanohybrids.41
Most of the N and P nutrients applied through UHN were
retained in the soil; however, in the UHN_HRD, the plant
uptake was higher than the N applied, indicating the uptake
from soil reserves. It can be observed that NH 4 -N
concentrations in ponding and leachate water were relatively
higher than those in NO3-N. Hence, it can be assumed that the
NH4-N concentration was strongly adsorbed to clay minerals
and organic matter present in the soil, thus increasing the P
retained in the soil.60 The retention of P in soil may indicate a
higher level of aluminum, iron oxides, or calcareous soil,61
where most of the P was added as HNs remained in the Ca-P
fraction.62 However, the release of P from the HNs can be
regulated by maintaining the pH.
Overall, the application of UHN as a nanofertilizer improves
plant agronomic parameters even at half the recommended
dose. It also reduces the leaching of N and P nutrients, and
there is a higher rate of plant uptake than the conventional
bulk fertilizer. The highest NUE was observed in the
UHN_HRD treatment for N and P nutrients, thus indicating
that the application rate can be reduced to half of the
recommended rate, which will reduce the nitrogen loss.
Moreover, increasing the application rate for UHN does not
significantly impact the yield. Therefore, excess UHN
application to soil may not be recommended since the study
revealed that the N and P nutrients are mostly retained in the
soil. Since the rice crop shows improved (UHN_RD) and at
par (UHN_HRD) yields compared to CNT treatments, UHN
could be used both as an N and P supplier and carrier of other
elements required by rice crops with the added benefits of
reduced leaching and increased NUE.
■ AUTHOR INFORMATION
Corresponding Author
Damodhara Rao Mailapalli − Associate Professor, Department
of Agricultural and Food Engineering, Indian Institute of
Technology Kharagpur, Kharagpur, West Bengal 721302,
India; orcid.org/0000-0003-3443-2461;
Email: mailapalli@agfe.iitkgp.ac.in
Author
Chwadaka Pohshna − Research Scholar, Department of
Agricultural and Food Engineering, Indian Institute of
Technology Kharagpur, Kharagpur, West Bengal 721302,
India
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsagscitech.1c00191
Notes
The authors declare no competing financial interest.
110
■
pubs.acs.org/acsagscitech Article
ACKNOWLEDGMENTS
The authors thank the Agricultural and Food Engineering
Department, Indian Institute of Technology Kharagpur, for
providing facilities for carrying out this research in the related
area.
■
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