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New generation of controlled release phosphorus fertilizers based

on biological macromolecules: Effect of formulation properties on
phosphorus release

Saloua Fertahi, Isabelle Bertrand, Mohamed Ilsouk, Abdallah

Oukarroum, M'Barek Amjoud, Youssef Zeroual, Abdellatif
Barakat

PII: S0141-8130(19)38114-0
DOI: https://doi.org/10.1016/j.ijbiomac.2019.12.005
Reference: BIOMAC 14032

To appear in: International Journal of Biological Macromolecules

Received date: 8 October 2019

Revised date: 25 November 2019
Accepted date: 1 December 2019

Please cite this article as: S. Fertahi, I. Bertrand, M. Ilsouk, et al., New generation
of controlled release phosphorus fertilizers based on biological macromolecules: Effect
of formulation properties on phosphorus release, International Journal of Biological
Macromolecules(2019), https://doi.org/10.1016/j.ijbiomac.2019.12.005

This is a PDF file of an article that has undergone enhancements after acceptance, such
as the addition of a cover page and metadata, and formatting for readability, but it is
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version to give early visibility of the article. Please note that, during the production
process, errors may be discovered which could affect the content, and all legal disclaimers
that apply to the journal pertain.

© 2019 Published by Elsevier.

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New Generation of Controlled Release Phosphorus Fertilizers based on

Biological Macromolecules: Effect of Formulation Properties on

Phosphorus Release

Saloua Fertahi1,2,3,5, Isabelle Bertrand1, Mohamed Ilsouk2, Abdallah Oukarroum2, M’Barek

Amjoud3, Youssef Zeroual4 and Abdellatif Barakat2,5*

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1
Eco&Sols, Univ Montpellier, CIRAD, INRA, IRD, Montpellier SupAgro, 2, Place Pierre

Viala, 34060 Montpellier, France

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2
Mohammed VI Polytechnic University (UM6P), Hay Moulay Rachid, 43150 Ben Guerir,
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Morocco
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3
LMCN, Faculté des Sciences et Techniques Guéliz, Université Cadi Ayyad, 40000

Marrakech, Morocco
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4
OCP/ Situation Innovation, OCP Group, Jorf Lasfar Industrial Complex, BP 118 El Jadida,
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Morocco
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IATE, Univ Montpellier, CIRAD, INRA, Montpellier SupAgro, 2, Place Pierre Viala, 34060

Montpellier, France

*abdellatif.barakat@inra.fr

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Abstract

The main objective of this work was to study the possibility of using polysaccharides and

lignin as a coating material for water-soluble triple superphosphate (TSP) granular fertilizers.

In this study, composites based on three polysaccharides (sodium alginate (alginic acid

sodium salt): AL, kappa-carrageenan: CR and carboxymethyl cellulose sodium salt: CM) and

lignin (LG) were prepared. The lignin used was extracted from olive pomace (OP) biomass

using the alkali method. The morphological, mechanical, and surface properties as well as the

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thermal behavior of the coatings were characterized and compared. Their morphology and

thickness revealed by scanning electron microscopy (SEM) showed good adhesion between

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the fertilizer and coating materials. The results showed that the lignin-carrageenan
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formulation (LGCR) exhibited the highest water absorbency and elastic modulus. Release
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tests showed the effect of the TSP/biopolymer mass ratio and that the slowest P release was
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obtained with the LGCR@TSP formulation composite within 3 day. In addition, 59.5% and

72.5% of P was released after 3 days with the TSP/biopolymer mass ratios of 5/1 and 15/1,
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respectively, compared to 100% P release with the uncoated TSP.

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Keywords: Polysaccharide, Lignin, Biomass, Phosphorus Fertilizer, Coating, Controlled

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Release

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1. Introduction

Recently, much attention has been paid to fertilizers with slow release and water retention

properties due to their essential roles in the development of sustainable agriculture and

horticulture [1]. Plant growth and yield mainly rely on the nutrients available in soil and

water. When soil nutrients are missing or in short supply, fertilizers, mostly of chemical

origin, are applied. Their use is open to criticism because of their price, their negative impact

on the environment (water and air pollution) and the fossil origin of phosphorus fertilizers.

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Phosphorus fertilizers are one of the most highly demanded because P is often the most

limiting plant nutrient.3 This is not because the amount of total P in soil is low but rather

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because the P in soils is in chemical forms that are not available to plants [2,3]. The world
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phosphate fertilizer demand is expected to reach 45.858.000 tons (P2O5) in 2020, while it was
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41.151.000 tons in 2015 [4].. However, due to the low efficiency of soil P fertilizers, only 10-
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20% of this P is taken up by plants [1,5,6]. The currently available forms of P fertilizers

require further improvements to increase their bioavailability in soils. Controlled-release

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fertilizers (CRFs) may improve the efficiency of P fertilizers while reducing their negative

environmental effects [7,8]. CRFs employ either coating or encapsulation of mineral

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fertilizers in polymeric matrices. CRFs use is a new trend and a good alternative to
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conventional fertilizer to reduce fertilizer consumption and loss and to alleviate the negative

environmental effects of chemical fertilizers. In most cases, the fertilizer granule is

encapsulated inside an inert material [9]. The coating layer acts as a physical barrier that

controls nutrient release [7]. The release behavior of water-soluble fertilizers depends on

many parameters, including the porosity and structure of the coating material, coating

thickness, granule size and form, soil temperature and pH, humidity and microbial activity

[7,10–12]. The coating materials applied most frequently are sulfur [13,14], waxes [15],

polystyrene [16], polyethylene [15,17,18], poly(N-isopropylacrylamide) [19,20], polyurethane

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[19], polysulfone [21–24], polyacrylonitrile [23,24], etc. However, the combination of

fertilizer and polymeric coatings has some disadvantages. The majority of synthetic polymers

require organic solvents (e.g., N-dimethylformamide [24], chloroform [25]) for solubilization,

which are harmful to the environment. In addition, the polymers remain in the soil when the

nutrients are exhausted. According to Trenkel [26], the use of polymeric materials in coatings

could lead to an undesirable accumulation of plastic residues of up to 50 kg/ha/year. The

development of environmentally friendly CRFs using biodegradable polymers derived from

biomass, agricultural and agro-industrial waste (carbohydrates, lignin, etc.) is a much better

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solution. Compared to synthetic polymers, biological macromolecules are relatively

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inexpensive [27], biodegradable, nontoxic for soil organisms and contribute to the
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improvement of soil properties [28,29]. In addition, biological polymers appear to be a
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potential alternative to synthetic polymers for CRFs coatings [30] and could contribute

significantly to organic waste recycling and the circular economy. Lignin is a cheap and
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natural polymer available as a waste material, as it is recovered mainly as a byproduct from

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wood pulping processes, with approximately 100 million tons produced annually

worldwide[31]. Moreover, compared to other polymers, lignin is a renewable, biodegradable,

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amorphous, relatively hydrophobic biopolymer that is rich in recalcitrant carbon, which could
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contribute to increasing the soil organic matter content [9]. Studies using commercial lignin

blended with additives as a coating agent (rosins and linseed oil [8,9], alkenyl succinic

anhydride [32]) showed its efficiency at decreasing the release rate of nutrients from

fertilizers. Polysaccharides are also used in coating formulations. However, these compounds

have never been tested alone. They are always mixed with other polymers or other

components, such as clays [33]. Wan et al [34] reported that k-carrageenan-Na-alginate and k-

carrageenan-g-poly(acrylic acid)/celite composite superabsorbents were used as inner and

outer coating materials, respectively, for nitrogen fertilizer. This double-coated fertilizer had

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slow-release behavior and improved the water-holding capacity and water-retention properties

of the soil.

This work is a continuation of the investigations of new biobased formulations for CRF

production, initiated in our previous work recently published [30]. This study for objective to

use extracted lignin from olive pomace (OP) biomass and some commercial polysaccharides

(alginates (AL) from brown algae, carrageenan (CR) from red algae and carboxymethyl

cellulose (CM) from wood pulp) for the preparation of different formulations composites for

TSP fertilizer coating. The choice of these polysaccharides is based on the availability and

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dissimilarity of their basic materials (algae and wood), their ability to form films and their

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high water absorption capacity [34]. The main objective of this research was to evaluate the
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influence of different biopolymers coatings on the P release behavior of CRF granules.
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2. Experimental Section
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In this study, OP was used for lignin extraction. OP was provided from a Moroccan olive

press (Tadla region). Kappa carrageenan (CR) (CAS: 1114-20-8), sodium alginate (AL)
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(CAS: 9005-38-3), sodium carboxymethyl cellulose Mw~700.000 (CM) (CAS: 9004-32-4),

potassium carbonate K2CO3 (CAS: 584-08-7), sodium hydroxide NaOH (CAS: 1310-73-2)
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and phosphorus pentoxide (P2O5) (CAS: 1314-56-3) were purchased from Sigma-Aldrich.
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Triple superphosphate (TSP), a granular phosphate fertilizer (46% P2O5), was produced and

offered by OCP group, Morocco.

2.1. Lignin polymer extraction from OP biomass

The lignin polymer used in this study was extracted from OP biomass using the alkali method.

Details of the lignin (LG) alkali extraction and the chemical and structural analysis of the OP

and LG were presented and discussed in our previous work [30]. The elementary composition

of the LG biomass was estimated to be 58.24± 0.01% C, 7.89 ± 0.03% H, and 28.05 ± 0.07%

O, and the C/N ratio was 32.54.

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2.2. Preparation of formulations and polymer-based films

Formulations and composite films were prepared using lignin solution (LG), alginate (AL),

carboxymethyl cellulose (CM), and carrageenan (CR) in different ratios (Table 1). Black

liquor (33.34 g/L) was used directly without stirring for lignin formulation and film

preparation. Polysaccharide solutions (AL, CM, CR) were prepared separately in water (0.5

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w/w%) under constant stirring for 2 h at ambient temperature (Table 1). The lignin-

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polysaccharide-based composites were prepared as follows: 80% lignin was mixed with 20%

polysaccharides (w/w). All solutions were stirred overnight at room temperature. The same
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formulations were used for composite film preparation and TSP fertilizer coating. For the film
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preparation, the mixtures were deposited onto square Petri dishes (12 cm), and the water was
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evaporated by drying overnight at 40 °C. Films were made in triplicate.

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Table 1: Composition of prepared formulations. LG: lignin, AL: alginate, CM:

carboxymethyl cellulose, CR: carrageenan, LGAL: lignin-alginate, LGCM: lignin-

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carboxymethyl cellulose, LGCR: lignin-carrageenan

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Polymers-based formulations LG (%) AL (%) CM (%) CR (%)

LG 100 0 0 0

AL 0 100 0 0

CM 0 0 100 0

CR 0 0 0 100

LGAL 80 20 0 0

LGCM 80 0 20 0

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LGCR 80 0 0 20

2.3.Characterization of lignin-polysaccharide composite films

2.3.1. Contact angle

The hydrophobicity of the composite films was evaluated by analyzing the behavior of water

drops injected onto their surfaces. Before contact angle measurements, films were cut into

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small rectangles (0.5 cm*2 cm), and their support sides were glued to glass slides using

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double-sided tape. Samples were equilibrated for 5 days at 46% relative humidity (RH) in a

desiccator in the presence of K2CO3-saturated solution. A humidity detector was used to

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verify the obtained humidity. Contact angle measurements were realized with a goniometer
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(Digidrop, GBX, France) equipped with a diffuse light source and a CCD camera (25
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frames/sec). A droplet of ultrapure water (∼3 μL) was deposited on the film surface with a

precision syringe (Teflon needle, 0.82 mm external diameter). The method is based on image
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processing and curve fitting for the contact angle. The video was analyzed frame-by-frame
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with GBX software to determine the contact angle as a function of time [35,36]. Three

measurements were performed on each sample.

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2.3.2. Mechanical properties

The film elasticity (tensile modulus EM), tensile strength (TS) and elongation at break (EB)

were studied using tensile tests. Tests were performed on films using a texture analyzer (TA.

XT plus). The tensile specimens were cut into rectangles (80 mm in length and 10 mm in

width). The gauge length was fixed at 30 mm, and the speed of the moving clamp was 5

mm/min [37]. Measurements were carried out at room temperature. Three replicates were

characterized, and the results are reported as average values with standard deviations.

2.3.3. Thermogravimetric analysis (TGA)

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The different formulations were analyzed using TGA. TGA was conducted under nitrogen

(with a flow rate of 50 mL/min) using a TGA instrument (Mettler Toledo) with a 5 °C/min

heating rate from 25 to 900 °C. Ash content was determined under air (with a flow rate of 50

mL/min) with an isothermal segment (900 °C for 1 h).

2.4.Preparation and characterization of TSP fertilizer coatings

Granules of TSP fertilizer were sieved to select homogeneous granules with diameters of 2-3

mm and then placed into a rotary drum (12 rpm, capacity of 11 L) developed in our

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laboratory. The distance between the spray nozzle and the center of the rotary drum was 25

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cm. Fifty grams of TSP granules were covered with a layer of different formulations (3.33 g)

based on lignin and polysaccharides by spraying at regular time intervals. The mass ratio of
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TSP/polymer was 15/1. Then, the coated TSP granules were continuously dried in the rotary
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drum by a hot air stream (65°C). To study the effect of the solution concentration on coating
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thickness and phosphorus release behavior, the mass concentration of the coating solutions

was tripled (the ratio of TSP/polymer was 5/1).

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2.4.1. Morphology and thickness of the coating layer

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The morphology of the coated TSP was evaluated by a tabletop scanning electron microscopy
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(SEM) (Phenom ProX, Phenom-World) using a backscattered electron detector (acceleration

voltage of 10 kV, mode image). Three granules of each type of coated TSP fertilizer were

randomly chosen. These granules were cut in half with a razor blade and fixed on a support

using double-sided tape. To measure the thickness of the coating layers, the drawing rule

option of the SEM was used, and three measurements were performed on different areas of

each granule.

2.4.2. Hygroscopicity of uncoated and coated TSP

Coated TSP granules were dried at 50°C in a vacuum oven in the presence of P 2O5. Samples

were weighed to a constant weight (complete drying). Then, they were conditioned in
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humidity-controlled rooms at three relative humidities: 35, 60 and 80%. The water

absorbency of the coated TSP was monitored for 3 days [8]. Samples were weighed every 24

h, and the water absorption was determined by the weight difference between dried and

conditioned samples. All the determinations reported here are triplicate results with standard

deviations.

2.5. Slow release behavior of coated TSP in water

For release experiments, uncoated and coated fertilizers were equilibrated for 3 days at 60%

of
RH. Then, 0.25 g of each type of coated TSP was immersed in 50 ml of distilled water in

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glass bottles. The bottles were conditioned at a constant temperature of 25°C. After 1 and 6 h,

and 1, 2, 3, 4 and 5days, 1 ml of the different solutions was sampled for phosphorus
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concentration determination, and an additional 1 ml of distilled water was added to the bottles
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to maintain a constant volume. All release experiments were carried out in triplicate. The
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phosphorus concentration was determined using the colorimetric molybdenum vanadate

method [24]. The phosphorus release at each time was obtained by Equation 1, which was
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proposed by Rashidzadeh et al [38], and expressed in relation to the phosphorus concentration

and total weight of phosphorus contained in the TSP fertilizer. All the determinations reported
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here are triplicate results.

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𝑉𝑒 ∑𝐶𝑝𝑖 +𝑉0 𝐶𝑝𝑛

CR (%w/w) = *100 Equation 1
𝑚𝑝0

where CR is the cumulative amount of phosphorus released (%) from the TSP fertilizer, Ve is

the sampling volume, V0 is the initial volume of the release media, Cpi and Cpn are the

phosphorus concentrations (mg/ml), i and n are the sampling times, and mp0 is the total weight

of phosphorus contained in the TSP fertilizer.

2.6. Data analyses

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The average values were calculated for each treatment. Analysis of variance (ANOVA),

mixed models and correlation matrixes among treatments were performed using R version

3.4.2. The effect of formulation on contact angle (CA), Young’s modulus (EM), tensile

strength (TS), elongation at break (EB), and thickness of the coating agent was tested by one-

way ANOVA. Mixed models ((Package: lme4) were performed to analyze the effect of

formulation and time and on P release with formulation and time as fixed effects and the

bottle (containing fertilizer and water) as a random effect. If significant, Tukey’s (for

ANOVA) and Emmeans (for mixed models) post hoc tests were used for pairwise multiple

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comparisons (p < 0.05). Correlations between films and coated TSP characteristics (treated

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with lignin and lignin-polysaccharides) were analyzed using a correlation matrix.
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3. Results and discussion
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Different lignin-polysaccharide formulations were prepared using alkali extracted lignin from
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OP residue (Scheme 1). The objective of this study was to develop a new generation of

coating formulations based on lignin and polysaccharides and to study the effect of the
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biopolymers type on the formulation properties. Finally, this study sought to correlate the

physicochemical properties of different composite formulations on the P release behavior. For

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this purpose, we utilized two strategies (Scheme 1):

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i) Preparation of composite films and study of their surface, mechanical and thermal

properties.

ii) Coating of TSP granules using the same formulations and study of their water

absorption, morphology and P release.

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Lignin

- Water solubility
Alginates Carrageenan
- Hydrophobicity
(AL) (CR)
- Mechanical properties
- Thermal behavior
Precipitation - Structure

Casting « Film »

Carboxylmethylcellulose Lignin
(CM) (LG)

Knif milling (1mm) Centrifugation

Concentrated
+ Liquor « lignin »
NaOH 5%w/w Coating

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« TSP granule»
(2h, 70°C, 300 rpm) -- Water
Humidityabsorption
absorption
- Morphology

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- Porosity
- Release rate of P
Olive -p
Pomace (OP)

Solid Residue
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« cellulose »
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Scheme 1: Extraction details of lignin from OP and strategies used to coat TSP fertilizer and to

characterize the coating agents

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3.1.Lignin-polysaccharide composite formulations

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3.1.1. Surface properties (contact angle)

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The hydrophobic surface corresponds to a contact angle > 60°, while a contact angle < 60°

corresponds to a hydrophilic surface [36]. A significant difference in contact angle was

observed between different formulations (p-value < 0.05) (Fig. 1). The hydrophobicity of

formulation composites decreased in the following order: CM = CR > > LGCM = LGAL =

LGCR> AL= LG. No significant difference was observed between CM (98°) and CR (98°)

films, which are more hydrophobic than alginate and lignin film composites with contact

angles of 57° and 53°, respectively. The low contact angle of the lignin film could be

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- +
attributed to the presence of HO Na groups in lignin (after solubilization in NaOH) (Schema

1).

120

c
c
100

80
b
b b
Contact angle (°)

ab

of
60 a

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40 -p
20
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0
LG AL LGAL CM LGCM CR LGCR
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Fig. 1. Contact angle of composite films, LG: lignin, AL: alginate, CM: carboxymethyl

cellulose, CR: carrageenan, LGAL: lignin-alginate, LGCM: lignin- carboxymethyl cellulose,

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LGCR: lignin-carrageenan. Different letters between treatments indicate significant

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differences (P<0.05, n=3).

Notley and al [39] reported that the contact angles of softwood kraft lignin and softwood

milled wood film (thickness: 50-60 nm) were 46, 52.5 and 55.5°, respectively. Norgren [40]

also reported that softwood lignin films with a thickness of 20-140 nm had a contact angle of

46°, which is in good agreement with our study. In another study, Ramirez et al [41] reported

that the contact angle of CM was estimated to be 83, compared to 98° obtained for CM in this

study. This difference could be due to the difference in the total solid content, the thickness of

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the CM composite film and the surface roughness. Lijun Yang et al [42] obtained for alginate

film a contact angle of approximately 59° compared to 53° obtained in this study. They

attributed this value to the hydrophilic surface of this material due to hydrophilic hydroxyl

functional groups in the AL polymer (Scheme 1). The contact angle obtained for CR was 98°

in agreement with Karbowiak et al [36] The contact angle of iota-carrageenan ranged between

88.3°-115.2°. The authors attributed this hydrophobic behavior of the iota-CR film to the

three-dimensional helical structure of the carrageenan polymer, with strong intramolecular

hydrogen bonding beneath the film surface and no orientation of polar groups at the surface.

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Jayasekara et al [43] also observed this phenomenon with starch composite film. We also

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observed that the addition of lignin (LG) to the polysaccharide formulation with a mass ratio
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of 4/1 (LG/polysaccharides) modified the hydrophobicity of the composite formulations (Fig.
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1). The presence of
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lignin in the formulation tends to decrease the surface hydrophobicity of lignin-

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polysaccharide composites. Shankar et al [44] observed the same phenomenon. They reported

that the contact angle of agar-lignin films was lower than that of agar films, and this reduction
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in contact angle might be due to the roughness of the film after the addition of lignin.
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3.1.2. Mechanical properties of composite films

Table 2: Tensile modulus (EM), tensile strength (TS) and elongation at break (EB) of

composite films. LG: lignin, LGAL: lignin-alginate, LGCM: lignin-carboxymethyl cellulose,

LGCR: Lignin-carrageenan, n=3

Formulation EM (KPa) TS (KPa) EB (%)

LG 786,93 ± 385ab 1135.09 ± 766a 1.46 ± 0.11a

LGCR 1191,51 ± 356a 3674.11 ± 318b 9.37 ± 1.99b

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LGCM 225.49 ± 96b 2510.98 ± 754ab 43.94 ± 15.99c

LGAL 612.53 ± 65ab 1653.57 ± 261a 2.79 ± 0.43a

Within a column, means followed by the same letter are not significantly different

3500 LG
LGCM
3000 LGAL
LGCR
2500
Stress (KPa)

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3500

2000

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3000

2500
Stress (KPa)

1500
2000
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1500

1000
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1000

500
500
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0
0 1 2 3 4 5 6 7
Strain (%)

0
0 10 20 30 40 50
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Strain (%)
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Fig. 2. Typical stress-strain curves of film composites: LG: lignin, AL: alginate, CM:

carboxymethyl cellulose, CR: carrageenan, LGAL: lignin-alginate, LGCM: lignin-

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carboxymethyl cellulose, LGCR: lignin-carrageenan, n=3

Fig. 2 shows the typical stress-strain curves of different composite films. The elastic modulus

(EM), tensile strength (TS) and elongation at break (EB) depends on the type and structure of

the polysaccharides in the composites (p-value < 0.05) (Table 2). The EM, TS and EB of the

obtained composite films varied between 225-1191 KPa, 1135-3674 KPa and 1.5 - 44%,

respectively. The TS of the lignin (LG) film was 1135.09 ± 766 KPa, which is lower than that

of the polysaccharide-incorporated composite films (Table 2). Aadil et al [36] reported that

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the tensile strength of lignin films extracted from acacia wood and blended with alginate was

413 ± 2 KPa, while the tensile strength increased to 625 ± 7, 569 ± 12, 466 ±6 KPa with the

addition of the different plasticizers, glycerol, epichlorohydrin and PEG 4000, respectively.

Lignin extracted from OP (this study) has a greater tensile strength than acacia wood lignin,

even when blended with alginate and plasticizers. This is probably due to the presence of fatty

acids in lignin from OP, as discussed in our previous work [30]. Fatty acids are usually used

as plasticizers in composite formulations [45], and their presence can play a role in natural

plasticizers in different lignin formulations. The lignin-carrageenan (LGCR) composite

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exhibited higher EM (1191 KPa) and TS (3674 KPa) than the LGAL and LGCM composite

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films. We can also see from the results that TS and EB were significantly increased by 224%
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and 542%, respectively, with the addition of CR compared to LG, while the addition of CM
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significantly increased the EB by 2910%. This increase in EB compared to LG film can be

explained by the hygroscopicity of polysaccharides. These compounds are more hygroscopic

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than LG polymers; hence, water uptake could explain the plasticization behavior [46].
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However, in the case of lignin loaded with alginate, no strong effect on mechanical properties

was observed compared to the LG film. The lignin polymer has a tridimensional and porous
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surface structure that might aid in compatibility with the polysaccharides. These phenomena
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have also been observed in the plant cell wall, confirming the lignin-polysaccharide

interaction [48,49].

3.1.3. Thermogravimetric analysis (TGA)

The thermal stability and degradation behavior of polysaccharides and lignin-polysaccharide

composites were assessed using TGA and weight loss curves. Fig. 3A presents the TGA

analysis of the polysaccharide films. From these curves, we can observe that the thermal

degradation of all polysaccharides occurs in three steps. The first step at 25-105 °C

corresponds to water desorption, with approximately 9-13% overall weight loss due to

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dehydration. The second decomposition stage starts at 192°C for the AL and CR films and

230°C for the CM film. This step is attributed to the thermal degradation of polysaccharides.

In the last step, the AL and CM films lost approximately 50% of their weight at 340°C, while

the CR film had to reach 422°C to lose the same percentage of weight. This mass loss is

related to the formation of byproducts of polysaccharides during the thermal degradation

process [50]. Based on the TGA analysis (Fig. 3B) of LG and composite films, the lignin film

had fast thermal degradation compared to the lignin-polysaccharide blended film. The thermal

behavior of the LGAL and LGCM composites seemed to be similar. These films exhibited the

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slowest thermal degradation, followed by the LGCR and LG films. The 50% weights of LG

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and LGCR were lost at 450°C and 454°C, respectively, while LGCM and LGAL lost 50% of
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their initial mass at 464°C.
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Fig. 3. TGA of (A) polysaccharide films (AL: alginate, CM: carboxymethyl cellulose, CR:

carrageenan) and (B) LG and composite films (LG: lignin, LGAL: lignin-alginate, LGCM:

lignin- carboxymethyl cellulose, LGCR: lignin-carrageenan)

The blending of lignin with polysaccharides enhanced the thermal stability of the three

materials. LG, CM and CR films underwent the active weight loss step at 25-290 °C, while

this step occurred at 25-500°C with the addition of lignin. In general, the mass loss of

composite-polymer films occurred between 25 and 500°C [51,52]. Changhua Liu [51]

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reported similar intervals of degradation temperatures of lignin-poly (4-vinylpyridine) films.

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3.2.Coated TSP fertilizer properties
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3.2.1. Morphological characterization of coated TSP fertilizers

C D E
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A
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F G H
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B I J K

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Fig. 4. Real image of noncoated TSP (A) and coated TSP at the TSP/polymer ratio of 15/1

with (B) LG (lignin), (C) AL (alginate), (D):CM (carboxylmethyl cellulose), (E) CR

(carrageenan), (F) LGAL, (G) LGCM and (H) LGCR, and at the TSP/polymer ratio of 5/1

with (I) LGAL, (J) LGC and (K) LGCR

A B C

of
ro
-p
D E F
re
lP
na
ur
Jo

Fig. 5. SEM of cross-section of the coated TSP fertilizer at the TSP/polymer mass ratio of

15/1 with (A) LGAL (lignin-alginate, (B) LGCM (lignin- carboxymethyl cellulose and (C)

LGCR (lignin-carrageenan) and at the TSP/polymer ratio of 5/1 with (D) LGAL, (E) LGCM

and (F) LGCR

Fig. 4 presents pictures of coated TSP. The interactions of TSP granules and coatings were

observed using SEM (Fig. 5). The thickness of the coating layers was determined for the

coated TSP fertilizers. The thickness of the layers (TSP/polymer ratio of 15/1) was

18
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71.3±23.6m on average. The coating formulation has no significant effect on coating

thickness (p-value > 0.05).

200
TSP/Polymer ratio: 5/1 b
180 TSP/Polymer ratio: 15/1
160
b

140 b
Coating thickness (µm)

120 a a
100 a
a a a
a

of
80
a
60
40
ro
-p
20
re
0
P

P
P

P
P

P
P
TS

TS
TS

TS
TS

TS
TS
lP
@
@

R@
@
L@
L@

R@
LG

M
M
A
A

C
C
C
LG

LG
LG
na

Fig. 6. Thickness of coating layers on TSP granules coated with LG (lignin), AL (alginate,

LGAL (lignin-alginate), CM (carboxylmethyl cellulose), LGCM (lignin- carboxylmethyl

ur

cellulose), CR (carrageenan) and LGCR (lignin-carrageenan). Different letters between

Jo

treatments indicate significant differences (P<0.05, n=9).

The coating thickness is an important parameter that can control the nutrient release rate

[24,53]. The effect of two ratios of TSP/polymers (15/1 and 5/1) on the coating agent

thickness was studied, and the results are shown in Fig. 6. A significant effect on coating

agent thickness was observed between ratios for the granules coated with the three

formulations. The coatings formed with a higher polymer concentration exhibited higher

thickness (135.6±20.9m) for the TSP/polymer ratio of 5/1 than the 71.3±23.6 m observed

19
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for the TSP/polymer ratio of 15/1. This result is in agreement with the previous report of

Anna Jarosiewicz et al [24], suggesting an increase in the thickness with increasing polymer

concentration in the coating solution.

3.2.2. Hygroscopicity of uncoated and coated fertilizers

Fig. 7. illustrates the water absorption of uncoated and coated TSP within 3 days at different

RHs (35%, 60% and 80%). The water absorption of all formulations increased with increasing

air humidity and with time. LGCR@TSP, LGAL@TSP and LGCM@TSP exhibited the

of
highest hygroscopicity in the following order: LGCR@TSP > LGAL@TSP > LGCM@TSP.

ro
According to Liang et al [54], the water absorption of coating polymers depends on many

factors, such as the amount of hydrophilic groups and elasticity of the polymer networks. As
-p
previously mentioned in Table 2, LGCR exhibited the highest elastic modulus (EM)
re
(1191.51±356 KPa), followed by LGAL (612.53 ± 65 KPa) and then LGCM (225.49±96
lP

KPa). The major result was that the water absorption of the coating increased when the

elasticity increased, which could improve the swelling properties of the coated fertilizers. It is
na

noteworthy that a coated fertilizer with swelling and slow release behavior could effectively

improve the utilization of both fertilizer and water resources [54].

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Jo

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Humidity absorption (%)

TSP AL@TSP
A
CM@TSP CR@TSP
LGAL@TSP LGCM@TSP
LGCR@TSP LG@TSP
2

0
4
B
Humidity absorption (%)

of
1

ro
0
10
9
-p C
Humidity absorption (%)

8
re
7
6
5
lP

4
3
2
1
na

0
0 1 2 3
Time (days)
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Fig. 7: Water absorption (WA) of uncoated and coated fertilizers over time at different

relative humidities: (A) 35%, (B) 60% and (C) 80% RH with LG (lignin), AL (alginate), CM
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(carboxylmethyl cellulose, CR (carrageenan) LGAL (lignin-alginate), (G) LGCM (lignin-

carboxylmethyl cellulose) and LGCR (lignin-carrageenan), n=3.

3.3.Slow-release behavior of phosphorus from coated TSP fertilizers

Table 3: Release behavior of TSP and coated TSP with different polymers in water, TSP

coated with LG: lignin, AL: alginate, CM: carboxymethyl cellulose, CR: carrageenan, LGAL:

lignin-alginate, LGCM: lignin- carboxymethyl cellulose, LGCR: lignin-carrageenan, n=3.

Formulation TSP/ P-release in water (%) over time (h)

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Polymer 6 24 48 72 96 120

ratio

TSP - 72.0 ± 0.4a 85.0 ± 14a 95.0 ± 2.7a 99.5 ± 4.3a - -

LG@TSP 15/1 34.3 ±4ab 55.5±6.4a 64.1±1bc 65±9.8bcd 71.6± 1.8abcd 76±0.7a

CR@TSP 15/1 44.9 ± 4.9ab 60.9 ± 0.7a 69.5 ± 7.8ab 78.1 ± 5.7abcd 84.7 ± 15a 90.2 ± 3.8b

CM@TSP 15/1 39.7 ± 7.6ab 77.1 ± 0.1a 73.8 ± 4.7bc 79.5 ± 3.5abc 75.1 ± 1.7abc 73.7 ± 1.1a

AL@TSP 15/1 19.3 ± 13b 76.7 ± 0.1a 77.9 ± 6.6abc 80.6 ± 10ac 77.3 ± 5.5ac 75.3 ± 4.4a

LGCR@TSP 15/1 28.2 ± 4.8ab 52.0 ± 6.5a 59.0 ± 8.9abc 72.5 ± 1.2abcd 78.8 ± 2.0abcd 75.3 ± 4.0abcd

LGCM@TSP 15/1 55.7 ± 9.4ab 66.7 ± 0.8a 73.1 ± 4.8bc 71.9 ± 0.5bcd 69.6 ± 0.9abcd 68.5 ± 1.1ad

LGAL@TSP 15/1 51.7 ± 9.9ab 74.5 ± 0.1a 67.1 ± 1.7bc 68.3 ± 3.1bcd 68.7 ± 3.1abcd 64.9 ± 0.5acd

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LGCR@TSP 5/1 - 59.1 ± 1.9a 60.0 ± 1.0c 59.5 ± 1.9bd 60.4 ± 3.0bcd 59.3 ± 1.6cd

5/1 - 59.9 ± 1.8a 59.0 ± 1.4c 58.9 ± 2.4d 57.4 ± 0.8bd 59.2 ± 2.2cd

ro
LGCM@TSP

LGAL@TSP 5/1 - 56.3 ± 3.3a 61.7 ± 3.9bc

-p 57.9 ± 5.5d 55.1 ± 3.7d 55.8 ± 3.5c

Within a column, means followed by the same letter are not significantly different
re
As shown in Table 3, the untreated TSP released approximately 72±0.4, 85±140 and

99.5±4.3% of P within 6, 24, and 72 h, respectively. In contrast, the fertilizers coated with
lP

only lignin or only polysaccharides or with lignin-polysaccharides (the TSP/polymer ratio of

na

15/1) released only 19.3-55.7%, 52-77.1% or 68.3-80.6% within 6, 24, and 72 h, respectively.

Statistical analysis showed a significant effect of coating formulation and time on the delay of
ur

P release (p<0.05). The slowest P release was observed with the LGCR@TSP formulation
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within the first and second days.

To understand the relationship between P release behavior and the physicochemical properties

of film composites of coated TSP discussed previously in this work, a correlation matrix was

constructed (Fig. 8). P release is strongly negatively correlated with EM (R= -0.81), while it

is strongly positively correlated with EB (R=0.93). The young modulus (EM) represents the

elastic deformation. When the coating material is elastic, the shell is able to resist the internal

pressure created inside the core upon contact with water, and the P is released slowly without

the shell being destroyed. A moderate negative correlation between P release and CA was also

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revealed (R= -0.49). This phenomenon could be explained by the fact that, when the contact

angle is large, the coating material is hydrophobic, and then the affinity between the layer and

water is weak. This lack of affinity prevents the penetration of large quantities of water inside

the fertilizer core and then decreases the dissolution of TSP. For TS and WA, a weak or no

correlation was observed with P release (R<0.11). From these data and discussion, we

concluded that the LGCR formulation is the most efficient coating for mineral fertilizer due to

its high elastic modulus, high CA, high water absorption and, as a consequence, slow release

of P.

of
ro
-p
re
lP
na
ur
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Fig. 8. Correlation matrix between the properties of composite films and coated TSP. Film

properties: EM (elastic modulus), TS (tensile strength), EB (elongation at break) and CA

(contact angle). Coated TSP properties: P release within 1 day and WA (water absorption at

RH 35% within 1 day). Positive correlations are displayed in blue, and negative correlations

are displayed in red. Color intensity and circle size are proportional to the correlation

coefficient, R. On the right side of the correlogram, the legend color shows the correlation

coefficients and the corresponding colors.

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The release behaviors of TSP coated with LGCR, LGCM and LGAL formulations at

TSP/biopolymer ratios of 15/1 and 5/1 are shown in Table 3. A statistical study showed a

significant effect of TSP/biopolymer ratios (the effect of coating thickness) on the release

response from LGAL@TSP and LGCM@TSP (p-value<0.05) but not LGCR@TSP. As

previously presented in Fig. 5B, a high TSP/biopolymer ratio resulted in a high thickness. A

higher polymer coating concentration decreased the P release of coated TSP granules due to

the increase in coating layer thickness. After 3 days, TSP coated with LGCR, LGCM and

LGAL formulations at the TSP/biopolymer ratio of 15/1 (thickness=71.3±23.6m) released

of
72.5%, 71.9% and 68.3% of P, respectively, while TSP coated with the same formulations

ro
using a TSP/biopolymer ratio of 5/1 (thickness=135.6±20.9m) released only 59.5, 58.9 and
-p
57.9% of P. These results are in accordance with other studies in the literature. Lubkowski et
re
al [55] showed that the release of phosphate from uncoated fertilizer was very fast and that all
lP

phosphates were released within 50 min, while coated NPK with different thicknesses (0.047–

0.5425 mm) revealed a smaller release of phosphate in comparison with the initial NPK.
na

Jarosiewicz et al [24] showed that the release rate of NPK can be controlled by adjusting the

thickness of the coating. They argued that NPK granules with double or triple-layered
ur

coatings (high thickness) released nutrients much slower than granules coated with one layer.
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NPK granules coated with one layer of 17% polyacrylonitrile (thickness ≈ 0.2 mm) released

93.7% of K+ within 5 h, while granules with three layers of the same formulation (thickness ≈

0.49 mm) released only 11.7%. Behin et al [56] confirmed that the release of nitrogen

depends strongly on the thickness of the coating. They reported that the dissolution rate

decreases with increasing coating percentage. For urea coated with acetylated kraft lignin and

sulfite lignin, dissolution rates of 88 and 97%, respectively, were obtained after 24 h for the

sample with a 5.0% coating, whereas only 43 and 72% were obtained for the sample with a

15.0% coating.

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Table 4: Comparative studies of different works using lignin as a coating material to control

nutrient release

of
Coating materials Fertilizer Granule T drying Coating Thickness Release rate(%) Ref

size (mm) (oC) methods (m)

ro
Lignin + TSP 2-3 65 Rotating Noncoated 100% after 3 d This work

Polysaccharides pan
-p77-211 Coated 57-58% after 3d

Commercial lignin + TSP 2 Rotating 83-106 Noncoated 80% after 3days Garcıa et al
re
rosins pan Coated 20% after 3 days [8]

Commercial lignins Rotating Noncoated >80% after 30min

lP

+ plasticizers + - 70 pan - Coated 60-80%after 30min Mulder et al

hydrophobic compounds Urea [32]

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Commercial lignin Urea 0.5-5 - Matrix - Non-treated 100% after <5h Perez et al

Matrix 40-90% after 1h [57]

ur
Jo

Table 4 provides a comparative study of the results obtained in this work and those from

previous studies using lignin as a coating material. It can be deduced from the work of Perez

et al [57] that using lignin alone does not improve the delayed release of urea in water, which

can be explained by the presence of the polar groups on its surface and the resulting good

affinity with water. Mulder et al [32] also employed lignin coupled with plasticizers and some

other hydrophobic compounds and reported that complete nitrogen release through these

coating materials still occurred within 1 h. To improve its coating properties, lignin has also

been mixed with rosins as a coating system for soluble fertilizers such as phosphate fertilizer

[8] According to Garcia et al [8], only 20% of P was released was this method. In comparison

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with these previous works, it can be concluded that our study is interesting in that we used

low-cost materials based on OP, which can potentially be a good candidate for coating

fertilizers and slowing the release rate of nutrients; however, our materials remain less

efficient in this regard than synthetic polymers.

4. Conclusion

This work reports the valorization of lignin extracted from OP biomass with polysaccharides

of
as a new coating material for water soluble TSP fertilizer. Films containing lignin and

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carrageenan show the best mechanical properties. The blending of lignin with polysaccharides

reduced the hydrophobicity of the composites compared to that of the pure polysaccharide
-p
films but still showed higher hydrophobicity than the lignin film. The coating materials based
re
on lignin and polysaccharides appear to have a good interaction and adhesion with the mineral
lP

fertilizer surface, confirming the effect of different formulations on the delay of P release. The

results showed that more than 95% of P was released from uncoated TSP within 48 h, and
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100% of P was released within 72 h, while the release of P with the lignin-

polysaccahrides@TSP formulations decreased to approximately 60% within 72 h with a

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TSP/polymer ratio of 5/1.

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Acknowledgments

We would like to thank the OCP Group, INRA, and University Mohamed VI Polytechnic

(UM6P) for providing financial support for this study (Atlass Project). We are grateful to

Philippe Deleporte for his help with the statistical analysis.

References

[1] Y.P. Timilsena, R. Adhikari, P. Casey, T. Muster, H. Gill, B. Adhikari, Enhanced

efficiency fertilisers: A review of formulation and nutrient release patterns, Journal of

the Science of Food and Agriculture. 95 (2015) 1131–1142. doi:10.1002/jsfa.6812.

26
 Journal Pre-proof

[2] I. Bertrand, P. Hinsinger, B. Jaillard, Dynamics of phosphorus in the rhizosphere of

maize and rape grown on synthetic , phosphated calcite and goethite Dynamics of

phosphorus in the rhizosphere of maize and rape grown on synthetic , phosphated

calcite and goethite, Plant and Soil. 211 (1999) 111–119. doi:10.1023/A.

[3] P. Hinsinger, Bioavailability of soil inorganic P in the rhizosphere as affected by root-

induced chemical changes : a review, Plant and Soil. 237 (2001) 173–174.

doi:10.1023/A:1013351617532.

[4] FAO, World Fertilizer Trends and Outlook to 2020, Food and Agriculture Organization

of
of the United Nations (FAO): Rome, 2017.

ro
[5] M.L. Lan Wu, Preparation and characterization of cellulose acetate-coated compound
-p
fertilizer with controlled-release and water-retention, Polym Adv Technol. 17 (2006)
re
395–418. doi:10.1002/pat.

[6] K. Rop, G.N. Karuku, D. Mbui, I. Michira, N. Njomo, Formulation of slow release
lP

NPK fertilizer (cellulose-graft-poly(acrylamide)/nano-hydroxyapatite/soluble fertilizer)

na

composite and evaluating its N mineralization potential, Annals of Agricultural

Sciences. 63 (2018) 163–172. doi:10.1016/j.aoas.2018.11.001.

ur

[7] B. Azeem, K. Kushaari, Z.B. Man, A. Basit, T.H. Thanh, Review on materials &
Jo

methods to produce controlled release coated urea fertilizer, Journal of Controlled

Release. 181 (2014) 11–21. doi:10.1016/j.jconrel.2014.02.020.

[8] M.C. García, A. Vallejo, L. García, M.C. Cartagena, Manufacture and Evaluation of

Coated Triple Superphosphate Fertilizers, Industrial & Engineering Chemistry

Research. 36 (1997) 869–873. doi:10.1021/ie960153o.

[9] M. García, J.A. Díez, A. Vallejo, L. García, M.C. Cartagena, Use of Kraft Pine Lignin

in Controlled-Release Fertilizer, Industrial & Engineering Chemistry Research. 35

(1996) 245–249. doi:10.1021/ie950056f.

27
 Journal Pre-proof

[10] N.Z. Lupwayi, C.A. Grant, Y.K. Soon, G.W. Clayton, S. Bittman, S.S. Malhi, B.J.

Zebarth, Soil microbial community response to controlled-release urea fertilizer under

zero tillage and conventional tillage, Applied Soil Ecology. 45 (2010) 254–261.

doi:10.1016/j.apsoil.2010.04.013.

[11] Z. Majeed, N.K. Ramli, N. Mansor, Z. Man, A comprehensive review on biodegradable

polymers and their blends used in controlled-release fertilizer processes, Reviews in

Chemical Engineering. 31 (2015) 69–95. doi:10.1515/revce-2014-0021.

[12] X. Jia, G. Zhang, J. Hu, X. Zhang, Z. Liu, H. Wang, F. Zhou, pH-Responsive

of
Controlled-Release Fertilizer with Water Retention via Atom Transfer Radical

ro
Polymerization of Acrylic Acid on Mussel- Inspired Initiator, J Agric Food Chem. 61
-p
(2013) 5474–5482. doi:10.1021/jf401102a.
re
[13] D.W. Rindt, G.M. Blouin, J.G. Getsinger, Sulfur coating on nitrogen fertilizer to reduce

dissolution rate, Journal of Agricultural and Food Chemistry. 16 (1968) 773–778.

lP

doi:10.1021/jf60159a015.
na

[14] G.M. Blouin, D.W. Rindt, O.E. Moore, Sulfur-coated fertilizers for controlled release:

Pilot plant production, Journal of Agricultural and Food Chemistry. 19 (1971) 801–
ur

808. doi:10.1021/jf60177a039.
Jo

[15] S.M. Al-Zahrani, Utilization of Polyethylene and Paraffin Waxes as Controlled

Delivery Systems for Different Fertilizers, Industrial and Engineering Chemistry

Research. 39 (2000) 367–371. doi:10.1021/ie980683f.

[16] J. Abraham, V.N. Rajasekharan Pillai, Membrane‐ encapsulated controlled‐ release

urea fertilizers based on acrylamide copolymers, Journal of Applied Polymer Science.

60 (1996) 2347–2351. doi:10.1002/(SICI)1097-4628(19960627)60:13<2347::AID-

APP6>3.0.CO;2-E.

[17] O. A. Salman, Polyethylene-coated urea. 1. Improved storage and handling properties,

28
 Journal Pre-proof

Industrial & Engineering Chemistry Research. 28 (1989) 630–632.

doi:10.1021/ie00089a021.

[18] O.A. Salman, G. Hovakeemian, N. Khraishi, Polyethylene-coated urea. 2. Urea release

as affected by coating material, soil type and temperature, Ind Eng Chem Res. 28

(1989) 633–638. doi:10.1021/ie00089a022.

[19] A.S. Mathews, S. Narine, Poly[N-isopropyl acrylamide]-co-polyurethane copolymers

for controlled release of urea, Journal of Polymer Science Part A: Polymer Chemistry.

48 (2010) 3236–3243. doi:10.1002/pola.24090.

of
[20] Z. Ma, X. Jia, J. Hu, Z. Liu, H. Wang, F. Zhou, Mussel-Inspired Thermosensitive

ro
Polydopamine- graft -Poly( N -isopropylacrylamide) Coating for Controlled-Release
-p
Fertilizer, Journal of Agricultural and Food Chemistry. 61 (2013) 12232–12237.
re
doi:10.1021/jf4038826.

[21] M. Tomaszewska, A. Jarosiewicz, Encapsulation of mineral fertilizer by polysulfone

lP

using a spraying method, Desalination. 198 (2006) 346–352.

na

doi:10.1016/j.desal.2006.01.032.

[22] M. Tomaszewska, A. Jarosiewicz, Use of polysulfone in controlled-release NPK

ur

fertilizer formulations, Journal of Agricultural and Food Chemistry. 50 (2002) 4634–

Jo

4639. doi:10.1021/jf0116808.

[23] M. Tomaszewska, A. Jarosiewicz, K. Karakulski, Physical and chemical characteristics

of polymer coatings in CRF formulation, Desalination 146 (2002) 3 19-323. 3 (2002)

19–323. doi:10.1016/S0011-9164(02)00501-5.

[24] A. Jarosiewicz, M. Tomaszewska, Controlled-Release NPK Fertilizer Encapsulated by

Polymeric, J Agric Food Chem 2003, 51, 413-417. 51 (2003) 413–417.

[25] Milene M. E. Costa, Elaine C. M. Cabral-Albuquerque, Tito L. M. Alves, José Carlos

Pinto, and Rosana L. Fialho, Use of polyhydroxybutyrate and ethyl cellulose for

29
 Journal Pre-proof

coating of urea granules, Journal of Agricultural and Food Chemistryand. 61 (2013)

9984–9991. doi:10.1021/jf401185y.

[26] M.E Trenkel, Slow and Controlled-Release and stabilized Fertilizers, International

Fertilizer Industry Association: Paris, France, 2010.

[27] Y.C. Yang, M. Zhang, Y. Li, X.H. Fan, Y.Q. Geng, Improving the quality of polymer-

coated urea with recycled plastic, proper additives, and large tablets, Journal of

Agricultural and Food Chemistry. 60 (2012) 11229–11237. doi:10.1021/jf302813g.

[28] S.V. Patil, B.K. Salunke, C.D. Patil, R.B. Salunkhe, Studies on amendment of different

of
biopolymers in sandy loam and their effect on germination, seedling growth of

ro
Gossypium herbaceum L., Applied Biochemistry and Biotechnology. 163 (2011) 780–
-p
791. doi:10.1007/s12010-010-9082-1.
re
[29] I. Chang, J. Im, A.K. Prasidhi, G.C. Cho, Effects of Xanthan gum biopolymer on soil

strengthening, Construction and Building Materials. 74 (2015) 65–72.

lP

doi:10.1016/j.conbuildmat.2014.10.026.
na

[30] S. Fertahi, I. Bertrand, M. Amjoud, A. Oukarroum, M. Arji, A. Barakat, Properties of

Coated Slow-Release Triple Superphosphate (TSP) Fertilizers Based on Lignin and

ur

Carrageenan Formulations, ACS Sustainable Chemistry & Engineering. 7 (2019)

Jo

10371−10382. doi:10.1021/acssuschemeng.9b00433.

[31] D.S. Bajwa, G. Pourhashem, A.H. Ullah, S.G. Bajwa, A concise review of current

lignin production, applications, products and their environmental impact, Industrial

Crops and Products. 139 (2019) 111526. doi:10.1016/j.indcrop.2019.111526.

[32] W.J. Mulder, R.J.A. Gosselink, M.H. Vingerhoeds, P.F.H. Harmsen, D. Eastham,

Lignin based controlled release coatings, Industrial Crops and Products. 34 (2011)

915–920. doi:10.1016/j.indcrop.2011.02.011.

[33] Y. He, Z. Wu, L. Tu, Y. Han, G. Zhang, C. Li, Encapsulation and characterization of

30
 Journal Pre-proof

slow-release microbial fertilizer from the composites of bentonite and alginate, Applied

Clay Science. 109–110 (2015) 68–75. doi:10.1016/j.clay.2015.02.001.

[34] Y. Wang, M. Liu, B. Ni, L. Xie, K-Carrageenan-sodium alginate beads and

superabsorbent coated nitrogen fertilizer with slow-release, water-retention, and

anticompaction properties, Industrial and Engineering Chemistry Research. 51 (2012)

1413–1422. doi:10.1021/ie2020526.

[35] G. Blancher, M.H. Morel, E. Gastaldi, B. Cuq, Determination of surface tension

properties of wheat endosperms, wheat flours, and wheat glutens, Cereal Chemistry. 82

of
(2005) 158–165. doi:10.1094/CC-82-0158.

ro
[36] T. Karbowiak, F. Debeaufort, D. Champion, A. Voilley, Wetting properties at the
-p
surface of iota-carrageenan-based edible films, Journal of Colloid and Interface
re
Science. 294 (2006) 400–410. doi:10.1016/j.jcis.2005.07.030.

[37] M. El Achaby, Z. Kassab, A. Aboulkas, C. Gaillard, A. Barakat, Reuse of red algae

lP

waste for the production of cellulose nanocrystals and its application in polymer
na

nanocomposites, International Journal of Biological Macromolecules. 106 (2018) 681–

691. doi:10.1016/j.ijbiomac.2017.08.067.
ur

[38] A. Rashidzadeh, A. Olad, Slow-released NPK fertilizer encapsulated by NaAlg-g-

Jo

poly(AA-co-AAm)/MMT superabsorbent nanocomposite, Carbohydrate Polymers. 114

(2014) 269–278. doi:10.1016/j.carbpol.2014.08.010.

[39] S.M. Notley, M. Norgren, Surface energy and wettability of spin-coated thin films of

lignin isolated from wood, Langmuir. 26 (2010) 5484–5490. doi:10.1021/la1003337.

[40] M. Norgren, S.M. Notley, A. Majtnerova, G. Gellerstedt, Smooth model surfaces from

lignin derivatives. I. Preparation and characterization, Langmuir. 22 (2006) 1209–1214.

doi:10.1021/la052284c.

[41] C. Ramírez, I. Gallegos, M. Ihl, V. Bifani, Study of contact angle , wettability and

31
 Journal Pre-proof

water vapor permeability in carboxymethylcellulose ( CMC ) based film with murta

leaves ( Ugni molinae Turcz ) extract, Journal of Food Engineering. 109 (2012) 424–

429. doi:10.1016/j.jfoodeng.2011.11.005.

[42] L. Yang, J. Guo, J. Wu, Y. Yang, S. Zhang, J. Song, RSC Advances Preparation and

properties of a thin membrane based on sodium alginate grafting acrylonitrile, RSC

Advances,7 (2017) 50626–50633. doi:10.1039/c7ra08532j.

[43] R. Jayasekara, I. Harding, I. Bowater, G.B.Y. Christie, G.T. Lonergan, Preparation ,

surface modification and characterisation of solution cast starch PVA blended films,

of
Polymer Testing. 23 (2004) 17–27. doi:10.1016/S0142-9418(03)00049-7.

ro
[44] S. Shankar, J.P. Reddy, J. Rhim, Effect of lignin on water vapor barrier, mechanical,
-p
and structural properties of agar/lignin composite films, International Journal of
re
Biological Macromolecules. 81 (2015) 267–273. doi:10.1016/j.ijbiomac.2015.08.015.

[45] L. Montero De Espinosa, A. Gevers, B. Woldt, M. Graß, M.A.R. Meier, Sulfur-

lP

containing fatty acid-based plasticizers via thiol-ene addition and oxidation: Synthesis
na

and evaluation in PVC formulations, Green Chemistry. 16 (2014) 1883–1896.

doi:10.1039/c3gc42172d.
ur

[46] E.S. Abdou, M.A. Sorour, Preparation and characterization of starch/carrageenan

Jo

edible films, International Food Research Journal. 21 (2014) 189–193.

[47] S. Shankar, J. Rhim, Preparation and characterization of agar / lignin / silver

nanoparticles composite fi lms with ultraviolet light barrier and antibacterial properties,

Food Hydrocolloids. 71 (2017) 76–84. doi:10.1016/j.foodhyd.2017.05.002.

[48] X. Kang, A. Kirui, M.C. Dickwella Widanage, F. Mentink-Vigier, D.J. Cosgrove, T.

Wang, Lignin-polysaccharide interactions in plant secondary cell walls revealed by

solid-state NMR, Nature Communications. 10 (2019). doi:10.1038/s41467-018-08252-

0.

32
 Journal Pre-proof

[49] L. Muraille, V. Aguié-Béghin, B. Chabbert, M. Molinari, Bioinspired lignocellulosic

films to understand the mechanical properties of lignified plant cell walls at nanoscale,

Scientific Reports. 7 (2017) 1–11. doi:10.1038/srep44065.

[50] M.S. Islam, M.S. Rahaman, J.H. Yeum, Electrospun novel super-absorbent based on

polysaccharide-polyvinyl alcohol-montmorillonite clay nanocomposites, Carbohydrate

Polymers. 115 (2015) 69–77. doi:10.1016/j.carbpol.2014.08.086.

[51] L.R. Rane, N.R. Savadekar, P.G. Kadam, S.T. Mhaske, Preparation and

Characterization of K-Carrageenan/Nanosilica Biocomposite Film, Journal of

of
Materials. 2014 (2014) 1–8. doi:10.1155/2014/736271.

ro
[52] C. Liu, C. Xiao, H. Liang, Properties and structure of PVP-lignin “blend films,”
-p
Journal of Applied Polymer Science. 95 (2005) 1405–1411. doi:10.1002/app.21367.
re
[53] N.N.R. Ahmad, W.J.N. Fernando, M.H. Uzir, Parametric evaluation using mechanistic

model for release rate of phosphate ions from chitosan-coated phosphorus fertiliser
lP

pellets, Biosystems Engineering. 129 (2015) 78–86.

na

doi:10.1016/j.biosystemseng.2014.09.015.

[54] R. Liang, M. Liu, L. Wu, Controlled release NPK compound fertilizer with the function
ur

of water retention, Reactive and Functional Polymers. 67 (2007) 769–779.

Jo

doi:10.1016/j.reactfunctpolym.2006.12.007.

[55] K. Lubkowski, Coating fertilizer granules with biodegradable materials for controlled

fertilizer release, Environmental Engineering and Management Journal. 13 (2014)

2573–2581.

[56] J. Behin, N. Sadeghi, Utilization of waste lignin to prepare controlled-slow release

urea, International Journal of Recycling of Organic Waste in Agriculture. 5 (2016)

289–299. doi:10.1007/s40093-016-0139-1.

[57] C. Guo, L. Zhou, J. Lv, Effects of expandable graphite and modified ammonium

33
 Journal Pre-proof

polyphosphate on the flame-retardant and mechanical properties of wood flour-

polypropylene composites, Polymers and Polymer Composites. 21 (2013) 449–456.

doi:10.1002/app.

Graphical abstract

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lP
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Coating
« TSP granule»
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- Water solubility
- Hydrophobicity
- Mechanical properties
- Thermal behavior
- Release rate of P

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Abdellatif Barakat, Ph.D.

INRA UMR IATE 1208
2, Place Pierre Viala
34060 Montpellier cedex 1 France

Author statement

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Saloua Fertahi: Investigation, Formal analysis, Writing- Original draft preparation, Writing-
Reviewing and Editing Isabelle Bertrand: Supervision, Visualization, Writing- Original draft

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preparation. Mohamed Ilsouk: Investigation, Writing- Original draft preparation. Abdallah
Oukarroum: Resources, Writing- Original draft preparation. M’Barek Amjoud:
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Supervision, Visualization. Youssef Zeroual: Funding acquisition, Visualization. Abdellatif
Barakat: Project administration, Supervision, Writing- Original draft preparation, Writing-
Reviewing and Editing
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lP
na
ur
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35