Slow ReleaseFertilizersbasedonLignin SodiumAlginatebiopolymericblendforsustainedN Pnutrientsrelease
Slow ReleaseFertilizersbasedonLignin SodiumAlginatebiopolymericblendforsustainedN Pnutrientsrelease
Slow ReleaseFertilizersbasedonLignin SodiumAlginatebiopolymericblendforsustainedN Pnutrientsrelease
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fertilizer granules against water contact for gradual mechanical resistance, and their effect on the water-
nutrients release.6–8 holding capacity of soil was examined as well.
Organic-based and inorganic-based coating materi-
als are two main categories that have been extensively
used to produce slow-release fertilizers using coating Experimental section
technology. In particular, polymers are currently the
main applied materials as coatings due to their good Materials
film-forming properties.7–10 Among these polymers,
polyurethane,3 polyolefin,11 dicyclopentadiene, glyc- The fertilizer used as a model in this study is the di-
erol ester, polysulfone,12 and polystyrene10,13 were ammonium phosphate (DAP). Its diameter ranges
largely exploited for coated fertilizers production. between 2 and 4 mm, and it was provided by OCP
However, these synthetic materials are unsafe to the Group, Morocco. Lignin alkali (Lignin, Kraft, CAS
environment since they are nondegradable. Even number: 8068-05-1), sodium alginate (alginic acid
though these petroleum-based polymers showed better sodium salt, CAS number: 9005-38-3) and sodium
control of nutrients release, they are expensive, and hydroxide (CAS number: 1310-73-2) were purchased
they usually require toxic organic solvents for dissolu- from Sigma-Aldrich. Glycerol bidistilled 99.5% (CAS
tion.14 In recent years, these environmental concerns number: 56-81-5) was supplied from VWR Chemicals.
have attracted increasing interest for reducing the All the chemical products were used without further
potential toxicity of nondegradable coating residues by purification.
developing biodegradable coating materials including
bio-based polymers7,8,15–18 and aliphatic polyesters.19
Among these eco-friendly materials, lignin is a Preparation of SA-L coating formulations
biosourced polymer which is available in abundant
quantities from the existing papermaking and biore- Three different formulations based on lignin and
finery waste streams.20,21 It has a good prospective to sodium alginate were prepared; two formulations
form bio-based coating formulations of fertilizers due containing a dominant phase either lignin or sodium
to its interesting functional properties, namely its high alginate [SA/L (75 wt.%/25 wt.%), SA/L (25 wt.%/
carbon content that imparts lignin with interesting 75 wt.%)] and one formulation containing similar
hydrophobic character compared to other biopolymers percentage of both polymers [SA/L (50 wt%/
(chitosan, cellulose, starch, etc.).22 On the other hand, 50 wt.%)]. In the first step, different amounts of lignin
the microbial degradation of lignin generates phenolic in 500 mL of 3 wt.% NaOH aqueous solution were
compounds that can inhibit the nitrification process prepared under magnetic stirring at 50C for 30 min,
and volatilization losses.23,24 In this regard, lignin has then sodium alginate powder was added gradually to
been widely employed for elaborating slow-release the lignin solutions under the same conditions, and the
fertilizers. Among others, Li et al.25 reported the use of mixtures were left for 1 h to homogenize. Finally,
polylactic acid blended with industrial softwood kraft a few drops of glycerol (2.5 mL) were added to the
lignin as a coating material to provide sustained release mixtures to increase the plasticity of the films. Subse-
nitrogen fertilizers. In another study, Fertahi et al.26 quently, homogeneous solutions were obtained with
used lignin extracted from olive pomace in coating high, medium, and low viscosity for SA/L (75 wt.%/
formulations to enhance the slow-release behavior of 25 wt.%), (SA/L (50 wt.%/50 wt.%), and SA/L
triple superphosphate fertilizer. (25 wt.%/75 wt.%), respectively. The different formu-
Despite several existing studies about the use of lations were referenced by codes, as shown in Table 1.
lignin as coating material for SRF, there are few
studies on the coated fertilizers using a bio-based
mixture of lignin and other biopolymers using fewer Preparation of coated DAP fertilizers
toxic solvents.23 Such preparation requires the biopoly-
mers to have good compatibility with lignin consider- A fluidized bed machine (DIOSNA MiniLab RC,
ing its high hydrophobicity as compared to other LINXIS Group, Germany) was used for preparing
natural polymers. Furthermore, the elaboration of coated DAP fertilizers (Fig.S1). The different formu-
coated fertilizers should be simple and economical lations were applied onto DAP granules under the
adopting affordable coating materials in order to same experimental conditions (Scheme 1). In the
enable large-scale coated fertilizers production. To beginning, DAP granules were sieved (m = 50 g) to
this end, a novel polymeric coating membrane based obtain a homogeneous size interval. Then, granules
on a simple blend of lignin and sodium alginate was were put inside the coating chamber and dried at 70C
developed in this work. The obtained mixtures were with a fluidization air flow rate of 45% for 20 min.
further characterized and applied onto di-ammonium After that, a fixed amount of each formulation (V =
phosphate (DAP) fertilizers using a fluidized bed 140 mL) was pumped at a controlled rate by a
machine. Then, the final products were evaluated peristaltic pump (20 rpm), atomized via pressurized
mainly in terms of their slow-release capability and air (P = 0.2 bar) through the nozzle, and sprayed onto
J. Coat. Technol. Res.
Table 1: Weight fraction (%) and nomenclature used to Morphology, thickness, and elementary analysis
identify all SA-L formulations
The surface morphology of the studied fertilizer gran-
Formulations Weight fraction of Weight fraction of ules before and after the coating process was exam-
sodium alginate (wt%) lignin (wt%) ined using scanning electron microscopy (Tescan-
Vega3, Tescan Orsay Holding, a.s., Brno, Czech
SA75-L25 75 25
Republic) at an accelerating voltage of 10 kV. An en-
SA50-L50 50 50
ergy dispersive X-ray (EDAX) analyzer coupled with
SA25-L75 25 75
SEM was employed to reveal the elementary compo-
sition of the coated and uncoated DAP granules sur-
face. All samples were attached to SEM specimen
holders with double-sided carbon tape and coated
Table 2: Physicochemical properties of soil used in this with a thin layer of gold using sputter coater (Quorum,
work Q150 Plus Series, UK).
Particle size distribution (%) Clay 38
Silt 34
Sand 28 Mechanical strength
pH (H2O) 8.25
Electrical conductivity (mS/cm) at 25C 0.33 The mechanical resistance of coated and uncoated
Total organic matter content (%) 3.00 DAP granules was investigated using mechanical com-
Total nitrogen content (%) 0.14 pression tests (Shimadzu’s EZ Test EZ-X Series
Total phosphorus content (%) 0.53 compact tabletop). The granules were sorted with a
Total potassium content (%) 0.44 diameter ranged between 2 and 3 mm, and then they
were individually compressed in the radial direction
between two rigid plates. The charge at which the
the granules surface. The air temperature was kept at granule fractured was recorded as the crushing
70C, and the fluidization air flow rate was increased to strength. The compression tests were carried out on
60%. 20 granules, and the average mechanical strength was
All prepared coated products (named SA-L-c-DAP) then calculated for each case.
are referred as SA75-L25-c-DAP, SA50-L50-c-DAP,
and SA25-L75-c-DAP, corresponding to coated DAP
with different SA-L compositions. N–P nutrients release experiments in water
NaOOC OH
O O
OH O
O OH DAP fertilizer
O
OH NaOOC
Sodium alginate
HO
OH OH
OCH3
H3CO
H3CO OCH3 OH
O HO OH
OH O
HO O Fluidized bed
O OCH3 SA-L coating formulation
HO O
O
coating machine
HO
OCH3
HO
O SA-L-c-DAP product
HO
O OH
O
O
OCH3
OH
O OCH3
OH
OH
OCH3
Lignin
Scheme 1: Overall steps for elaboration of SA-L coated DAP using fluidized bed coating machine
(a) (b)
0
10
Viscosity (Pa.s)
10–1
10–2 SA25-L75
SA50-L50
SA75-L25-D SA75-L25 SA50-L50 SA25-L75
SA75-L25-UD
10–3
1 10 100
Shear rate (1/s)
Fig. 2: (a) Viscosity versus shear rate of SA-L coating formulations, (b) photographs of SA-L formulations
Fig. 4: SEM images of the surface of uc-DAP (a), SA75-L25-c-DAP (b), SA50-L50-c-DAP (c) and SA25-L75-c-DAP (d)
facilitate the water molecules penetration into the water diffusion rate. Hence, it will slow down the
DAP core, leading eventually to the fast release of nutrients release from the fertilizer. The changes in
nutrients.41,42 Generally, the existence of more surface granules surface after the coating process confirm the
irregularities promotes immediate nutrients dissolution results observed under naked eyes.
and diffusion outside the granules.43 After applying Figure 5 displays the cross section of uncoated and
one layer of different coating formulations, the coated DAP fertilizers. The outer and inner surface of
smoothness and uniformity of granules surface in- the film is perfectly homogeneous. Moreover, it does
creased while preserving their initial shape. Further- not reveal any holes or cracks, indicating the good
more, the coating corrected the surface imperfections choice of sodium alginate to form a highly compatible
and fulfilled all the microcavities. The resulting smooth blend with lignin leading to the formation of a very
and compact polymeric coating can limit or reduce the compact and dense coating film. Despite the roughness
J. Coat. Technol. Res.
Fig. 5: SEM images of the cross section of uncoated DAP (a), SA75-L25-c-DAP (b), SA50-L50-c-DAP (c) and SA25-L75-c-
DAP (d)
4000 7000
(a) O (b)
6000
O
Intensity (Counts–1)
Intensity (Counts–1)
3000
5000
4000 Na
2000
3000
S
P
2000 C
1000
N
1000
C Mg K P S
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. 6: EDX spectra of uncoated DAP (a) and coated DAP (b)
of DAP fertilizer, there was a good adhesion between coated products performances and to compare the
the granule and the different films, and this may be different results in the next sections.
related to the existence of physical interactions, The EDX analysis enables us to perform elementary
specifically hydrogen bonding interactions at their analysis of the studied materials. Figure 6 illustrates
interface. Indeed, the fertilizer surface is composed the EDX spectra of uncoated and coated DAP
mainly of nitrogen and phosphorus pentoxide soluble fertilizers. The analysis was carried out on three
in water, and the coatings contain polar hydroxyl different areas in each granule surface, and then the
groups at the end of chains, resulting in a well adherent average intensities were determined. The EDX results
coating layer. The average coating thicknesses calcu- of coated fertilizer granules surface was gathered in a
lated from the magnified cross-sectional SEM images, single spectrum since they revealed the presence of the
were approximately 103, 109, and 112 lm for SA75- same elements with almost identical intensities. The
L25-c-DAP, SA50-L50-c-DAP, and SA25-L75-c-DAP, spectrum of uncoated DAP (Fig. 6a) shows the
respectively. existence of its basic elements (P, O, and N), which
It can be remarked that the thicknesses were not were detected with significant intensities. Additionally,
significantly different. In fact, the coating thickness it was clearly noticed that the intensity of oxygen and
influences the slow-release property. Previous studies phosphorus was higher than that of nitrogen because
have demonstrated the proportionality between the the DAP contains more phosphorus and oxygen
nutrient’s retention and the coating thickness.39,44,45 In (P2O5) than nitrogen (N). Sulfur (S) is a secondary
the current study, we aimed to obtain almost similar element, and Mg, C, and K detected are trace ele-
thicknesses in order to neglect their effect on different ments. Regarding the surface of the coated granules
(Fig. 6b), high carbon and oxygen concentrations were
J. Coat. Technol. Res.
detected and neither nitrogen nor phosphorus were the fertilizer granule should be treated as a defect and
present (only some traces were detected). This con- the reason for the stress concentration, which impacts
firmed that there was a homogeneous coating layer adversely its mechanical properties.45 Besides, fertiliz-
deposited on the entire surface of fertilizer core, which ers are considered as typical materials with a brittle
formed a barrier limiting any diffusion of these failure mode. Their granules are porous, with many
nutritive elements to the external environment. This flaws, dislocations, and crystal edges.47,48 Compared to
observation is consistent with the chemical composi- the starting DAP fertilizer, SA-L coated granules
tion of both polymers used in the experiment. C and O exhibited significantly higher resistance toward the
are principally the atoms forming their backbone. The crushing force. The maximum crushing force has been
signal of sodium was relatively high; it comes mainly greatly improved, reaching the values of 94.6 ± 5.2,
from the chemical structure of sodium alginate. 112.9 ± 11, and 131.4 ± 5 N for SA50-L50-c-DAP,
Beside the slow-release property, the mechanical SA75-L25-c-DAP, and SA25-L75-c-DAP, correspond-
strength of fertilizers is also indispensable. This feature ing to pressures of about 9.4, 11.2, and 13.1 kg/granule,
has an important role in minimizing the mechanical respectively (Fig.7). This remarkable increase could be
disturbances caused during handling processes, bags simply explained by the fact that different coatings
storage, delivery operations, and finally application to have corrected the surface defects and irregularities by
the field. Indeed, a low crushing strength renders the forming a uniform and compact polymeric film, hence,
fertilizer mechanically unstable,12 facing various issues, extending the granule breaking time. Among all
including caking, dustiness, poor flowability, segrega- samples, SA25-L75-c-DAP granules showed the high-
tion, and excessive hygroscopicity.46 In a previous est crushing strength, which was approximately 2.5
study, it was found that the crushing strength values of times greater than that of uncoated DAP. This coating
DAP granules slightly decreased after its coating.40 In is composed predominantly by lignin, which proves
contrast, it is required that the coating material explicitly the high resistance of this biopolymer toward
enhance the fertilizer hardness after coating or at least the crushing force, since alginate is known to have a
preserve its initial one. weak mechanical strength and is destructible.49 For this
The crushing strength is defined as a measure of the reason, sodium alginate is found usually combined with
resistance of granules to deformation or fracture under other biopolymers in order to enhance its mechanical
pressure. In the current study, the crushing strength properties and its brittleness.50,51 This result was in line
was measured for uncoated and coated DAP. For each with the previous report of Garcia et al.,52 who has
sample, 20 parallel measurements were performed, and demonstrated that the crushing strength increased
the average value of the crushing strength was then directly and proportionally to the lignin-based coating
calculated. In general, it is necessary to crush at least percentage of the fertilizer. In the light of such results,
10 and preferably more granules to obtain an average it may be concluded that the prepared products by
evaluation.46 The obtained results are illustrated in coating DAP granules enhanced considerably the
Fig. 7. The average mechanical strength of uncoated physical properties of the initial fertilizer which are
DAP was around 54.28 N, corresponding to a pressure required for handling and transport.
of 5.4 kg/granule, with a standard deviation of 2.14.
This result was confirmed by Hignett, who found that
the pressure required to destroy the DAP granule was Slow-release behavior in water
about (5.2 kg).46 As previously discussed in the fertil-
izer’s morphology section, uncoated DAP surface In this study, immersion testing using water, one of the
contains small cavities; further, any discontinuity in simplest and most used methods in the literature was
applied to evaluate the prepared SRFs use efficiency,
in particularly their slow-release capability.53 The
140 cumulative release profiles of P and N in water from
uncoated and coated DAP granules with different
120
Mechanical strength (N)
100 100
% of cumulative N release
% of cumulative P release 80 80
100 100
80
60 80
60
60 60
40 40
40 40
Uc-DAP Uc-DAP
SA75-L25-c-DAP SA75-L25-c-DAP
20 SA50-L50-c-DAP 20
20 20 SA50-L50-c-DAP
SA25-L75-c-DAP SA25-L75-c-DAP
0 0
0 1 2 3 4 5
0 1 2 3 4 5
0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (hours) Time (hours)
Fig. 8: Phosphorus and nitrogen cumulative release rate in water from uncoated (uc-DAP) and coated DAP (SA-L-c-DAP)
complete release in water, in less than 2 h.6,54 Other- the complete release in water within 9 h for P and 10 h
wise, another study indicated that the untreated DAP for N, while SA50-L50-c-DAP and SA25-L75-c-DAP
granules reached the complete release in water within released within the same duration only 89% and 77%
almost 14 h.39 These differences in nutrients complete of P and 85% and 74% of N, respectively. It can be
release time might be attributed either to the fertilizer deduced that increasing the lignin content had a direct
initial composition or its manufacturing process. In effect on the slow-release behavior. This proportional
contrast, all the prepared SRFs exhibited significantly relation between lignin content and nutrients release
slower release rates compared to the untreated one. rate can be related to the lignin effect on water
The percentages of released nutrients from SA75-L25- diffusion. In fact, lignin has a relatively hydrophobic
c-DAP, SA50-L50-c-DAP, and SA25-L75-c-DAP nature.22,25,26,60 Thus, increasing its content led to
were 90%, 77%, and 67% for phosphorus and increased water repellence of the coating, reducing the
85%, 65% and 58% for nitrogen within the first 4 h water diffusion into the fertilizer core and dissolution
of immersion in water, respectively. In fact, the of its components, resulting in lower release rates. In
different coating layers were very compact and strong addition, lignin exhibit low porosity,26 compared to
that they survived and resisted after immersion in other biopolymers, restricting consequently high water
water, which is effectively in accordance with the penetration. Moreover, lignin has a filler role, due to
microscopic observations. Despite its hydrophilic its highly complex aromatic heteropolymer network of
nature, sodium alginate showed lower affinity to water phenylpropane units. It was used as a reinforcing agent
when it was combined with lignin, which was trans- for urea-crosslinked starch films, and as a consequence,
lated by the remarkable slow-release behavior, gener- it reduced the latter hydrophilicity and minimized the
ated from the construction of a physical barrier nitrogen release.61 All these characteristics confirmed
between the fertilizer core and water. The possible the abovementioned obtained release results and made
explanation for this performance is that the polar side the lignin an efficient material with high added value
chain groups of alginate were bound to lignin when it is used for developing slow-release fertilizers
molecules, leading to a reduced exposure of the (SRFs). Compared with other similar studies, the as-
hydrophilic groups of alginate with water molecules. prepared SA-L coated granules were able to retard the
Indeed, lignin interacts with alginate molecules by the release of nutrients better than other lignin-based
formation of hydrogen bonds that substituted poly- coatings, in which more than 90% of nutrients were
mer–polymer interaction and impeded the formation released in water in less than 4 h.22,25,62 More impor-
of polymer–water hydrogen bonds in the amorphous tantly, the current water release study showed that the
areas.37 Additionally, it was found that alginate time required to reach maximum nutrients release
increased the compactness of the film and hence from SA50-L50-c-DAP and SA25-L75-c-DAP was
minimized the coating porosity which eventually achieved within 26 h and 53 h for P and 29 h and
slowed down the release of nutrients.23,55 However, 57 h for N, respectively.
the high amount of alginate in SA75-L25-c-DAP The coatings prepared from SA-L act as selective
revealed the faster nutrients release compared to the barriers and the components from the granule were
two other products because alginate is known to released at different rates. Besides, the release of
exhibit a burst release in the beginning followed by a ammonium ions was slower than that of phosphates.
slow-release of the remaining nutrients.49,56,57 As a Taking the example of SA25-L75-c-DAP, after 23 h of
result, it is frequently incorporated with multiple other soaking in water, the cumulative release of ammonium
biopolymers.1,53,55,58,59 The SA75-L25-c-DAP achieved and phosphate ions was 83% and 87%, respectively.
J. Coat. Technol. Res.
The average difference between the release of phos- Effect of SRFs on water-holding
phate and ammonium ions was 4%. This phenomenon and water-retention capacities of soil
was explained by many reasons, such as the presence of
interactions between ions inside the granule,12,45 dif- The presence of water in soil is mandatory for vegeta-
ferences in each nutrient solubility,45 hydrogen bond- tion growth. Water ensures the feeding of plants with
ing between the functional groups of both polymers nutritive elements, which boost their better growth.64
and fertilizer compounds,63 as well as electrostatic However, water losses, caused by various phenomena,
interactions.64,65 The latter can be considered in our such as evaporation, infiltration, and drainage, lead to
case between NH4+ and the negatively charged car- poor water use efficiency.53,66 To overcome this prob-
boxylate –COO and hydroxyl –OH groups in the lem and ensure better living conditions for crops, water
SA-L networks which might be responsible on the losses should be reduced. Among the benefits from the
slightly retarded release of nitrogen as compared to use of biopolymers as coating material, is that some of
phosphate (Fig.9). them have the capability to increase the water-holding
From these results, it can be concluded that the (WHC) and water-retention capacities (WRC) of soil.49
optimum and most favorable formulation for the In fact, the network of the polymeric coating captures
coating of DAP granules was SA25-L75. The coated water molecules in moist soil and gradually releases
fertilizer in this case released 53 times less phosphorus them to the soil under drought conditions, acting as a
(P) than the uncoated DAP. This remarkable release regulator to adjust soil moisture.49,63 This attribute is
delay is principally originated from the physical barrier considered as one of the most effective ways to improve
property of lignin-based coating material. water use efficiency and durability. The effect of the as-
prepared products on water-holding and water-reten-
Fig. 9: Schematic representation of different chemical interactions between SA-L and DAP
J. Coat. Technol. Res.
90 100 70
80
70 80
60 50
60
50 40
30
(Control)
20 20 Soil
Soil + SA75-L25-c-DAP
10 Soil + SA50-L50-c-DAP
Soil + SA25-L75-c-DAP
0 0
0 2 4 6 8 10 12 14 16 18 20 22
Time (days)
Fig. 10: Soil maximum water-holding (a) and water-retention capacity (b) without and with different SRFs
tion capacities of soil was studied, and the results are L75-c-DAP exhibited the best performance, and this
illustrated in Fig. 10. would probably be due to the higher number of free
As shown in Fig. 10a, the maximum water-holding hydroxyls available in lignin to interact and retain
capacity of the control (soil without fertilizers), was water molecules inside the polymeric network.68 This
around 50.64%, whereas that of amended soil with finding was in accordance with a previous work in
SA75-L25-c-DAP, SA50-L50-c-DAP, and SA25-L75- which they demonstrated that the swelling ratio was
c-DAP reached a percentage of 51.95%, 53.89%, and proportional to the lignin content.69 The compactness
77.49%, respectively. The soil water-holding capacity of the film might also affect the WRC and WHC. When
significantly increased after the addition of coated the film is compact and dense, the water molecules are
fertilizers; it can be noted that amended soil retains diffused and released slowly through the polymeric
more water than the control. Additionally, the increase coating, which guarantee the long-term availability of
in lignin content from one coating to the other had a water and lower vaporization rate. From the previously
large effect on the WHC. The WHC of the soil mixed discussed results, it can be concluded that all the
with only 1 g SA25-L75-c-DAP was almost 27% products had a positive effect on both WHC and WRC
greater than the control. This proved the ability of of the soil. Besides, the optimal coating formulation
the polymeric network to absorb and retain water, allowing the best retention of water and prolonging its
especially when increasing the lignin rate. The same storage period in soil was that of SA25-L75-c-DAP.
behavior was recognized for the soil water-retention as Therefore, the latter can be used to enhance the water
well (Fig. 10b); SA25-L75-c-DAP had the highest use efficiency and to improve the soil quality by
WRC, followed by SA50-L50-c-DAP and SA75-L25-c- maintaining its moisture in dry conditions.
DAP. The soil moisture after 9 days was 33%, 35.6%,
36.5%, and 38% for the control, SA75-L25-c-DAP,
SA50-L50-c-DAP, and SA25-L75-c-DAP, respectively. Nutrients release in soil
The coated products effectively improved the WRC of
soil, even at a very low application rate (0.5 g of SRFs The release characteristics of DAP and newly designed
in 50 g of soil). Indeed, the SA25-L75-c-DAP pre- SRFs in soil are very similar to their behavior in water.
served 5% more of the initial retained water compared As expected, the uncoated DAP exhibited a fast
to the control. The presence of ions in the medium may release rate compared to SRFs; the nutrients easily
impede the absorbency behavior of the polymers.12,65 escaped from the fertilizer core, since there were no
The weak performance observed for the coated fertil- physical impediments. In fact, after 2 days of incuba-
izers with dominated alginate content SA75-L25-c- tion in soil, it released almost 80% of phosphorus.
DAP, is most likely due to the alkalinity of the soil Meanwhile, SA75-L25-c-DAP, SA50-L50-c-DAP, and
used in this study (pH = 8.25) with contribution of Na+ SA25-L75-c-DAP released only 52%, 60%, and 26%
from alginate network. In fact, the cations present in of P, respectively (Fig. 11).
soil (such as Na+, K+, Ca2+, and Mg2+) penetrated in Although its release was quick in soil, the uncoated
the polymer network and created a screening effect on DAP showed slower release rate compared to its
the anionic carboxylate groups (–COO) that are release in water. Indeed, it was completely dissolved
believed to attract water molecules.65,67 This phe- within 4 days. At the same time, the coated DAP with
nomenon led to reduced performances regarding the both SA75-L25 and SA50-L50 released approximately
water absorbency of the polymer. In the same context, 70%, while the SA25-L75-c-DAP released less than
it was found that increasing the alginate concentration 40%. In this period, the release behavior of both SA75-
decreases the water absorption properties.55 SA25- L25-c-DAP and SA50-L50-c-DAP was almost the
J. Coat. Technol. Res.
100 100
% of cumulative N r elease
% of cumulative P r elease
80 80
100 100
60 80 60 80
60 60
40 40 40 40
20
20
20 Uc-DAP 0 20 Uc-DAP 0
0 2 4 6 8
0 1 2 3 4 5 6 7 8
SA75-L25-c-DAP SA75-L25-c-DAP
SA50-L50-c-DAP SA50-L50-c-DAP
SA25-L75-c-DAP SA25-L75-c-DAP
0 0
0 5 10 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40
Time (days) Time (days)
Fig. 11: Phosphorus and nitrogen cumulative release rate in soil from uncoated and coated DAP
same. But, once exceeding the first 4 days, the release The release decreased with increasing the lignin
behavior of SA50-L50-c-DAP became slower than that concentration in the SA-L granules, as shown in
of SA75-L25-c-DAP. From the nutrients release pro- Fig. 11, going over 30 days. It is worth mentioning
files illustrated in Fig. 11, it was noticed that the that among the beneficial effects of the lignin structure
release rate after 4 days became slower. This was is the inhibition of hydrolysis and nitrification by soil
mainly due to the decrease of nutrients concentration microorganisms, which ensure efficient nitrogen
inside the cores, which caused a decline of the osmotic absorption by plants. The mechanism of lignin’s
pressure inside and outside the fertilizer granules, inhibition of nitrification includes hydrogen-bond for-
resulting in a decrease in the water absorbency1,65 and, mation between lignin hydroxyl groups and ammo-
thus, decreased nutrients diffusion. At the same time, nium, impeding subsequently the latter
more ions and soil particles were absorbed by the transformation.25 The coated DAP fertilizers in the
polymeric network. These ions and soil particles played current study showed interesting results regarding the
a role of physical barrier, together with the coating slow-release property; however, it is still difficult to
layer.1 All the SRFs revealed a retardant release compare these results with other biopolymers coated
compared to their behavior in water. In fact, the fertilizers previously reported in the literature, because
release process in soil takes more time than the release the nutrients release from fertilizers is affected by
in water because, on the one hand, the total amount of many factors, such as fertilizer particle size, coating
water available in soil is lower, taking more time until process, coating thickness, temperature, soil moisture,
enough water penetrates the polymeric coating, dis- its bacterial activity, and its pH and so many other
solves nutrients and subsequently, allowing the release parameters. Based on the available experimental data,
process.68 On the other hand, the presence of soil it may be concluded that the most efficient coating
particles surrounding the coated fertilizers hinders the from a kinetic point of view is that of SA25-L75,
water penetration rate and slows down the release. and the DAP release in this case was largely delayed
After being incubated for two weeks in soil, nutri- from less than 1 week to more than 1 month.
ents were thoroughly released from SA75-L25-c-DAP.
The latter was the faster in reaching the complete
nutrients release among the other coated products.
Besides, nutrients release from polymer-coated fertil- Conclusions
izers is mainly controlled by diffusion.45 In fact, there is
a direct relationship between the polymers pore size The present study provides a cost-effective slow-
and nutrients diffusion rate. Indeed, alginate is a pH- release system based on sodium alginate and lignin
sensitive polysaccharide; its pore size is enlarged at biopolymers. This system would reduce the costs of
high pH values,56 thus, confirming the fastest release repeated application since it showed a sustained
results obtained when it was predominant, since the release of both nutrients P and N in water as well as
release was conducted in a moderately alkaline soil. in soil, going from four days to over one month before
Note that all the arguments and explanations men- reaching the complete release of nutrients. The SRFs
tioned earlier (water release experiments section), developed in this study that were believed to enhance
justifying the order of nutrients release in water from nutrients uptake by crops had also enhanced the water
the 3 different SRFs, remain valid for the release use efficiency, improved the fertilizer morphology, and
results obtained in soil. increased the granules hardness. It can be said that this
coating could help in the development of the next
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