Journal of Bioresources and Bioproducts 7 (2022) 116–127

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Journal of Bioresources and Bioproducts

journal homepage: http://www.keaipublishing.com/en/journals/journal-of-
bioresources-and-bioproducts/

Hydrochar-embedded carboxymethyl cellulose-g-poly(acrylic

acid) hydrogel as stable soil water retention and nutrient release
agent for plant growth
Yufei Zhang a,1, Xinyue Tian a,1, Qiuyue Zhang a,b, Huifang Xie a,∗, Bingyu Wang a,∗,
Yanfang Feng b
a
Jiangsu Key Laboratory of Chemical Pollution Control and Resources Reuse, School of Environmental and Biological Engineering, Nanjing
University of Science and Technology, Nanjing 210094, China
b
Key Laboratory of Agro-Environment in Downstream of Yangtze Plain, Ministry of Agriculture and Rural Affairs, Institute of Agricultural Resources
and Environment, Jiangsu Academy of Agricultural Sciences, Nanjing 210014, China

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

Keywords: The cellulose-based hydrogel has been widely applied for soil water retention and nutrient re-
Hydrogel lease agents for several decades. Embedding the inorganic materials into hydrogels is an excellent
Hydrochar strategy to improve the inherent limits of the cellulose-based hydrogel. Notably, municipal sludge-
Stable phosphorus-release
derived hydrochar (HC) has reduced the environmental burden and offered a potential hydrogel
Water retention
carrier to control water-retention and nutrient-release. However, the above function for plant
Plant growth
growth of hydrochar-embedded carboxymethyl cellulose-g-poly(acrylic acid) (CMC-g-PAA/HC)
is unknown, and relevant reports are lacking. This study investigated the water retention, nutri-
ent release behavior, and effect of germination and plant growth of CMC-g-PAA/HC hydrogel.
Characterization results showed that HC was successfully incorporated into CMC-g-PAA/HC with
6.0% higher thermostability, 7.2–21.0% lower swelling ratio (SR) in water, and substantial SR
in phosphate solution (P-solution). The water loss rate of CMC-g-PAA/HC in P-solution or wa-
ter owned a more significant temperature response (7.9–15.0 folds) than CMC-g-PAA (8.2–10.0
folds). Moreover, 4.0% higher n value and more 18.5% released P for CMC-g-PAA/HC were also
observed. These phenomena were due to restricting the polymer chains movement and the wa-
ter molecules diffusion inside the hydrogels with HC. Phytotoxicity assessments showed that HC
in CMC-g-PAA/HC could effectively alleviate the inhibition effects on rape germination retained
with 78.3% germination vigor and 80.0% germination ratio, even dramatically improved plant
growth to 28 d. The results of this study demonstrated a new route for developing eco-friendly
CMC-g-PAA/HC hydrogel, advantageous as a water retention agent and nutrient carrier in arid
and semiarid regions.

1. Introduction

Water and fertilizer are the two critical factors controlling crop yield; thus, soil moisture and nutrient management to reduce
water consumption and optimally use nutrients, especially for arid or semiarid regions, is critical to ensure crop yield (Wen et al.,
2016). Hydrogels with three-dimensional hydrophilic polymer networks could absorb water or aqueous solutions in their network

∗
Corresponding authors.
E-mail addresses: [email protected] (H. Xie), [email protected] (B. Wang).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.jobab.2022.03.003
Received 20 November 2021; Received in revised form 21 January 2022; Accepted 27 January 2022
Available online 24 March 2022
2369-9698/© 2022 The Author(s). Published by Nanjing Forestry University. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)
Y. Zhang, X. Tian, Q. Zhang et al. Journal of Bioresources and Bioproducts 7 (2022) 116–127

structures without loss of structural integrity (Chen and Chen, 2019; Liu et al., 2021c). Using hydrogels as soil amendments is a good
strategy applied in agricultural fields in arid or semiarid to improve crop yield, retain excessive irrigation water and plant nutrients,
and facilitate crop efficiency utilizing water and nutrients (Li and Chen, 2020a). The past several decades have witnessed encouraging
hydrogel application to large-scale agricultural land, reducing water scarcity and irrigation frequency, controlling fertilizer release
in soil, and promoting plant growth (Pushpamalar et al., 2018; Li and Chen, 2020b; Liu et al., 2021c). Therefore, many efforts have
been made to achieve functional hydrogels with well agricultural applications.
Cellulose has been widely studied as raw material to fabricate functional hydrogel because of its biocompatible and biodegradable
characteristics (Hashem et al., 2013; Bai et al., 2020). However, cellulose-based hydrogel usually had inherent limits for their further
applications, such as low gel strength, low tolerance to salt, and high production cost (Zhou et al., 2013; Dai et al., 2018). Therefore,
many kinds of inorganic materials, such as clays (Olad et al., 2018), metal oxide (Namazi et al., 2019), graphene oxide (Yan et al.,
2018), and biochar (An et al., 2020), were incorporated into hydrogels. Biochar has been intensively used in environmental restoration
and soil amendment (Yu et al., 2019a; Xiang et al., 2020) to improve soil water retention and plant nutrients, which is attributed to its
wealthy hydrophilic functional groups and high porosity (Dai et al., 2020; Wang et al., 2019a). For example, An et al. (2020) reported
a new biochar-embedded-semi-interpenetrating polymer network, exhibiting a much higher water-retention capacity, slower release
of nutrients, and a higher degradation ratio. Therefore, biochar was the candidate for improving porous structures and generating
abundant cross-linking points, responsible for improving the properties of cellulose and its derivatives.
Hydrothermal processing is an emerging technique of biochar production to treat waste with high moisture content, such as
municipal sludge (MS). The MS was an inevitable byproduct during municipal wastewater treatment and has been a secondary
environmental pollution source. The hydrothermal product, hydrochar (HC), retained plenty of nutrients, ash, and surface functional
groups, suitable as a soil amendment for promoting plant growth compared to pyrolytic biochar (Huang and Tang, 2016). Based
on this, the conversion of MS into MS-derived HC through hydrothermal processing reduced the environmental burden and offered
a potential hydrogel carrier to control water-retention and nutrient-release, especially for phosphorus (P)-release. The P is a vital
nutrient in crop yield with the most significant influence on limiting plant growth and development (Hosseini et al., 2021). Thus, the
functionality of P-release hydrogel could not only reduce P pollution problems but also improve P utilization efficiency. For example,
Fei et al. (2019) found that MS-derived HC could adsorb a high amount of phosphate and mediate soil P retention due to alternating
between P releasers and P adsorbents depending on the environmental P concentration. Most recent research centered on the effect of
incorporating traditional inorganic materials on the swelling ratio, water retention, thermal stability. According to this, MS-derived
HC-embedded cellulose hydrogel was speculated to hold great promise to combine the benefits of HC and cellulose when applied as
a soil water retention and nutrient release agent. To the best of our knowledge, little about the employment of MS-derived HC in
cellulose-based hydrogel preparation has been reported; moreover, the effect of HC-embedded cellulose hydrogel on plant growth
was still unclear and highly needed to clarify (Rashidzadeh et al., 2014; An et al., 2020).
Considering the potential use of HC-embedded carboxymethyl cellulose (CMC) hydrogels as soil amendments, a novel HC-
embedded CMC-g-poly(acrylic acid) (CMC-g-PAA/HC) composite hydrogel was synthesized by grafting PAA onto CMC and MS-derived
HC by the hydrothermal method in the present study. The characteristics and behaviors such as swelling and water retention un-
der different temperatures and mediums were analyzed. Effects of CMC-g-PAA/HC hydrogel on germination and growth were also
investigated.

2. Materials and methods

2.1. Materials

The HC was prepared from MS (collected from Nanjing East Sewage Treatment Plant, Jiangsu Province, China) in a closed self-
pressurized hydrothermal reactor for one hour at 220 °C. The obtained HC was dried at 90 °C and sieved through 2 mm (10 mesh) (Fu
et al., 2021). Sodium carboxymethyl cellulose (CMC-Na, Laboratory Reagent) and acrylic acid (AA, analytical grade) were purchased
from Chengdu Chron Chemicals Co., Ltd. N, N’-methylene bisacrylamide (MBA, analytical grade) was supplied by Rhawn Chemical
Technology Co., Ltd. Ammonium persulfate (APS, analytical grade) was supplied by XIYA Reagent Co., Ltd. All other chemicals were
analytical grade, and pure water was used. Market-bought rape seeds were used to carry out germination and growth experiments.

2.2. Preparation of CMC-g-PAA/HC hydrogel

The CMC-g-PAA/HC composite hydrogel was prepared in the hydrothermal reactor: 12wt% (according to AA) CMC and 0.6wt%
HC were added to deionized water (30 mL, deionized water). After CMC dissolution to form a homogeneous solution at 60 °C, nitrogen
(N2 ) was purged for 30 min to remove dissolved O2 . Then, 0.5wt% APS initiator aqueous solution (5 mL) was added to the mixture
and stirred for 10 min. When the temperature decreased to 50 °C, 7.2 g of AA (80% neutralization degree adjusted with 40% NaOH
solution) and 0.5wt% MBA were poured into the reactor. Then the reactor was sealed and put into the 80 °C oven for 3 h reaction. The
obtained product was rinsed with deionized water 3 times and dried at 70 °C, marked as CMC-g-PAA/HC. CMC-g-PAA was prepared
in the same procedure without the addition of HC.

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2.3. Characterization

The surface of hydrogel was characterized by using a field emission scanning electron microscope (FE-SEM, Hitachi S-4800,
Japan). The digital images and the microscope images of hydrogel were taken by using the smartphone and the optical microscope
with an imaging system (Olympus CX31, Japan), respectively. The surface functional groups of hydrogel were characterized by
Fourier transform infrared spectroscope (FT-IR, Nicolet iS5, USA) in the range of 4000–400 cm–1 with a resolution of 2 cm–1 . The
X-ray diffraction (XRD) measurements of hydrogel were carried out using an XRD (Bruker D8, Germany). Thermal stability analysis
of hydrogel was performed on thermal gravimetric analysis (TGA) by using a thermal gravimetric analyzer (TGA5500, USA) from 50
to 500 °C under N2 atmosphere at a heating rate of 10 °C/min.

2.4. Swelling and water retention measurement

Swelling and water retention behaviors are the basic characteristics of hydrogels as a soil water retention and nutrient release
agent, exhibiting multiple responses to external conditions, such as temperature and ambient media (Liu et al., 2021a). Thus, the
swelling and water retention of prepared hydrogels in deionized water and phosphate solution (P-solution, containing P 20 mg/L, pH
7.0) were measured at different temperatures.

2.4.1. Swelling measurement

The swelling ratio (SR) of hydrogel was measured using the tea-bag method (León et al., 2019) and calculated according to Eq.
(1). The tea-bag (a 100-mesh nylon screen) containing hydrogels (∼0.1 g) was immersed in excessive deionized water or P-solution
at 30, 60, and 90 °C, respectively. The tea-bag was hung up for 10 min to remove the excess aqueous solution and weighed per hour.
( )
𝑆𝑅 = 𝑚𝑡 − 𝑚0 ∕𝑚0 (1)

where SR is the swelling ratio of hydrogel (g/g); mt and m0 is the mass of swollen hydrogel at time t and initial hydrogel (g),
respectively.

2.4.2. Water retention measurement

Hydrogels were initially swelled up in tea-bags to equilibrium in deionized water and P-solution and subsequently weight. Then
swelled hydrogels were drying at 30, 60, and 90 °C, respectively, and weighted at several intervals (1–5 h). The value of water retention
(R) was calculated by Eq. (2):

𝑅 (%) = 𝑚𝑡 ∕𝑚eq × 100% (2)

where mt and meq are the mass of swollen hydrogel at time t and equilibrated hydrogel (g), respectively.

2.5. P release experiment

The P release experiments of P-loaded hydrogels were conducted to investigate the P nutrient release. The P-loaded hydrogel
was prepared by immersing dried hydrogel (∼100 mg) in tea-bags in a P-solution for 10 h at room temperature. The sorbed P in the
hydrogels were calculated according to the concentration of the prepared P-solution and the SR determined at equilibrium. Then, the
P-loaded hydrogel was hung in deionized water (500 mL) under slowly stirring for 0.5 h, fresh deionized water was pumped at the
rate of 5.0 mL/min by a peristaltic pump, and a fraction collector collected a water sample per 5 min. The P release in deionized water
was determined following a spectrophotometric metric method (GB 11893-89, China) using an ultraviolet-visible spectrophotometer
(UV-2600, Sunny Hengping, China).

2.6. Plant germination and growth experiment

The effects on plants are obvious when hydrogels are used in soil, so the germination and growth experiments of rape seeds were
carried out.

2.6.1. Effects on plant germination

Cotton was spread at the germination box and soaked with 50 mL of deionized water. Then, 0.1 g of hydrogel particles were placed
evenly on the cotton for 10 h. After swelling equilibrium, 30 seeds were scattered on the surface and germinated in a growth chamber
at 25 °C. Controls without adding hydrogels were carried out at the same time. The germination vigor (GV) and germination ratio
(GR) were calculated according to Eqs. (3) and (4):

𝐺𝑉 (%) = (Germinated seeds at Day3∕Total seeds) × 100% (3)

𝐺𝑅 (%) = (Germinated seeds at Day7∕Total seeds) × 100% (4)

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Fig. 1. Schematic process of preparation of hydrochar-embedded carboxymethyl cellulose-g-poly(acrylic acid) (CMC-g-PAA/HC).

2.6.2. Effects on plant growth and water retention of soil with hydrogels
Two groups of pot experiments were performed to compare and analyze the effects of hydrogel on plant growth and water
retention of soil. The pot experiments chose deionized water (Group I, with nutrient soil and vermiculite) and P-solution (Group II,
with vermiculite).
For Group I, the soil was a mixture of vermiculite and nutrient soil (w꞉w = 10꞉1), and water was the main factor affecting plant
growth. At first, 0.5 g of dry hydrogel was swollen with deionized water in tea-bag, and the sorbed water was weighted. Then the
swollen hydrogel was placed under a 30 g mixture of soil. The 15 rape seeds were sown in each pot, and deionized water was added
to maintain the total water (including free water and the sorbed water in swollen hydrogel) of 80 mL. Two groups of control (CK1 and
CK2) without adding hydrogels were carried out simultaneously. In the CK1 group, water (80 mL) was added to each pot. In the CK2
group, only the same amount of free water (80 mL, the amount of sorbed water in swollen hydrogel) was added to the corresponding
pot. After growing for 28 d, the GR was calculated, the mass of pot, including hydrogel, solution, and soil, was weighed every day
(mis ), the stems were collected to measure the length and dry mass.
For Group II, the 30 g of vermiculite was used, and the water in the system was taken place by the P-solution. Both P nutrient and
water released from hydrogel will affect plant growth. The other steps were the same as Group I. All the treatments were carried out
in triplicate. The water retention in the soil Ris was calculated by Eq. (5) (Wu et al., 2012):

𝑅is (%) = 𝑚is ∕𝑚0s × 100% (5)

where m0s is the initial weight of pot at day 0; mis is the weight of pot at different days.

3. Results and discussion

3.1. Preparation and characterization of CMC-g-PAA/HC

The CMC-g-PAA/HC hydrogels were fabricated via a free radical polymerization with CMC and AA as monomers, MBA and HC as
a crosslinking agent, and APS as an initiator (Fig. 1). During the preparation of CMC-g-PAA/HC, the radicals were formed because
the sulfate anion radicals decomposed from initiator APS extracted hydrogen from the -OH group of CMC or HC. Then, monomer
AA closed to the reaction sites was the accepter of radicals to result in chain initiation, which converted into free radical donors
at the neighboring molecules and extended the chain. Next, the end vinyl groups of the crosslinker MBA and surface functional
groups of HC acting as the multi-functional crosslinking agent were reacted with chains, similar to the roles of clays in the hydrogel
modification process (Da and Huang, 2017; Wang et al., 2017). The CMC-g-PAA/HC hydrogel was facilely synthesized by crosslinking
and grafting AA onto CMC and HC in the hydrothermal reactor. Thus, HC could be loaded into polymers during the propagation of the
chain.
The SEM image of HC in Fig. S1a illustrated that the surface morphology of HC is relatively irregular. The XRD patterns of HC in
Fig. S1b showed no prominent peaks, declaring that the HC possessed a feeble crystallization degree. The FT-IR spectrum of HC in
Fig. S1c proved that the HC possessed –OH (3340 cm–1 ), C=O (1710 cm–1 ), C=C (1570 cm–1 ), −COO− (1450 cm–1 ) surface functional

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Fig. 2. (a) Digital (1 ×) and (b) scanning electron microscope (SEM) images of CMC-g-PAA and hydrochar-embedded CMC-g-PAA (CMC-g-PAA/HC)
before swelling; (c) Digital (1 ×) and (d) microscope (400 ×) images of CMC-g-PAA and CMC-g-PAA/HC after swelling.

groups. Besides, the band at around 997 cm–1 was assigned to Si–O–Si and C–O stretching (Liu et al., 2021b). The TGA curve of HC
was depicted in Fig. S1d, only showing a 27.33% weight loss from 50 to 500 °C and representing the excellent thermostability of HC.
The ultimate analysis determined that the HC contained 1.69% nitrogen, 27.05% carbon, 3.60% hydrogen, 4.87% sulfur, and 5.12%
oxygen elemental composition. The proximate analysis of HC determined that a high ash content (62.54%) was contained in HC,
consistent with good thermostability of HC.
The CMC-g-PAA and CMC-g-PAA/HC hydrogels were small block shape before swelling (Fig. 2a). As seen from the SEM image
of CMC-g-PAA/HC before swelling, HC was distributed on the hydrogel surface (Fig. 2b). After swelling, the HC was distributed
uniformly in the hydrogels (Fig. 2c) and adhered to the hydrogel particles (Fig. 2d). The band of CMC at around 3340 cm–1 was
due to the abundance of O–H and N–H in CMC (Fig. 3a). Compared with the spectrum of CMC, the band of CMC-g-PAA and CMC-g-
PAA/HC at around 3340 cm–1 showed apparent broader changes due to the absorption of –OH groups in AA (CH2 =CHCOOH) observed
at around 3340 cm–1 (Zhang et al., 2016). The more substantial peak at around 2982 cm–1 in CMC-g-PAA and CMC-g-PAA/HC was
attributed to the stretching vibrations of methyl and methylene groups, indicating the successful polymerization of AA into PAA and
formation of the network by MBA (Nakasone and Kobayashi, 2016). At the same time, the new band at approximately 1670 cm–1
(C=O stretching) was observed in CMC-g-PAA and CMC-g-PAA/HC, confirming the PAA chains grafting onto the CMC backbone.
The band related to the asymmetric stretching vibration of –COO− groups shifted from 1580 cm–1 to 1550 cm–1 , which indicated
the introduction of PAA into the graft polymer composite. The band intensity at 1451 cm–1 of CMC-g-PAA was enhanced than CMC,
attributed to the symmetric stretching vibration of –COO− groups (Bao et al., 2011; Wen et al., 2016). Moreover, the band intensity
at 1451 cm–1 of CMC-g-PAA/HC was continued to enhance than CMC-g-PAA, mainly attributed to the symmetric stretching vibration
of –COO− groups in HC.
As seen in Fig. 3b, CMC exhibited a strong peak at about 2𝜃 = 20° corresponding to the typical diffraction peaks of the CMC in the
XRD pattern. Compared with CMC, the peak at 2𝜃 = 20° dramatically decreased in intensity for CMC-g-PAA and wholly disappeared
for CMC-g-PAA/HC, which indicated that AA and HC would participate in the grafting reaction and dispersed randomly inside the
hydrogels in the amorphous phase. In conclusion, it could be confirmed that AA was successfully grafted and HC was homogeneously
embedded by the photographs, SEM images, FT-IR, and XRD.
The TGA and derivative thermo gravimetric (DTG) curves were depicted in Fig. 3c,d. For CMC, the weight-loss stage mainly
appeared from 270 °C to 310 °C in the TGA curve and the peak at 292 °C in the DTG curve, attributed to the thermal degradation
of functional groups (−COOH and –OH group) in CMC (Da and Huang, 2017). This peak became weak and shifted to 261 °C for
CMC-g-AA and disappeared for CMC-g-PAA/HC. The reason might be that more functional groups participate in the grafting reaction
in CMC-g-PAA/HC. This result was consistent with kaolin/sepia ink-loaded cellulose-g-AA hydrogel (Da and Huang, 2017). The DTG
curves of prepared CMC-g-PAA and CMC-g-PAA/HC showed the first peak at around 92 °C and 81 °C, respectively, corresponding
to the adsorbed or bound water loss. Furthermore, both CMC-g-PAA and CMC-g-PAA/HC were found to have a new weight-loss
stage from 435 °C in TGA curves and the corresponding new peaks at about 455 °C in DTG curves. These results were blamed for
the formation of anhydride, the scission of the main chain, and the breaking of cross-linked network structure (Bao et al., 2011).
Compared with good thermostability of HC (a 27.33% weight loss), CMC-g-PAA and CMC-g-PAA/HC retained 57.9% and 54.4%
weight loss, respectively, which demonstrated that the thermostability of CMC-g-PAA/HC was enhanced due to the addition of HC,
similar to the results reported by the insertion of clay particles (Da and Huang, 2017; He et al., 2019).

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Fig. 3. (a) Fourier transform infrared spectroscope (FT-IR) spectra, (b) X-ray diffraction (XRD) patterns and (c) thermal gravimetric analysis (TGA)
curves and (d) derivative thermo gravimetric (DTG) curves of carboxymethyl cellulose (CMC), hydrochar (HC), CMC-g-PAA and CMC-g-PAA/HC.

3.2. Swelling, water retention and P release behavior

3.2.1. Swelling of CMC-g-PAA and CMC-g-PAA/HC

The dynamics swelling behaviors of hydrogels under the deionized water and the P-solution were carried out at different temper-
atures, as depicted in Fig. 4a,b. In deionized water, the SR values of CMC-g-PAA and CMC-g-PAA/HC increased with temperature,
and CMC-g-PAA responded to temperature much more obviously than CMC-g-PAA/HC. The CMC-g-PAA/HC showed a similar SR as
CMC-g-PAA at 30 °C while SR values at 60 °C and 90 °C were lower than CMC-g-PAA. This result was consistent with previous studies
that reported that several kinds of clay would decrease the swelling capacity of the polymer-inorganic particles (Gao et al., 2016;
Wang et al., 2017). This phenomenon is mainly attributed to the presence of inorganic particles in the hydrogel networks, which
may restrain the interactions between hydrogel and water or restrict polymer chains’ movement, resulting in decreased SR (Patra et
al., 2010; Bao et al., 2011; Haraguchi et al., 2015). Noteworthily, CMC-g-PAA and CMC-g-PAA/HC had similar swelling behaviors
in the P-solution. The P-solution decreased the SR value of CMC-g-PAA dramatically at 90 °C than deionized water; however, CMC-
g-PAA/HC showed similar SR values in P-solution and water, indicating that CMC-g-PAA/HC had better phosphate tolerance than
CMC-g-PAA due to the HC as suitable carriers of P-solution.
The swelling data are usually described by using the following equation proposed by Ritger and Peppas as Eq. (6) to determine
the water diffusion type in the hydrogel (Rashidzadeh et al., 2014). The observed swelling kinetics for both hydrogels are similar,
and the obtained data in Fig. 4a,b were fitted well to the model.

𝑚𝑡 ∕𝑚eq = 𝑘s 𝑡𝑛 (6)

where mt and meq is the amount of water uptake at time t and the equilibrium time (g/g), respectively, ks is the diffusion constant
(h−1 ), and n describes the type of diffusion mechanism.

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Fig. 4. Swelling ratio (SR) and water retention (WR) of CMC-g-PAA and CMC-g-PAA/HC at different temperatures (30 °C, 60 °C, and 90 °C). (a) SR
in pure water; (b) SR in P-solution; (c) WR for water-loaded swollen hydrogels; (d) WR by P-loaded swollen hydrogels; (e) The P-release ratio for
P-loaded CMC-g-PAA and CMC-g-PAA/HC in water (w and weq are the mass of preloaded P swollen hydrogel at time t and equilibrate time (g)).

According to the classification of the water diffusion type, n ≤ 0.5 represents the Fickian diffusion mechanism, corresponds to a
slower water diffusion rate compared with the relaxation rate of hydrogels; 0.5 < n < 1.0 represents the non-Fickian or anomalous
diffusion, which indicates both diffusion and polymer relaxation mechanisms are operative; n = 1.0 means case-II diffusion (relaxation-
controlled diffusion), corresponds to a faster water diffusion rate compared to relaxation rate of hydrogels; and n > 1.0 means the
supercase-II diffusion (Patil et al., 2018; Zhou et al., 2019). According to the fitted results in Table 1, the n values were 0.695–0.816 for
CMC-g-PAA and 0.715–0.927 for CMC-g-PAA/HC, reflecting that the diffusion mechanism is of a non-Fickian diffusion. The diffusion
constant ks indicated the water diffusion rate, also known as the swelling rate of the hydrogels in this study (Kumar et al., 2015;
Wang et al., 2019b). It was shown that the highest swelling rate of CMC-g-PAA and CMC-g-PAA/HC was in the water at 60 °C, and
the swelling rate was increased from 30 °C to 90 °C in the P-solution. The CMC-g-PAA/HC hydrogel had a lower swelling rate than
CMC-g-PAA, indicating that HC particles in the hydrogel networks maybe restrict the movement of polymer chains and the diffusion
of water molecules inside the hydrogels. Although, the presence of HC resulted in a lower swelling rate in the water and P-solution

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Table 1
Swelling kinetic parameters for CMC-g-PAA and CMC-g-PAA/HC.

CMC-g-PAA CMC-g-PAA/HC
Medium Index
30 °C 60 °C 90 °C 30 °C 60 °C 90 °C

Water ks (h−1 ) 0.273±0.009 0.328±0.029 0.277±0.005 0.253±0.036 0.307±0.044 0.262±0.030

n 0.811±0.025 0.706±0.054 0.816±0.006 0.870±0.095 0.754±0.082 0.861±0.060
R2 0.9959 0.9945 0.9750 0.9897 0.9888 0.9816
P-solution ks (h−1 ) 0.279±0.033 0.305±0.025 0.334±0.019 0.226±0.001 0.279±0.022 0.321±0.031
n 0.806±0.068 0.740±0.053 0.695±0.043 0.927±0.002 0.796±0.052 0.715±0.057
R2 0.9915 0.9965 0.9790 0.9942 0.9865 0.9828

Note: ks is the diffusion constant (h−1 ).

Table 2
Deswelling kinetic parameters for CMC-g-PAA and CMC-g-PAA/HC.

CMC-g-PAA CMC-g-PAA/HC
Medium Index
30 °C 60 °C 90 °C 30 °C 60 °C 90 °C

Water kr 0.048±0.016 0.186±0.030 0.479±0.005 0.043±0.005 0.317±0.063 0.647±0.065

R2 0.9409 0.9957 0.9424 0.9423 0.9858 0.9552
P-solution kr 0.045±0.013 0.188±0.036 0.367±0.033 0.073±0.006 0.238±0.044 0.578±0.050
R2 0.8878 0.9888 0.9916 0.8700 0.9890 0.9724

Note: kr is the rate constant.

of CMC-g-PAA/HC compared with CMC-g-PAA, CMC-g-PAA/HC still held well SR characteristics in the P-solution and faster swelling
rate in higher temperature, proving that the addition of HC particles was highly feasible for agricultural and horticultural applications
and the CMC-g-PAA/HC hydrogel could be used as carriers of P-containing solution in hot and arid areas.

3.2.2. Water Retention of CMC-g-PAA and CMC-g-PAA/HC

Water retention is one of the vital characters of hydrogels for agriculture and horticulture application; thus, the water retention
for swollen in water and P-loaded hydrogels were investigated as Fig. 4c,d. Gao et al. (2016) synthesized a series of superabsorbents
by graft co-polymerization of AA, wheat bran, and various clays, and the superabsorbent was reserved 61%–85% at 60 °C for 1 h. This
study was also conducted at this condition (at 60 °C for 1 h). It was found that water-swollen CMC-g-PAA and CMC-g-PAA/HC reserved
83% and 78% of the absorbed water; the reserved water in P-loaded hydrogels was 81% for CMC-g-PAA and 80% for CMC-g-PAA/HC,
respectively. The data in Fig. 4c,d were fitted well to the first-order kinetics Eq. (7) (Wang et al., 2017):

𝑚𝑡 ∕𝑚𝑒𝑞 = 𝑒−𝑘r 𝑡 (7)

where mt and meq are the mass of swollen hydrogel at time t and equilibrated hydrogel (g), respectively; kr is the rate constant, and
the fitted results are listed in Table 2.
Water retention during deswelling was related to hydrogen bonds and Van der Waal’s force interaction between the hydrogel
networks and water molecules (Patra et al., 2010). The interactions weakened or disrupted at higher temperatures (Wang et al.,
2017). As shown in Table 2, both swollen in water and P-loaded hydrogels showed increased water loss rate (kr ) with increased
temperature, and CMC-g-PAA/HC responded temperature more obviously (7.9–15.0 folds) than CMC-g-PAA (8.2–10.0 folds). The
results revealed that incorporating HC might make the interaction between the hydrogels networks and water molecules more easily
weakened or disrupted in swollen CMC-g-PAA/HC, consistent with CMC-g-PAA/HC swelling characteristic.

3.2.3. P release of P-loaded CMC-g-PAA and CMC-g-PAA/HC

The stable release of nutrients is essential for applying nutrients-loaded hydrogels, so the P release behaviors of P-loaded hydrogels
were investigated and shown in Fig. 4e. After 150 min, about 27% and 32% of preloaded P were released from CMC-g-PAA and CMC-
g-PAA/HC, respectively. Moreover, CMC-g-PAA/HC showed a more stable release than CMC-g-PAA. Data in Fig. 4e were also fitted
well to the Ritger and Peppas model, Eq. (8) (Ritger and Peppas, 1987):

𝑤𝑡 ∕𝑤eq = 𝑘p 𝑡𝑛 (8)

where wt and weq are the mass of preloaded P swollen hydrogel at time t and equilibrate time (g), kp is a release factor, and n is the
diffusion parameter. The n values (0.843–0.877) showed that the P release mechanism was a non-Fickian diffusion. The 4.0% higher
n and more 18.5% released P for CMC-g-PAA/HC maybe due to the weaker interactions between hydrogels and water in swollen
hydrogels in CMC-g-PAA/HC than that in CMC-g-PAA (Zonatto et al., 2017).

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Table 3
Water retention in soil kinetic parameters for CMC-g-PAA and CMC-g-PAA/HC.

Medium Index CK1 CK2 CMC-g-PAA CMC-g-PAA/HC

Water kis 0.060 ± 0.001 0.055 ± 0.001 0.029 ± 0.002 0.033 ± 0.002
R2 0.9465 0.9973 0.9540 0.9884
P-solution kis 0.059 ± 0.001 0.058 ± 0.001 0.031 ± 0.003 0.038 ± 0.001
R2 0.9402 0.9859 0.9635 0.9845

Notes: kis is the rate constant; CK1 represents the addition of 80 mL of water to each
pot; CK2 represents adding the same free water (80 mL, the amount of adsorbed water in
swollen hydrogel) to each pot.

3.3. Phytotoxicity of CMC-g-PAA and CMC-g-PAA/HC

It was reported that acidic PAA hydrogels showed inhibition to germination of zoospores originating from Laminaria angustata
(Katsuyama et al., 2002). Thus, the phytotoxicity of the hydrogels was assessed in soilless conditions by rape germination in Fig.
5a,b. The actual pictures of germination in soilless conditions at day 3 are shown in Fig. S2. Compared with CK, CMC-g-PAA hydrogel
showed apparent inhibition to the germination of rape when the seeds were contacted directly with CMC-g-PAA. The GV and GR of
CMC-g-PAA decreased from 80.0% and 86.7% to 56.7% and 60.0%, respectively. Interestingly, the adverse effects were alleviated for
CMC-g-PAA/HC due to the embedding of HC, and GV and GR only decreased to 78.3% and 80.0%, respectively. Thus, the reason for
reducing the phytotoxicity was due to its plenty of ash content in HC (62.54%) that could neutralize the acidic CMC-g-PAA hydrogel,
consistent with the finding of Katsuyama et al. (2002).
In order to reduce the adverse effects, the swollen hydrogels in tea bags were buried in soil conditions, and there was no direct
contact between the seeds and hydrogels. As shown in Fig. 5c,d, CMC-g-PAA also inhibited the rape germination ratio in two groups.
The actual pictures of germination in soil conditions at day 14 are shown in Fig. S3. Consistent with the previous result, the inhibition
effects were also alleviated for CMC-g-PAA/HC due to the presence of HC. Moreover, a negligible decrease in the average length of
stem and dry mass was observed for geminated plants between adding treatments and controls in Fig. 5e–h. Compared with CMC-
g-PAA, the promoting effects of CMC-g-PAA/HC were observed, indicating that HC embedded in hydrogels was beneficial for plant
germination. These results were also confirmed by the positive effects of HC on plant growth promotion and water retention (Abel
et al., 2013; Yu et al., 2019b).

3.4. Water retention with hydrogels in soil

It is crucial to study the water retention properties of hydrogels in soil for agriculture application. Fig. 6 depicted the water-
retention changes in CMC-g-PAA and CMC-g-PAA/HC hydrogels during plant growth. Both CMC-g-PAA and CMC-g-PAA/HC hydrogels
could improve the water retention capacity (Ris ) calculated by Eq. (5) in soil conditions with water and P-solution, similar to the
previous study (Chen and Chen, 2019). The data in Fig. 6 were fitted well to the first-order kinetics Eq. (9):
𝑚is ∕𝑚0s = 𝑒−𝑘is 𝑡 (9)
where m0s is the initial pot weight at day 0; mis is the pot weight at different days; kis is the rate constant, and the fitted results are
listed in Table 3. The results showed that CMC-g-PAA/HC in soil condition had a moderate water loss rate constant (kis ) and water
retention capacity (Ris ) between CKs and CMC-g-PAA treatments.
The CK1, including the addition of 80 mL water (Group I) or P-solution (Group II), supported the plant growth for 20 d. In
contrast, the CK2, including the same amount of free water (∼43 mL in Group I) or P-solution (∼43 mL in Group II), could only
support the plant growth for 16 d due to the water scarcity hindered plant growth. Thus, swollen hydrogels could be the available
soil water reservoir of the plant. It is worth noting that the water scarcity in soil conditions was alleviated with CMC-g-PAA and
CMC-g-PAA/HC hydrogels in water. For example, Ris was 61.25% and 54.45% for CMC-g-PAA and CMC-g-PAA/HC at 16 d in water
(Group I), noticeably higher than 34.91% and 39.40% in CK1 and CK2. Moreover, CMC-g-PAA prolonged the plant growth period to
22–23 d, and CMC-g-PAA/HC notably supported the plant growth of more than 28 d. Similar water loss trends were observed in the
P-solution (Group II), illustrating that CMC-g-PAA/HC showed the most sustainable supporting effects on the growth of rape.
Soil moisture management, especially in arid or semiarid regions, is critical to ensure crop yield (Wen et al., 2016). As discussed
above, swollen hydrogels could hold water because of hydrogen bonding and Van der Waal’s force (Patra et al., 2010). However, it
might be difficult for plants to use the water when absorbed strongly inside the hydrogel. The presence of HC maintained a suitable
hydration level for the plant during the water loss period. The price of major raw materials in China were list in Table S1 and the
material cost of CMC-g-PAA according to the average price was about 6900 yuan (RMB)/t. As the resource product of wastewater
treatment sludge by hydrothermal technology, HC has no commercial products on the market by now; thus, it is not easy to accurately
evaluate the price of CMC-g-PAA/HC. Based on the current sludge disposal cost (200 yuan (RMB)/t wet sludge with 80% moisture
content) and dosage in preparation of CMC-g-PAA/HC, HC only accounts for about 1.2% of the raw material cost; based on the
average commercial biochar price (860 yuan (RMB)/t) in China, HC accounts for about 5.2% of the raw material cost (Table S1).
However, the addition of HC did not require a significant adjustment of the producing process of CMC-g-PAA but slightly raised the

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Y. Zhang, X. Tian, Q. Zhang et al. Journal of Bioresources and Bioproducts 7 (2022) 116–127

Fig. 5. Effects of CMC-g-PAA and CMC-g-PAA/HC on the germination vigor (GV) (a) and germination ratio (GR) (b); on the germination in soil
with water (c) and phosphorus/P-solution (d); length of the stem in soil with water (e) and P-solution (f); mass of plant in soil with water (g) and
P-solution (h). The CK represents the water without adding hydrogel. CK1 represents the addition of 80 mL water to each soil pot. CK2 represents
the addition of the same free water (80 mL, the amount of adsorbed water in swollen hydrogel) to each soil pot.

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Y. Zhang, X. Tian, Q. Zhang et al. Journal of Bioresources and Bioproducts 7 (2022) 116–127

Fig. 6. Water-retention capacities of soil with CMC-g-PAA and CMC-g-PAA/HC. (a) Group of water (Group I); (b) Group of P- solution (Group II).
The CK1 represents the addition of 80 mL of water to each pot; CK2 represents adding the same free water (80 mL, the amount of adsorbed water
in swollen hydrogel) to each pot.

yield (0.4%); thus, the raw material cost of CMC-g-PAA/HC is flat with CMC-g-PAA. At present, the price of superabsorbent polymers
used in agriculture and horticulture in China is approximately 10 000 yuan (RMB)/t (Table S1). Therefore, CMC-g-PAA/HC in this
study has potential competitiveness in the market. Therefore, our results showed that the existence of HC in the CMC-g-PAA/HC
hydrogel was advantageous for the potential use of hydrogels in agriculture as a water and nutrient carrier.

4. Conclusion

A novel CMC-g-PAA/HC hydrogel was synthesized with the facile hydrothermal method. Characterization results proved the
successful incorporation of HC into the crosslinking structure and higher thermostability. The water transport in CMC-g-PAA/HC
exhibited non-Fickian diffusion with a 7.2%–21.0% lower SR in water and substantial SR in P-solution. Moreover, the water loss rate
of CMC-g-PAA/HC owned a more significant temperature response (7.9–15.0 folds) than CMC-g-PAA (8.2–10.0 folds). Furthermore,
germination and growth experiments showed that CMC-g-PAA/HC was retained with 78.3% GV and 80.0% GR and dramatically
improved plant growth to 28 d. The results indicated that as-prepared eco-friendly CMC-g-PAA/HC could be a water retention agent
and nutrient carrier in arid and semiarid regions.

Declaration of Competing Interest

There are no conflicts to declare.

Acknowledgments

This work was funded by the National Undergraduate Training Program for Innovation and Entrepreneurship (No.
202010288024Z), National Natural Science Foundation of China (No. 42107398), Natural Science Foundation of Jiangsu Province
(BK20210358), and China Postdoctoral Science Foundation (2020M68618).

Supplementary materials

Supplementary material associated with this article can be found, in the online version, at doi:10.1016/j.jobab.2022.03.003.

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