Methyl Cenlulozo

International Journal of Biological Macromolecules 221 (2022) 398–415
Contents lists available at ScienceDirect
International Journal of Biological Macromolecules

journal homepage: www.elsevier.com/locate/ijbiomac
Methylcellulose/lignin biocomposite as an eco-friendly and multifunctional

coating material for slow-release fertilizers: Effect on nutrients
management and wheat growth
Fatima-Zahra El Bouchtaoui a, El-Houssaine Ablouh a, *, Manal Mhada b, Ihsane Kassem a,
Mohamed Hamid Salim a, Salma Mouhib b, Zineb Kassab a, Houssine Sehaqui a,
Mounir El Achaby a, *
a
Materials Science, Energy and Nanoengineering Department (MSN), Mohammed VI Polytechnic University (UM6P), Lot 660 – Hay Moulay Rachid, Benguerir 43150,
Morocco
b
AgroBioSciences Department (AgBS), Mohammed VI Polytechnic University (UM6P), Lot 660 – Hay Moulay Rachid, Benguerir 43150, Morocco
A R T I C L E I N F O A B S T R A C T
Keywords: To obviate adverse effects from the non-biodegradability of certain polymer-based slow-release fertilizers (SRFs)
Slow-release fertilizer and to offset higher operational costs, the use of biopolymers as coating material has recently caught interest in
Biopolymers the research circles. The present work aims to design a sustainable coating material based on biodegradable
Coating
polymers. To this end, Alfa plant was initially exploited as a viable sustainable source for the extraction of lignin
Lignin
Biodegradation
(LGe), which was in turn integrated into the development of a three-dimensional cross-linked network, including
Wheat crop methylcellulose (MC) as a matrix and citric acid (CA) as a cross-linking agent. Then, the designed coating ma
terial was applied onto Di-ammonium Phosphate (DAP) and Triple Superphosphate (TSP) water-soluble fertil
izers in a rotating pan machine. Chemical, physical, and biodegradation studies have confirmed that the coating
material is environmentally-friendly. Nutrients release experiments in water as well as in soil environments have
proved the effectiveness of the MC and MC/LGe coating layers in delaying the nutrients discharge. Besides, the
nutrients release from coated DAP and TSP lasted longer than 30 days. Furthermore, the coating film enhanced
the fertilizers mechanical resistance and boosted the soil water retention capacity. The agronomic evaluation has
also confirmed their remarkable potential in enhancing wheat leaf area, chlorophyll content and biomass, in
addition to the roots architecture and the final fruiting efficiency. These results showed that this hybrid com
posite could be used as an efficient coating material to produce slow-release fertilizers with multifunctional
performances.
1. Introduction developed to enhance nutrients use efficiency and to achieve sustainable

and efficient application [6,7]. Besides, they decrease the frequency of
Fertilizers play an essential role in improving crop production to fertilizer applications because of their long-lasting effects [8], which in
meet the increasing world population expansion [1], however the con turn greatly reduce both time and energy consumption [9]. Slow-release
flict between human population and the limited land for crop farming fertilizers (SRFs) can be classified into two basic categories: compounds
(due to urbanization, industrialization, desertification, etc.) has become of low solubility and coated or encapsulated water-soluble fertilizers
a widespread concern [2]. As a result, farmers are applying enormous [10]. To date, various materials have been exploited to produce SRFs,
quantities of fertilizers to maximize the agricultural yield [3]. Never including polymer-coated fertilizers. Numerous petroleum-based syn
theless, the immediate dissolution drives these fertilizers toward many thetic polymers, such as polyurethane, polyvinyl chloride, polysulfone,
losses via rain, irrigation, volatilization, etc. [4]. Hence, nutrients could and polyacrylate [11–13] have served as coating materials to physically
not be fully absorbed by the crops [5]. To alleviate these issues, the so- encapsulate water-soluble fertilizers. Unfortunately, most of these
called controlled/slow-release fertilizers (C/SRFs) have been widely polymers require organic solvents to dissolve, which is harmful to the
* Corresponding authors.
E-mail addresses: elhoussaine.ablouh@um6p.ma (E.-H. Ablouh), mounir.elachaby@um6p.ma (M. El Achaby).
https://doi.org/10.1016/j.ijbiomac.2022.08.194
Received 21 June 2022; Received in revised form 20 August 2022; Accepted 30 August 2022
Available online 5 September 2022
0141-8130/© 2022 Elsevier B.V. All rights reserved.
F.-Z. El Bouchtaoui et al. International Journal of Biological Macromolecules 221 (2022) 398–415
environment [14,15]. Furthermore, after the total nutrients consump Methyl Cellulose (MC, Viscosity 400 cPs, CAS number: 9004-67-5) was
tion, a huge amount of non-functional polymer (residues) remains in the purchased from Alfa Aesar. Citric acid monohydrate (CA, CAS No.5949-
soil, estimated to approximately 50 kg/ha per year [16]. The resultant 29-1) was supplied from ENSIGN. Both chemical products were used
environmental pollution and economical inefficiency limit the market without further purification. The fertilizers used in this study are the Di-
expansion of these polymers [17], as they are harmfully impacting the ammonium Phosphate (DAP) and Triple Super Phosphate (TSP). Their
soil fertility and inducing losses of agricultural lands [18]. As an effi average diameter varies between 2 and 4 mm, and they were provided
cient, safe, and green alternative, polysaccharide-based composites, by OCP Group, Morocco.
blends, or mixtures represents a new category of environmentally
friendly materials for agricultural applications, owing to their abun
dance, renewability, nontoxicity, low cost, and biodegradability 2.2. Extraction of lignin from alfa fibers
[19–22]. Among various available biopolymers and polysaccharides,
lignin is one of the most abundant naturally aromatic biopolymers in Raw alfa fibers (R-ALF) were first treated with hot water at 60 ◦ C for
nature. It is a low-cost waste product from the paper pulp manufacturing 1 h and then subjected to an alkaline treatment with (10 % NaOH (w/v))
process [23], with approximately 100 million tons produced annually aqueous solution in order to extract lignin. The suspension was main
worldwide [24]. It has the potential to be a bio-based substitute for tained under mechanical stirring at 80 ◦ C for 2 h, the solid-to-liquid ratio
petrochemical products because of its unique physicochemical proper used was 1:20. At the end of the reaction, the fibrous materials were
ties, such as biodegradability, hydrophobicity, and antioxidant activity filtered to obtain the black liquor. Then, sulfuric acid (H2SO4) was added
[25]. In addition to its high carbon content that could interestingly serve to the black liquor until reaching pH 2, suitable for the acidified lignin's
in increasing the soil organic matter. On the other hand, cellulose is the precipitation; this was later collected and washed by centrifugation until
most abundant polysaccharide in the plant kingdom [26]. One of the reaching neutral pH then dried (Scheme 1).
most important cellulose derivatives is methylcellulose [27]. This
biopolymer is obtained by replacing the hydroxyl groups of cellulose
with methoxyl groups. However, methylcellulose itself cannot be satis 2.3. Coating of DAP and TSP fertilizer granules with methylcellulose/
factorily used in slow-release systems due to its hydrophilicity that gives lignin (MC/LGe) hybrid polymeric formulations
rise to a poor barrier capacity. Consequently, its combination with other
biopolymers is needed to overcome such drawbacks. MC/LGe formulations were synthesized from methylcellulose and
Notably, lignin has a filler role due to its highly complex aromatic lignin using the solution blending method. Four formulations with
heteropolymer network of phenylpropane units that contribute to identical concentrations (20 g/L), were developed with different meth
enhance other biopolymers hydrophobicity [28]. In addition to its ylcellulose and lignin ratios. As a first step, methylcellulose powder was
recalcitrant nature, that confers an excellent resistance to microbial dissolved in cold water under mechanical stirring for 3 to 4 h. Then
degradation due to the random bonding pattern of its phenolic units lignin was added gradually to the different mixtures under mechanical
[29,30]. Furthermore, cross-linking as well is a technique employed to stirring at room temperature. The whole solution was sonicated to
highly improve the properties of a specific material by introducing an incorporate the lignin within the polymeric matrix. The formulation
agent that stimulates interactions between separate polymer chains, colour was subsequently transformed to a blackish colour. Citric acid
thus enhancing their overall properties [31]. was added to the mixtures as a cross-linking agent (5 % w/v), then, the
This work aims to design a novel green polymeric coating material, different solutions were mechanically stirred under 60 ◦ C for 5 h
based on a biocomposite, that will be obtained through loading a (Scheme 1). The formulation's colour was turned to a yellowish colour as
methylcellulose matrix with natural lignin, extracted from Alfa plant, in shown in the fig. S1. These different formulations were prepared by
the presence of citric acid as a cross-linking agent. The resulting material varying the lignin content from 0 to 40 %. The weight ratios of MC and
effect will be further investigated, mainly in terms of the slow-release LGe were set as 100:0, 85:15, 75:25, and 60:40, and the corresponding
capability from two different types of fertilizers: Di-Ammonium Phos codes were represented as MC, MC85/LGe15, MC75/LGe25, and MC60/
phate (DAP) and Triple Superphosphate (TSP), afterwards the impact of LGe40 (see Fig. S1 for their digital photographs). The viscosity of
the latters on the growth and productivity of wheat crop (Triticum Aes different coating formulations was measured to assure its suitability for
tivum), that was chosen as a model in this study, will be evaluated as the coating process (Table S1). MC and MC/LGe solid films were ob
well. Generally, the choice of one of these fertilizers depends principally tained by the solvent-casting method. Briefly, the obtained MC and MC/
on the farmer preference, the crop, the economics, the application LGe formulations were poured into petri-dishes and air-dried in a fume
method, and the combination of nutrients required. hood at room temperature for 3 days to evaporate water, resulting in the
For instance, TSP may be a better choice than DAP when applied on production of films with high quality, smooth surface, and good flexi
legume crops because the latters do not require N, and TSP is a N-free P bility (Fig. 3).
source [32]. On the other side, ammonium phosphate formulations The coating of DAP and TSP fertilizers was performed using a
provide the advantage of N + P joint application. Then, the Ca2+ present rotating pan equipped with a spray-drying system. The different for
in TSP can offer supplemental nutritional benefits, particularly in Ca- mulations were applied onto DAP and TSP granules under the same
deficient soils [33]. In contrast, ammoniated phosphates could also be experimental conditions. In the first stage, DAP and TSP granules (100 g)
more effective than TSP in highly calcareous soils, due to the limited were put inside the pan and preheated at 100 ◦ C for 20 min. After that, a
dissolution of TSP [34]. Therefore, the selection of these fertilizers de fixed amount of each formulation (500 mL) was pumped at a controlled
pends mainly on the targeted application. To the best of our knowledge, rate via a peristaltic pump, atomized via pressurized air through the
few studies about SRFs reported the use of lignin extracted from bio nozzle, and sprayed onto the surface of the granules. The air tempera
resources (mostly use of commercial lignins), and this is the first work to ture was kept at 100 ◦ C. In the second stage, the coated fertilizers were
use lignin extracted from Alfa plant, incorporated within a methylcel placed in the oven at 140 ◦ C for 40 min to make the cross-linking occur
lulose matrix as a biocomposite coating material to make SRFs. (Scheme 1). All prepared coated products (named MC/LGe-c-DAP&TSP)
are denominated as MC-c-DAP, MC-c-TSP, MC85/LGe15-c-DAP, MC85/
2. Experimental details LGe15-c-TSP, MC75/LGe25-c-DAP, MC75/LGe25-c-TSP, MC60/LGe40-
c-DAP and MC60/LGe40-c-TSP, corresponding to coated DAP and TSP
2.1. Materials with different MC/LGe compositions (Fig. S2). After each coating ses
sion, the dried granules were collected and weighed in order to calculate
The Lignin used in this study was extracted from Moroccan Alfa. the coating percentage using the following equation:
399
Scheme 1. Overall steps for lignin extraction, coating formulations preparation and coating process of DAP and TSP fertilizer granules.
W1 − W0 duplicate, and the average values were taken as final results.

%Coating = × 100
W1
2.6. Effect of coating material composition on nutrients release in soil
where W0 is the weight of fertilizers before coating, and W1 is the final
product weight.
The release behaviour of N and P in soil was analysed by conducting
soil incubation experiments. The properties of the soil used in this work
2.4. Biodegradation experiments are presented in Table S2. Firstly, 0.5 g of coated fertilizers were placed
in plastic mesh-bags and interred in the middle of a plastic cup holding
The method applied to assess the soil burial degradability of the 50 g of air-dried soil. The soil moisture was maintained at 30%wt., then
coating films was adapted from SR EN ISO 846/2000 with some modi the cups were covered with a plastic film and were incubated under
fications by using natural active soils [35]. The test specimens of the MC controlled temperature (25 ± 1 ◦ C). At specific time intervals, two bags
and MC/LGe films were first cut into equal dimensions of a square form from each treatment were randomly removed and dried at room tem
(2 × 2 cm2). Then, the specimens were weighed and buried 25 mm deep perature, and then the fertilizers were retired from the bags and dis
in the soil under controlled environmental conditions at room temper solved in distilled water to determine their N and P remaining content.
ature and humidity of 65 % for 30 days. The films were then cleaned and The nutrients residual content was quantified using the same method
dried in an oven at 45 ◦ C overnight. After that, the film samples were followed for the release in water. Averaged values were taken after
weighed, and their weight losses were calculated. The films were also duplicating the release tests.
qualitatively studied using SEM to compare the morphology before and
after biodegradability. 2.7. Design of pot experiment & agronomic parameters measurement
2.5. Effect of coating material composition on nutrients release in water Pots were randomized under the greenhouse using RCBD experi
mental design using 20 pots for each treatment. Plant performance was
The nutrients release from uncoated and coated DAP and TSP fer investigated using three samplings (1st January, 1st February, and 14th
tilizers was carried out in a beaker filled with a specific volume of March 2022) to evaluate plants morphological, physiological, and yield-
distilled water. In the first step, a fixed weight (100 mg) of fertilizers was related parameters. To understand the effect of the designed coated
soaked in 200 mL of distilled water at room temperature and the release fertilizers on the plant metabolism, especially photosynthesis, the
was followed under a continuous gentle stirring. At regular time in chlorophyll content (CC) was measured using CCM-200 portable chlo
tervals, 100 μL of the solution was sampled and diluted 100 times. rophyll meter and the leaf area (LA) was measured using LI-3100C Area
Supplemental 100 μL of distilled water was added to the beaker to meter. Shoots and roots dry weight was determined after drying at 70 ◦ C
maintain a constant volume. Then, all the samples were analysed by UV- for 2 days. Roots were extracted and washed before analysis, and their
spectrophotometer (PerkinElmer Lambda 1050) according to architecture was assessed using WinRHIZO™ root scanning to measure
ammonium-molybdate colorimetric method for phosphorus and phenol the root number (RN) and root length (RL). The experiment was started
colorimetric method for nitrogen. All the tests were carried out in on 1st December and monitored for three months until the seed maturity
400
stage. The spikes were collected and dried at 70 ◦ C for 48 h to measure The XRD pattern of the extracted lignin showed the typical broad signal
their dry weight (SDW), then seeds were extracted to count the grain around 19.48◦ , representing its amorphous structure [47]. Moreover,
number (GN) in order to evaluate the fruiting efficiency (FE). small signals at 11.06, 12.46, 21.41, 24.98, and 31.62◦ were observed,
Fruiting efficiency (%) was calculated as reported by Slafer et.al which are more characteristic of the crystalline domains of cellulose and
[36]: hemicelluloses [48]. As a result, XRD analysis revealed the presence of
few impurities in the extracted lignin. The CrI of the extracted lignin was
Grain number
%Fruiting efficiency (FE) = × 100 10.27 %, proving that extracted lignin has an amorphous characteristic.
Spike dry weight at anthesis
The obtained TGA and DTG curves of raw alfa fiber and extracted
lignin samples are presented in Fig. S4. From these findings, all samples
2.8. Statistical analysis show a weight loss at temperatures below 100 ◦ C, which is attributed to
the moisture evaporation bonded on the surface of the materials. For R-
Statistical analysis was performed using statistical software package ALF fibers, the onset temperature (Tonset) was observed at 207 ◦ C and the
R in R-4.2.0. Two-way analysis of variance (ANOVA) was used to corresponding major maximum temperature (Tmax) was determined at
examine the effect of coated products on the measured agronomic pa 368 ◦ C, which was attributed to the decomposition of all organic com
rameters. In addition, Tukey Honest Significant Difference (HSD) post pounds, such as cellulose, lignin, hemicellulose, and pectin, that are
hoc test was used to compare and assess the significance of the mean present in R-ALF sample [49]. Remarkably, the extracted lignin sample
values at P ≤ 0.05. shows a Tonset of 204 ◦ C and a major Tmax of 330 ◦ C. This decomposition
is due to the degradation processes of components of carbohydrates in
3. Results and discussions the lignin samples, which are converted to volatile gases such as CO,
CO2, and CH4 [50]. The final stage of lignin degradation occurred over a
3.1. Characterization wide range of temperatures above 400 ◦ C, associated with the decom
position of aromatic rings and char formation [51]. Thermal degrada
3.1.1. Characteristics of extracted lignin grass tion behaviour of extracted lignin was found to follow a similar pattern
Alfa, also called esparto grass or Stipa tenacissima was collected from identical to that reported for lignin extracted from sugarcane straw and
the oriental region of eastern Morocco and used for lignin extraction wheat straw [52].
according to standard alkaline treatments. The successful extraction
process of lignin was confirmed by FT-IR spectroscopy, X-ray diffraction, 3.1.2. Chemical structure investigation of MC and MC/LGe coating
and thermogravimetric analysis (See supporting information for more material solid films
details about the characterization process). FTIR was employed to The functional groups forming MC and MC/LGe films were identified
investigate the structural and chemical composition of raw alfa (R-ALF) by ATR-FTIR, and the recorded spectra are shown in Fig. 1. Neat
and extracted lignin (LGe). As shown in Fig. (S3, a), the spectrum of raw methylcellulose shows three characteristic peaks, appearing around
alfa displays peaks with sharp and broad shapes, whereas the spectra of 3429, 2919, and 2836 cm− 1, which are attributed to hydroxyl groups
lignin are mainly showing tiny peaks. Moreover, the absorption peak and C–H asymmetric and symmetric stretching vibrations, respectively.
intensity of R-ALF is stronger than that of lignin. The spectrum of R-ALF The absorption peak detected at about 1642 cm− 1 corresponds to the H-
shows hydrogen-bonded OH stretching absorption around 3320 cm− 1 O-H stretching of adsorbed water. The weak absorption bands located at
and a prominent C–H stretching absorption around 2919 cm− 1 [37,38]. 1379 and 1452 cm− 1 are assigned to the vibration of deformation in the
In the fingerprint region, between 1700 and 890 cm− 1, many sharp and plane of δ(C–H) of methyl and methylene groups, respectively. Addi
discrete absorption bands pertaining to various functional groups pre tionally, the sharp peaks observed at 1050 and 1109 cm− 1 are ascribed
sent in R-ALF constituents are observed [20]. The band at 1733 cm− 1 to C–O–C symmetric and antisymmetric stretching vibrations of
observed in the R-ALF sample is assigned to the C– – O stretching vibra glycosidic units, respectively [43]. The absorption band recorded at 943
tion of the carbonyl and acetyl groups in the xylan component of cm− 1 is related to OCH3 groups.
hemicelluloses [37]. Furthermore, the bands at 1506 cm− 1 and 1245 These results were consistent with those previously reported in the
cm− 1 in the spectrum of the R-ALF sample are attributed to the C–C literature [53]. Comparatively, after the cross-linking reaction, an
stretching from aromatic skeleton vibrations in lignin and the stretching
vibration mode of the acyl oxygen CO–OR associated with the hemi
-1
celluloses, respectively [39]. In the extracted lignin, a peak is seen at -1 -1 1379 cm
2919 cm 1642 cm
-1
1452 cm
3354 cm− 1 due to the presence of hydroxyl groups related to the exis MC60/LGe40
tence of phenolic and alcoholic groups [40]. The lignin has abundant
side chains, which can be indicated by the presence of bonds at 2916 MC75/LGe25
cm− 1 and 2850 cm− 1 [41]. These peaks represent C–H stretching in
methyl of aromatic and methylene groups of side chains and aromatic
methoxyl groups [41]. The peaks at 1635 and 1600 cm− 1 were attrib MC85/LGe15
uted to the aldehyde group and aromatic skeletal vibration bands of

lignin [42]. The peak at 1513 cm− 1 is assigned to the aromatic skeletal
vibrations coupled with C–H in-plane deformations [43]. The peaks at MC
1238 and 1119 cm− 1 are possibly due to the C– – O stretching of syringyl
and guaiacyl rings [44]. The peak at 1039 cm− 1 corresponded to ending 3429 cm-1
2836 cm
-1 1452 cm
-1
vibrations of C–O in primary alcohols [45]. The small peaks at 967 and 1725 cm
-1
893 cm− 1 are attributed to the aromatic –CH stretch vibration [44].
-1
The XRD patterns of the R-ALF and lignin samples are depicted in 1109 cm
943 cm
-1
Fig. S3, b. As shown, the XRD pattern of R-ALF revealed two enlarged
diffraction peaks at 14.93◦ (arising due to diffraction from the (110) 4000 3500 3000 2500 2000 1500 1000
plane) and 22.35◦ due to reflections from (200) diffraction. The peak at Wavenumbers (cm ) -1
14.93◦ indicates the presence of amorphous elements such as lignin and
hemicellulose in raw fibers and is observed in most natural fibers [37]. Fig. 1. FTIR spectra of MC, MC85/LGe25, MC75/LGe25 and MC60/
Commonly, alfa fiber contains cellulose, lignin, and hemicellulose [46]. LGe40 films.
401
additional well-defined peak located at 1725 cm− 1 was observed for all 3.1.4. Swelling behaviour of MC/LGe solid films
the films spectra. This peak corresponds to the carbonyl group of esters, The swelling profiles of methyl cellulose-based coating material films
which indicates the formation of ester-linkages inside the polymeric loaded with different lignin contents in distilled water are presented in
network. This phenomenon was confirmed by other studies in the Fig. 4. The swelling ratio of all the prepared films increases with time but
literature [54]. Therefore, the appearance of this band could be reaches a maximum value (equilibrium) at a certain period of time. It
considered as evidence that the chemical cross-linking occurred suc can be noticed that the methylcellulose swells faster at the first stage,
cessfully. This reaction was conducted under heating conditions, and then the swelling rate decreases, reaching an equilibrium water
inducing the transformation of citric acid into citric anhydride via its absorbency of 144.4 % within almost 50 min. Accordingly, methylcel
dehydration [55]. The resulting cyclic anhydride intermediate reacts lulose can be considered as a good water absorbent. It can also be
with hydroxyl groups of methylcellulose and lignin [56], producing observed that increasing the lignin amount had a positive effect on the
consequently cross-links between the cellulosic chains (Fig. 2). composites swelling behaviour. Besides, the swelling rate increased in
the following order MC ˂ MC85/LGe15 ˂ MC75/LGe25 ˂ MC60/LGe40.
3.1.3. Surface hydrophobicity and wettability of MC/LGe solid films The moderate swelling ratios of 174.2 and 180 % reached within
The wetting properties of MC and MC/LGe films were evaluated approximately 62 min are attributed to both MC75/LGe25 and MC85/
using contact angle measurements. The water contact angles on LGe15 films, respectively, and the largest water uptake (225 %) was
different films surfaces are illustrated in Fig. 3. Generally, a lower recorded for the film doped with high lignin content within almost 187
contact angle value (˂60◦ ) implies a hydrophilic surface, or more spe min. Definitely, the lignin enhanced the water absorbency of methyl
cifically, it translates the high affinity of water molecules toward the cellulose, which might be occurred due to the high number of free hy
substrate [57]. At the same time, a larger one (˃60◦ ) corresponds to a droxyl groups present in the lignin structure that attract water molecules
hydrophobic surface [58]. The lowest water contact angle of 55.7◦ was [63]. These findings are in accordance with previous studies, where they
recorded for the cross-linked methylcellulose (MC) film. Typically, revealed that the presence of functional groups had a great influence on
native cellulose is hydrophilic with a water contact angle around 20–30◦ the swelling properties [64], and they also demonstrated that the
[59,60]. The value obtained for MC film was originated from the pres increased lignin weight fraction was proportional to the swelling ratio
ence of a high number of methoxyl groups instead of hydroxyl groups [65].
(responsible for water molecules attraction). The MC/LGe composite Moreover, Fig. 4 clearly shows that the film doped with high lignin
films exhibited different contact angles, depending on the lignin con content (MC60/LGe40), reached the equilibrium swelling state slower
centration. In fact, the water contact angle increased from 55.7◦ to than MC and the other composite films. In fact, when the film containing
59.3◦ , 66.6◦ and 70.7◦ when LGe content was 15, 25 and 40 %, only MC swelled to approximately 128 % within 20 min, the MC60/
respectively. Obviously, lignin strongly influenced the resulting external LGe40 swelled to only 46 % during the same duration. This phenomenon
surface and its wettability. Besides, lignin is known to have a relatively could be explained by the presence of a very compact and dense struc
hydrophobic nature compared to other biopolymers due to its high ture in the composite surface, impeding the quick diffusion of water
carbon content [61]. Indeed, it was reported elsewhere that the ratio of molecules to the bulk. This condensed structure resulted from the
oxygen to carbon O/C in lignin can be estimated to about 0.41–0.44, chemical cross-linking occurred using citric acid, which was based on an
which is much lower than the value of 1.11 in the case of cellulose [62]. esterification reaction between alcoholic groups of both polymers and
For this reason, lignin is frequently added to other biopolymers to dehydrated citric acid after the heating step.
improve their hydrophobicity [28]. Furthermore, the intertwining of
polymeric chains had an important role in the formation of a very
3.2. Biodegradability study
compact structure in the surface, restricting the rapid penetration of the
droplet. Otherwise, the values obtained are favourably required because
The biodegradability of MC and MC/LGe films in soil was determined
the coating film should be hydrophilic enough to allow the water
in order to estimate their degradation time and confirm their potential as
penetration and subsequently the fertilizer transport. On the other hand,
alternatives to synthetic polymers that take longer periods to degrade.
it should also be sufficiently hydrophobic to prevent the membrane from
Biodegradation is defined as the loss of mechanical properties, frag
damage or destruction engendered by the fast access of water. These
mentation, or chemical modifications due to the action of microorgan
results are consistent with those of the swelling tests. Likewise, the film
isms and enzymes present in nature [66]. It is influenced by the presence
based on MC60/LGe40 was the slowest in reaching the equilibrium
of gases, moisture, light, temperature, and biota. According to a recent
water absorbency.
study, the accumulation of microplastics produces detrimental effects on
soil organisms and increases the accumulation of other micropollutants,
Fig. 2. Crosslinking reaction of methylcellulose with citric acid.
402
MC MC85/LGe15 MC75/LGe25 MC60/LGe40
55.7° 59.3° 66.6° 70.7°
Fig. 3. Water contact angle of crosslinked-MC and MC/LGe composite films.
250
MC60/40LGe
200
Swelling ratio (%)
150 MC75/25LGe
100
MC85/15LGe
MC
50 MC85/LGe15
MC75/LGe25 MC
MC60/LGe40
0
0 50 100 150 200 250 0 50 100 150 200 250
Time (min) Swelling ratio (%)
Fig. 4. Swelling ratio of crosslinked-MC and MC/LGe hybrid composite films at different LGe contents.
such as heavy metals [67]. For this reason, the degradation of the observed on MC/LGe films can be explained by the evaporation-induced
coating films produced in this study was evaluated in a natural active self-assembly process. In theory, lignin displays self-assembly behaviour
soil from the experimental farm at African Plant Nutrition Institute, due to its amphiphilic nature composed of hydrophobic aromatic rings,
Morocco. The degradation of the MC and MC/LGe films was quantified that lead to the appearance of these structures [69].
by weight loss after being buried in soil for 30 days. The results showed After the biodegradation test, the SEM image of neat MC films
that lignin loadings decreased the biodegradation of MC films. After 30 (Fig. 5b) showed several huge cracks and holes, even with pieces of
days, the neat MC film degraded by 87 %, while degradation rates of 69 material stripping. The images of MC85/LGe15 and MC75/LGe25 after
%, 61 %, and 46 % were obtained for the films of MC85/LGe15, MC75/ degradation (Fig. 5d and f) showed fewer cracks and holes. The surface
LGe25, and MC60/LGe40, respectively. MC biodegradable film has OH of MC60/LGe40 (Fig. 5h) was observed to have very small thin cracks
functional groups as flexible active sites and can degrade with high rates with holes after degradation. The MC polymer was decomposed into
since these active groups enable the film to bind to enzyme sites faster small and soluble molecules by microorganisms in the soil, and they
than the case of lignin reinforced MC biodegradable films [68]. were released from the films, resulting in cracks and holes on the film
Furthermore, polymers with shorter chains are known to degrade faster surface, causing subsequently a significant weight loss. The MC films
than polymers with complex chemical structures that necessitate the use reinforced with lignin, more hydrophobic and compact in structure,
of additional enzymes or co-enzymes [69]. SEM images showed the were more repellent to the microorganisms in the soil, and thus retained
surface microstructure of the MC films before and after biodegradability an intact morphology and less weight loss. The results show that the
(Fig. 5). Before biodegradability, the images showed clear differences addition of lignin to the MC matrix can help solve MC film rapid
between films with and without lignin. The MC/LGe films (Fig. 5c, d, degradation. This further indicated that lignin reinforced MC films
and e) showed higher roughness than the neat MC films (Fig. 5a) that might also be used as a coating material for slow-release fertilizer and
presented a smooth and compact surface. The small aggregate structures could effectively improve crop growth.
403
Before biodegradation
(a) (c) (e) (g)
40 µm 40 µm 40 µm 40 µm
After biodegradation (30 days)

(b) (d) (f) (h)
40 µm 40 µm 40 µm 40 µm
Fig. 5. SEM images before and after biodegradability in soil of (a, b) MC, (c, d) MC85/LGe15, (e, f) MC75/LGe25, and (g, h) MC60/LGe40.
3.3. Morphology and mechanical resistance of coated DAP and TSP showed the presence of micro-pores and irregularities. Indeed, the lat
fertilizers ters can be readily permeated by moisture, giving rise to the quick
dissolution of nutrients inside the granules and effectively to their im
The scanning electron microscopy was performed to visualise the mediate availability [70].
morphology of DAP and TSP fertilizers before and after coating. The However, once applying different coatings, the surface became
SEM images of uncoated DAP and TSP external surfaces revealed that smoother and denser, and the irregularities were perfectly corrected
both have a non-spherical shape and a wrinkled rough surface; they also (Fig. 6b-e and g-j). Moreover, based on the magnified cross-sectional
Fig. 6. Surface morphology of uncoated DAP (a), MC-c-DAP (b), MC85/LGe15-c-DAP (c), MC75/LGe25-c-DAP(d), MC60/LGe40-c-DAP (e), uncoated TSP (f), MC-c-
TSP (g), MC85/LGe15-c-TSP (h), MC75/LGe25-c-TSP (i), MC60/LGe40-c-TSP (j).
404
SEM images (Fig. 7), it can be observed that the coatings exhibited a and TSP, revealed the presence of carbon and oxygen with high per
perfect adhesion with granules even with the surface coarseness. In centages originated basically from the polymeric coating structure based
addition, it can be noticed that the coating layer was very compact and on the starting polymers lignin and methylcellulose, thus confirming
uniform, which indicates that the lignin was well dispersed in the that the surface was well covered by the organic coating. Gold (Au) was
methylcellulose matrix. The coating percentages were 7.87, 7.22, 5.96 detected in all spectra since it was used as a preliminary coating to
and 6.40 % for MC-c-DAP, MC85/LGe15-c-DAP, MC75/LGe25-c-DAP enhance the fertilizer surface conductivity before the SEM investigation.
and MC60/LGe40-c-DAP, respectively, and 9.36, 6.14, 7.70 and 6.03 Furthermore, the existence of phosphorus and nitrogen traces on the SRF
% for MC-c-TSP, MC85/LGe15-c-TSP, MC75/LGe25-c-TSP, and MC60/ surfaces confirmed the dust observed in the SEM amplified images.
LGe40-c-TSP, respectively. Considering these results, it can be Slow-release fertilizers are subjected to the same process of nutrients
deduced that the MC/LGe coatings remarkably improved the surface release, regardless of the fertilizer type. Besides, the movement of the
morphology of both fertilizers by reducing their defects and imperfec nutrients is governed by diffusion, which is generated from water ingress
tions. Furthermore, it should be emphasized that the fertilizer into the fertilizer core through micro-pores in the coating surface,
morphology is considered as one of the key factors influencing the leading to the creation of a concentration difference (osmotic pressure
nutrient release, in effect, the presence of porosity catalyses the burst gradient) inside the granule and allowing the nutrients release subse
release [71]. Higher magnification images of coated granules surface quently. However, when the concentration is large, the material can
show the distribution of some micro-particles, which are generated from eventually break [71]. Therefore, the strength of the coating material is
the dust caused by granule-granule and wall-granule collisions during highly desired since it is directly linked to the nutrients release. Other
the rotation movement. A similar observation was noticed in other wise, the coating should not reduce the physical quality of the starting
studies [68,72]. fertilizers, because it is essential notably during handling, storage, and
The surface elemental composition of coated and uncoated fertilizer transportation. Herein, to investigate the presence of any mechanical
granules was analysed via EDX, and the results are illustrated in Fig. 8. alteration, the resistance of the as-prepared products was evaluated by
Regarding the spectrum of uncoated DAP surface, strong signals of conducting compression tests. Fig. 9 displays the crushing strength re
phosphorus and oxygen; proceeding from phosphate groups (P2O5), as sults of DAP and TSP fertilizers before and after their coating. The
well as nitrogen were detected. These three macro-elements are maximum resistance of DAP and TSP before the coating was 54.28 ±
considered as basic elements constructing the DAP core. In addition to 2.13 and 40.50 ± 5.19 N, corresponding to pressures of about 5.4 and 4
other trace elements such as Mg, S, and K that were also detected. The kg/granule, respectively. These values were comparable to those pre
surface of TSP also revealed the existence of its basic elements with viously reported in the literature [73]. Further, Hignett and al. found
prominent intensities, mainly phosphorus and oxygen, followed by that among all the fertilizer types, the hardest granules to break were
calcium with lower intensity. The other elements are trace elements (Na, those of diammonium phosphate with crushing strengths up to 5.2 kg/
Mg, K, and C). On the other hand, both coated products surfaces, DAP granule [74]. This difference in mechanical strength values between
Fig. 7. SEM cross-sectional images of uncoated DAP (a), MC-c-DAP (b), MC85/LGe15-c-DAP (c), MC75/LGe25-c-DAP(d), MC60/LGe40-c-DAP (e), uncoated TSP (f),
MC-c-TSP (g), MC85/LGe15-c-TSP (h), MC75/LGe25-c-TSP (i) and MC60/LGe40-c-TSP (j).
405
4000 9000
uc-DAP MC/LGe-c-DAP
7500
Intensity (Counts-1)
Intensity (Counts-1) 3000
6000 C
O
2000 4500
P
3000
1000 O
Au 1500
N S Au
Mg N
K P
0 0
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0
Energy (KeV) Energy (KeV)
12000 12000
O uc-TSP MC/LGe-c-TSP
10000 10000
8000 8000 C
P O
6000 6000
4000 4000
2000 Au 2000
Ca Au
C Na Mg P
K
0 0
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0
Energy (KeV) Energy (KeV)
Fig. 8. Surface chemical composition of DAP and TSP granules before and after coating.
82.80 ± 5.98 N for TSP coated with MC, MC85/LGe15, MC75/LGe25

MC60/LGe40-c-TSP and MC60/LGe40, respectively. From Fig. 9, it can be clearly noticed
that the MC60/LGe40-c-DAP and MC60/LGe40-c-TSP showed better
MC75/LGe25-c-TSP
mechanical stability with maximum breaking force, which was three
MC85/LGe15-c-TSP times greater than that of uncoated DAP and 2 times greater than that of
uncoated TSP. This dramatic rise is mainly generated from the quality of
MC-c-TSP the coating material that have fulfilled all the surface cavities, which are
uc-TSP acting as stress concentration points, resulting in a more stable and
compact structure. Moreover, the high mechanical strength interestingly
MC60/LGe40-c-DAP achieved when fertilizers were coated by MC60/LGe40, might also be
MC75/LGe25-c-DAP ascribed to the highly cross-linked network, due to the formation of a
three-dimensional interconnected structure that restricts the mobility of
MC85/LGe15-c-DAP the polymeric chains resulting in a more rigid structure [68,76]. Overall,
the addition of lignin as a filler endowed the resultant composite with
MC-c-DAP
higher stiffness, by increasing its ability to bear up higher resistances
uc-DAP [77].
0 20 40 60 80 100 120 140 160

3.4. Kinetics of nutrients release from coated TSP and DAP fertilizers in
Mechanical Strenght (N) water
Fig. 9. Average crushing strength of DAP and TSP fertilizer granules before and The slow-release behaviour of phosphorus and nitrogen was inves
after coating. tigated for uncoated and MC/LGe-coated fertilizers. Also, the different
formulations were evaluated in terms of their effectiveness, barrier
conventional fertilizers could probably be related to their chemical property, and suitability on the two types of fertilizers (DAP and TSP).
structure, as well as to the total number of defects at their surfaces that The results obtained in water are depicted in Fig. 10. The nutrients were
extensively contribute to the prompt granule destruction after briskly released from both uncoated fertilizers. Almost 68.38 % of
compression [75]. phosphorus and 88.24 % of nitrogen were released within the first thirty
The coating has greatly increased the resistance of fertilizers toward minutes of soaking in water, from uncoated DAP. Additionally, up to
the crushing force. In fact, the latter was increased from 54.28 N to 51.96 % was released from uncoated TSP within the same duration.
112.28 ± 3.67, 117.61 ± 5.74, 141.41 ± 9.46 and 146.41 ± 6.28 N for Later, nutrients were completely dissolved after only 1–2 h from both
DAP and from 40.50 N to 47.41 ± 6.52, 49.78 ± 4.59, 59.02 ± 3.77 and fertilizers. This quick behaviour is most likely due to the high affinity of
406
100 100
(a)
(b)
% of cumulative P release
% of cumulative N release
80 80
100
100
80
60 60
80
60
60
40
40
40 40
20 20
uc-DAP 0 uc-DAP 0
20 MC-c-DAP 0 1 2 3 4 5 20 MC-c-DAP 0 1 2 3 4 5
MC85/LGe15-c-DAP MC85/LGe15-c-DAP
0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (hours) Time (hours)
100
(c)
80
100
80
60
60
40
40
20
uc-TSP
0
20 MC-c-TSP 0 1 2 3 4 5
MC85/LGe15-c-TSP
MC75/LGe25-c-TSP
MC60/LGe40-c-TSP
0
0 10 20 30 40 50
Time (hours)
Fig. 10. Release profiles of Phosphorus (a,c) and Nitrogen (b) in water medium from coated and uncoated fertilizer granules at different LGe contents.
nutritive elements (PO3−4 , NH4 ) with water molecules, and the presence
+
of its initial content within the same period, when the lignin concen
of microcavities on their surfaces [78], which advocated consequently tration in the coating was 0 %, 15 %, 25 % and 40 %, respectively. In
their abrupt dissolution. Comparatively, all the developed SRFs exhibi addition, after 24 h of immersion in water the percentage of active in
ted sluggish release rates than the uncoated fertilizers. The diffusion of gredients released was approximately 95 %, 91 %, 86 % and 78 % of P
nutrients in the first hour sharply decreased from 100 % (uncoated and 95 %, 90 %, 83 % and 70 % of N, from coated DAP, and 100 %, 91 %,
fertilizers) to almost 55.33 %, 50.60 %, 26.82 %, and 17.75 % of P and 89 % and 83 % from coated TSP, when the cellulosic matrix was loaded
52.12 %, 45.83 %, 32.82 %, and 8.27 % of N in the case of coated DAP, with 0 %, 15 %, 25 % and 40 % of lignin, respectively.
meanwhile coated TSP released 52.59 %, 41.48 %, 23.48 % and 19.11 % The experimental data above indicated that the slow-release process
Scheme 2. Schematic representation of the chemical structure of the coating film.
407
is strongly dependent on the concentration of lignin. Besides, it can be h, 50 h, and 61 h. From this available data, it can be noticed that there
pointed out that increasing quantities of lignin loaded largely delayed was a slight difference in P complete release time from each type of
the release toward longer periods. This trend was attributed in previous fertilizer, which might be probably related to the intermolecular in
studies to the increase in the network compaction, which hamper the teractions that occurred between phosphate and other ions inside each
quick penetration of water molecules and the diffusion of nutrients, granule. It can also be easily recognized that nitrogen had a relatively
since the free volume decreases [79]. Correspondingly, it was also re slower release over phosphorus, this tendency was previously reported
ported that the denser the film is, the smaller the release rate is [78]. and assigned to the fertilizer-coating interactions [5]. Herein, DAP and
This compaction is generated from the formation of a highly intertwined TSP are physically bound to the polymeric membrane, either by
network established by ester linkages between citric acid and cellulosic hydrogen bonding interactions; constructed between the fertilizer's
chains, which was previously confirmed by the FTIR study (Scheme 2). inorganic salts (amino and phosphate groups) and functional groups of
Basically, nutrients are considered entrapped within the cross-linked both polymers, such as hydroxyl, ether, and carbonyl groups, or by
network which reduces their diffusion to the solution [55]. The sus electrostatic interactions, mainly between ammonium cations NH+ 4 in
tained release obtained for MC60/LGe40 could be also due to the higher the DAP and the free negatively charged hydroxyl groups proceeding
homogeneity, less porosity, and more hydrophobicity of the coating from lignin and MC in order to balance the charge deficit. Additionally,
film, as argued by other researchers [4,28]. Relatively, it was found that the slowest release behaviour of an element over the other can also
the incorporation of lignin has a high potential to decrease the film result from the difference in the solubility of nutrients depending on
porosity and enhance the hydrophobicity of other biopolymers [80], their chemical affinity to water [81]. These could be the main reasons
which is in line with the contact angle results, where it was found that behind the slightly retarded spread of N as compared to P. The incor
the most hydrophobic coating was that formed with 40 %wt of lignin poration of lignin within the MC matrix showed remarkable perfor
(70.7◦ ). Indeed, it was reported that an increase in methylcellulose mances regarding the slow-release behaviour. In fact, the DAP coated
content induced an increase in the hydrophilicity of the matrix, which with high lignin content released almost 60 times less nutrients as
led to high release capability [79]. These results agree with the swelling compared to the uncoated one, while the TSP released almost 28 times
tests as well, where the film doped with 40 wt% lignin was the tardiest in less phosphates. Therefore, it is noteworthy to mention that MC and MC/
achieving the equilibrium water absorbency. Phosphorus was totally LGe coating films succeeded to largely delay the nutrients release better
released from coated DAP within approximately 9 h, 30 h, 48 h and 60 h than other lignin and MC-based coatings previously reported in the
and from coated TSP within 8 h, 30 h, 40 h and 50 h, when the lignin literature [79]. For example, urea coated with a soda flax lignin (Bio
concentration was 0 %, 15 %, 25 %, and 40 %, respectively. At the same plast) released almost 80 % in <30 min [82], where 80 % of urea
time, total nitrogen was released from coated DAP after almost 24 h, 37 encapsulated within a pine kraft lignin was released in <4 h [83].
100 100
(a) (b)
% of cumulative N release
80 100
80 100
80 80
60 60 60
60
40 40
40 40 20
20
0 0
uc-DAP uc-DAP 0 1 2 3 4 5
0 1 2 3 4 5
20 MC-c-DAP 20 MC-c-DAP
0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time (days) Time (days)
100
(c)
80 100
80
60 60
40
40 20
0
0 1 2 3 4 5
uc-TSP
20 MC-c-TSP
MC85/LGe15-c-TSP
MC75/LGe25-c-TSP
MC60/LGe40-c-TSP
0
0 5 10 15 20 25 30
Time (days)
Fig. 11. Release profiles of Phosphorus (a,c) and Nitrogen (b) in soil environment from coated and uncoated fertilizer granules at different LGe contents.
408
Another study reported that almost 90 % of nitrogen was released within biodegradability tests since the composite film loaded with high lignin
approximately 2 h from urea entrapped in a lignin-modified starch films content, showing the best retardant performances, was the slowest to
[28]. biodegrade in soil. Moreover, it is worth to note that lignin was used in
numerous studies to retard the quick biodegradation of other poly
saccharides by decreasing their weight loss during the soil incubation
3.5. Kinetics of nutrients release from coated TSP and DAP fertilizers in
tests [29]. In this connection, an earlier work of Majeed and al. reported
soil
that the addition of lignin increased the resistance of a starch based
composite film to microbial attack, thus reducing its biodegradability
The release profiles in soil from coated DAP and TSP are shown in
[80]. The complete nutrients delivery to soil from both covered TSP and
Fig. 11. The behaviour of all these formulations is analogous to that in
DAP with MC60/LGe40 was reached within almost 30–35 days, the
water. More specifically, the developed SRFs preserved their order in
release rate decreased >6 and 8-fold, respectively, as compared to the
reaching the nutrients complete release. This confirms what was
uncoated ones. Promisingly, the designed composite provided better
mentioned earlier, the release experiments in water are considered as a
control of nutrients release; thereby the latter remains available for
fast and easy method for predicting the behaviour in soil since the latter
longer periods. Additionally, the present single coating had largely
needs longer periods of incubation. However, this time, the steady state
prolonged the nutrients release better than other biopolymers based
was reached in a more prolonged manner increasing from hours (in
single or even double coatings. Some literature examples are listed in the
water) to weeks (in soil). This phenomenon was discussed previously
Table 1.
and ascribed to two possible reasons; mainly the less quantity of water
available in soil [63], as well as the occlusion of the coating surface by
soil ions and particles [4], that are playing a role of physical barrier 3.6. Water holding and water retention capacities of the soil containing
together with the coating substrate [84], hence driving it toward a lower coated TSP and DAP fertilizers
water absorbency.
Expectedly, nutrients have abruptly migrated from both uncoated Over their undeniable role in offering long-term availability to nu
fertilizers cores, and >90 % was released within the first three days. trients in soil, biopolymers can also preserve the soil moisture which has
Meanwhile, only 76 %, 51 %, 49 % and 29 % of P and 79 %, 71 %, 69 % beneficial effects on vegetation growth. In order to shed light on this
and 36 % of N were released from coated DAP, and almost 81 %, 80 %, feature, water-holding and retention capacities were evaluated for all
66 % and 42 % were released from coated TSP, corresponding to a lignin the prepared products, and the results are depicted in Fig. 12. All the
content of 0 %, 15 %, 25 % and 40 %, respectively. Barely 1–2 days later, SRFs had moderately enhanced the water-holding capacity of the soil.
uncoated fertilizers were entirely solubilized in soil. Meantime, the Besides, the latter has increased from almost 61 ± 0.07 % (soil without
nutrients release rate from MC60/LGe40-c-DAP&TSP was less than half. SRFs) to 65.58 ± 0.02 % and 67.47 ± 0.1 % when coated DAP and TSP
Indeed, as claimed in the previous section, the increasing lignin con were integrated, respectively. On the other hand, as seen in Fig. 12b, the
centration had a substantial influence on the barrier property. Princi soil mixed with SRFs initially absorbed more water than the soil without
pally due to the chemical interaction between natural lignin and MC SRFs. In fact, during the 4th day, the water retention capacity of the
achieved via the cross-linking process, in addition to the lignin prom control was 63.66 ± 1.59 %, whereas that of the mixtures soil/SRFs was
ising physico-chemical properties. Otherwise, when the nutrients 70.54 ± 0.02 %, 72.44 ± 1.38 %, 72.54 ± 0.50 % and 72.13 ± 1.32 %,
release experiments are performed in water, the diffusion through the for soil with coated DAP, and 71.03 ± 0.13 %, 73.67 ± 0.81 %, 73.53 ±
membrane has a critical impact on the release patterns [85]. However, 0.38 % and 73.60 ± 0.44 %, for soil with coated TSP, corresponding to a
once the SRF is buried in soil, then other factors and parameters are lignin content in the coating of 0 %, 15 %, 25 % and 40 %, respectively.
involved, chiefly, micro-organisms and enzymes causing the degrada Furthermore, after two weeks, the control lost all the water retained;
tion of the coating film. Indeed, the degradation rate determines the meanwhile, the soil possessing coated fertilizers preserved a proportion
nutrients release rate. A burst biodegradability of the coating layer is of nearly 4.63–6.71 %.
undesired because it will eventually accelerate the nutrients escape from It is obvious that the mixtures soil/SRFs retained much less water
the core, yet a very slow or non-biodegradable material is unacceptable than the films previously immersed in water, this behaviour as explained
too since it will harm the soil (cumulative residues). Besides, the current earlier (release in soil), is eventually due to soil particles that are
release results are in good agreement with the MC and MC/LGe films- covering the polymeric layer and impeding the water molecules ingress,
Table 1
Research status of biopolymers-coated fertilizers.
Fertilizer type Coating material Coating method Film Nutrients release rate in soil Ref
thickness
N (Urea) *Inner coating: Natural rubber (NR)/Starch (ST) Rotary drum Double layer Urea beads: 100 % in 3 days Vudjung et al.
*Outer coating: Wax (W) coater Coated urea: 100 % in 24 days [86]
N (Urea) N + APT as the core Rotating Pan Double layer Uncoated product: 100 % in 5 Lü et al. [87]
*Inner coating: Starch acetate (SA) days
*Outer coating: Carboxymethyl Starch (CMS)/ Coated one: 100 % in 10 days
Xanthan (XG)
Ammonium Nitrate (NH4NO3) Ethyl Cellulose + Plasticizer Fluidized bed Single layer >90 % in 8 days Garcia et al. [4]
coater
N (Urea) *Inner coating: k-carrageenan (kC)-Sodium Rotating Pan Double layer 94 % within 25 days Wang et al. [84]
Alginate (SA)
*Outer coating: crosslinked kC-g-P (Acrylic acid)/
Celite
-Urea N + APT as the core Rotating Pan Double layer >98 % in 20 days Ni et al. [10]
-Ammonium Sulfate *Inner coating: Ethyl Cellulose (EC)
-Ammonium Chloride *Outer coating: CMC/HEC
-Di-ammonium Phosphate Crosslinked Methyl Cellulose (MC) /Lignin (LGe) Rotating Pan Single layer uc-DAP/TSP: 100 % in 4–5 This work
(DAP) days.
-Triple Superphosphate c-DAP/TSP: 100 % in 30–33
(TSP) days.
409
(a)
Soil_MC-c-TSP
Soil_MC60/LGe40-c-TSP
Soil_MC-c-DAP
Soil_MC60/LGe40-c-DAP
Control (only Soil)
0 10 20 30 40 50 60 70
Water-Holding Capacity
100
(b)
30
90
25
Water-Retention ratio (%)
80
20
70
15
60
10
50 5
10 11 12 13 14
40
Soil
30 Soil_MC-c-DAP
20 Soil_MC85/LGe15-c-DAP
Soil_MC-c-TSP
10 Soil_MC60/LGe40-c-TSP
0
0 2 4 6 8 10 12 14 16 18 20
Time (days)
Fig. 12. Water holding (a) and water retention (b) capacities of the soil containing coated TSP and DAP fertilizers.
in addition to the presence of many ions in soil solution that are parameters could be improved by the addition of the developed coated
generating a decline in the osmotic pressure inside and outside the fertilizers with the best formulation (MC60/LGe40-c-DAP&TSP). The
coating layer, resulting in a lower water absorbency. These results are in notation was simply switched to c-DAP and c-TSP, respectively. The
turn confirming the sustained release obtained in soil as compared to introduction of c-DAP and c-TSP significantly improved the growth
that in water. Nevertheless, in comparison to the control, the prepared traits (leaf area (LA), biomass, and root architecture), in addition to
products had decreased the water evaporation by improving both water some of the physiological responses of the wheat flag leaf, such as the
holding and retention capacities of soil. Therefore, they can be used as chlorophyll content in sequential harvests (Table S3 and Fig. 14). The
reservoirs to retain and supply moisture to crops over time and effec first harvest was conducted 30 days after sowing, at this stage, it was
tively prevent water losses. remarked that, compared to the control, the measured traits were not
significantly different for all the treatments (Fig. 13). This behaviour is
mainly due to the low nutrient requirements of wheat seedlings; hence
3.7. Effect of nutrients release on morphological, physiological, and the available nutrients were sufficient for proper growth (Table S2).
agronomic parameters At the second and third harvest, 60 and 100 days after sowing,
respectively, a substantial difference was observed regarding the leaf
Crop agronomic parameters are essential for the prediction of crop area and plant biomass (leaf and root dry weight (RDW and LDW)) be
growth [88,89]. Therefore, the main objective of this experiment was to tween the control, the soil amended with uncoated fertilizers, and that
investigate whether the wheat plant's above and below ground
410
Fig. 13. Leaf area, leaf and root dry weight, and leaf chlorophyll index in different harvests.
Fig. 14. Digital images of wheat shoots and roots after 100 days (third harvest).
411
Fig. 15. (a) Scan images of the roots extracted during the third harvest (after 100 days), (b) total roots length and (c) total roots number in different harvests.
amended with coated ones. This obvious increase is attributed to the exploitation of applied nutrients.
availability of nutrients (principally N and P) in the plant rhizosphere for
those harvests that coincided with the stem elongation and heading. 3.7.2. Fruiting efficiency (FE)
Thus, the highest values were recorded for the plants treated with coated Seeds are considered the most powerful sink that may interact with
DAP and TSP (Fig. 13a, b and c). Both coated fertilizers showed a very other sources like leaves and roots. In fact, any traits related to those
good potential for boosting the growth of plant shoots and roots. sources may determine and affect yield components. The fruiting effi
Photosynthesis is the source of biomass in plants [90,91]. However, ciency is an important trait to evaluate wheat yield potential. It is esti
many studies reported that P and N deficiencies restrain wheat growth mated as the ratio between grain number (GN) at maturity and spike dry
by decreasing leaf development and nutrients assimilation [92,93]. weight (SDW) at anthesis. Taken separately, the grain number and spike
Alternatively, appropriate phosphate or nitrogen fertilizers application dry weight were statistically significant between all treatments. Besides,
could effectively increase wheat's photosynthesis, as they are considered as reflected from the data given in Table 2, the fruiting efficiency of
as an important indicator for proper crop growth [94]. In this regard, wheat amended with coated fertilizers was better than the control and
based on Fig. 13d, it can be noticed that the controlled nutrients avail even more than the one amended with uncoated fertilizers. Obviously,
ability had a prominent impact on the Chlorophyll content, its value the FE that is strongly linked to the final yield is proportional to the grain
significantly increased in the leaves belonging to the plants amended number per unit area, confirming the latter's importance. Meanwhile,
with coated fertilizers, especially during the seedling and stem elonga other researchers showed that differences in FE are associated with dry
tion stages (first and second harvest). Conversely, in the third harvest matter partitioning within the spike at anthesis [95,96], which is in our
that coincided with the heading stage, the photosynthesis, nutrients case, largely affected by the presence or absence of the coating layer. All
assimilation, as well as translocation are moving toward seeds, as being things considered, it can be deduced that the gradual concentrations
the most demanding sink. These changes in the plant behaviour during released were essential and high enough to support the growth of wheat
the seed filling stage reduce subsequently the gap between treatments or plant, since the acquisition of nutrients has become more effective.
explicitly the metabolism-related traits including photosynthesis.
3.7.1. Roots architecture Table 2

As depicted in Fig. 15, the added bio-composite coating to both Fruiting efficiency.
fertilizers has highly improved the roots architecture. Indeed, as claimed Treatments GN SDW FE (%)*
in the previous section, wheat roots grown in the soil supplemented with
Control 9.46 277.85 3.404715 c
coated fertilizers had the highest roots dry weight as compared to those
uc-DAP 8.9 347.4 2.561888 b
planted in the control and soil with uncoated fertilizers. A similar trend c-DAP 18.63 402.25 4.631448 a
was recognized for roots length (RL) and roots number (RN) as well uc-TSP 11.15 294.85 3.781584 c
(Fig. 15b and c), with a preference for c-TSP in the third harvest. This c-TSP 14 312.67 4.477564 a
enhancement is linked to the gradual nutrients release in this period and *
Values followed by the same letter(s) are statistically similar according to
the strong root competition resulting ultimately in an efficient Tukey’s HSD test at p ≤ 0.05.
412
4. Conclusions [2] X. Han, X. Yan, X. Wang, J. Ran, C. Wu, X. Zhang, Preparation of chloride-free
potash fertilizers by electrodialysis metathesis, Sep. Purif. Technol. 191 (2018)
144–152, https://doi.org/10.1016/j.seppur.2017.09.022.
In view of above-mentioned results, lignin from Alfa plant, exploited [3] M.Y. Naz, S.A. Sulaiman, Slow release coating remedy for nitrogen loss from
to prepare biodegradable coating materials, is proving to be an ideal conventional urea: a review, J. Control. Release 225 (2016) 109–120, https://doi.
green candidate for designing a new family of slow-release fertilizers org/10.1016/j.jconrel.2016.01.037.
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macromolecules, RSC Adv. 11 (2021) 24206–24216, https://doi.org/10.1039/
This work was financially supported by the “Office Chérifien des D1RA02713A.
[21] A. Boussetta, E.-H. Ablouh, A.A. Benhamou, M. Taourirte, A. Moubarik,
Phosphates (OCP S.A.)” in Morocco, under a funded research project
Valorization of moroccan brown seaweeds: elaboration of formaldehyde-free
(Specific agreement OCP/UM6P #ASN◦ 34). The authors would like to particleboards based on sodium alginate–corn-starch - mimosa tannin wood
thank Dr. Hakim GHALFI from Innovation-OCP and Mehdi KHOULOUD adhesives, Int. J. Adhes. Adhes. 108 (2021), 102894, https://doi.org/10.1016/j.
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Methyl Cenlulozo

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International Journal of Biological Macromolecules 221 (2022) 398–415

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

Methylcellulose/lignin biocomposite as an eco-friendly and multifunctional

1. Introduction developed to enhance nutrients use efficiency and to achieve sustainable

W1 − W0 duplicate, and the average values were taken as final results.

uted to the aldehyde group and aromatic skeletal vibration bands of

Fig. 2. Crosslinking reaction of methylcellulose with citric acid.

MC MC85/LGe15 MC75/LGe25 MC60/LGe40

55.7° 59.3° 66.6° 70.7°

Fig. 3. Water contact angle of crosslinked-MC and MC/LGe composite films.

After biodegradation (30 days)

82.80 ± 5.98 N for TSP coated with MC, MC85/LGe15, MC75/LGe25

0 20 40 60 80 100 120 140 160

Scheme 2. Schematic representation of the chemical structure of the coating film.

Control (only Soil)

3.7.1. Roots architecture Table 2

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