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Opportunities and Challenges for Lignin Valorization in Food

Packaging, Antimicrobial, and Agricultural Applications
Alice Boarino and Harm-Anton Klok*

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ABSTRACT: The exploration of renewable resources is essential to help transition toward

a more sustainable materials economy. The valorization of lignin can be a key component of
this transition. Lignin is an aromatic polymer that constitutes approximately one-third of the
total lignocellulosic biomass and is isolated in huge quantities as a waste material of biofuel
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and paper production. About 98% of the 100 million tons of lignin produced each year is
simply burned as low-value fuel, so this renewable polymer is widely available at very low
cost. Lignin has valuable properties that make it a promising material for numerous
applications, but it is far from being fully exploited. The aim of this Perspective is to
highlight opportunities and challenges for the use of lignin-based materials in food
packaging, antimicrobial, and agricultural applications. In the first part, the ongoing research
and the possible future developments for the use of lignin as an additive to improve
mechanical, gas and UV barrier, and antioxidant properties of food packaging items will be
treated. Second, the application of lignin as an antimicrobial agent will be discussed to
elaborate on the activity of lignin against bacteria, fungi, and viruses. Finally, the use of lignin in agriculture will be presented by
focusing on the application of lignin as fertilizer.

1. INTRODUCTION underutilized biopolymer is, hence, attractive from both a

The world dependence on and excessive use of fossil fuels have sustainability and economic point of view.
led to climate change, which has forced researchers and Lignin biosynthesis takes place via oxidative radical
industries to focus their attention on the exploration of polymerization of coniferyl, sinapyl, and p-coumaryl alcohol9,10
renewable and green alternatives to oil, natural gas, and coal. that is triggered by a series of enzymes, which includes laccases
First-generation biorefineries address this issue through the and peroxidases as key players.11 Once incorporated in the
fermentation of corn, sugar cane, and wheat to obtain lignin polymer, these structural units are referred to as guaiacyl,
bioethanol1 and the transesterification of rapeseed and soybean syringyl, and p-hydroxyphenyl units, respectively.10,12−14 The
oil to produce biodiesel.2 Although these are well-established structure of lignin and these different building blocks is shown
processes to generate green energy, their sustainability is still in Figure 1. Since lignin is generated via coupling reactions
under debate because they utilize edible crops and, thus, between phenolic radicals, the molecular weight distribution
compete with food production. To avoid, for example, and composition of this biopolymer is very heterogeneous and
deforestation to free the extensive land that these crops need can widely vary depending on the plant species.14,15
and a potential increase of food price, a new generation of Lignin can be industrially isolated from various natural
biorefineries is being developed that aim to utilize nonedible sources, such as woody biomass, agricultural residues, and
lignocellulosic biomass.3,4 In particular, the valorization of energy crops.5 There are four main biorefinery processes used
lignin, one of the main biomass components, holds great for lignin extraction: sulfite, soda, kraft, and organosolv. As
promise for contributing to the successful development of summarized in Table 1, they present different features and
future biorefineries.5,6 Lignin is a cross-linked aromatic afford technical lignins with different properties. Generally
heteropolymer, which, together with cellulose and hemi- speaking, they apply high temperature and/or highly acid or
cellulose, is found in the plant cell wall (Figure 1) where it
provides mechanical support and protection against patho-
gens.7 Lignin makes up 15−35% of lignocellulosic biomass, Received: November 21, 2022
and ∼100 million tons of this biopolymer are yearly isolated as Revised: January 25, 2023
waste material from the paper and bioethanol industry.8 Less
than 2% of this enormous quantity is currently commercialized
as low-value products, such as surfactants and adhesives, while
the rest is mainly burned.5,8 The application of this
© XXXX The Authors. Published by
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Figure 1. Representation of cellulose, hemicellulose, lignin, and lignin structural units.

Table 1. Overview of Technical Lignin Extraction Processes, And Solubility, Weight-Average Molecular Weight (Mw),
Dispersity (Đ), and Impurities in the Different Types of Lignins
lignin type extraction process18,19 solubility20,21 Mw (kDa)20,21 Đ21,22 impurities20
kraft lignin 170 °C, NaOH, Na2S aqueous media pH > 10 0.1−3 2.5−3.5 sulfur
lignosulfonates 140 °C, SO2, Na+/Ca+/Mg+/NH4+ water 20−50 6.0−8.0 sulfur
organosolv lignin 150−200 °C, acetic acid/formic acid/organic solvents organic solvents 0.5−4 1.3−4.0 carbohydrates and ash
soda lignin 150−170 °C, NaOH aqueous media pH > 10 0.8−3 2.5−3.5 carbohydrates and ash

Figure 2. (A) Biodegradable polymers utilized in food packaging. (B) Properties that lignin incorporation can affect, when incorporated in a
biodegradable polymer film.

basic conditions that cleave the lignin ether bonds to result in Besides being both economically and environmentally
the formation of oligomers containing stable C−C bonds, friendly, lignin also presents intrinsic properties that make it
which cannot be further modified and, thus, hinder lignin an attractive material to be used in a wide range of
depolymerization into individual monomers. A number of applications, as reported in a number of review ar-
research groups have developed methods to avoid the ticles.12,13,23,24 The aim of this Perspective is to highlight
formation of C−C bonds during lignin extraction. This allows opportunities and challenges for the use of lignin-based
the depolymerization of lignin to produce a wide number of materials in three, which we believe are, important and
aromatic monomers.9,16,17 As a consequence, the valorization promising areas of application, namely food packaging,
of lignin can both involve the use and application of the whole antimicrobial applications, and agriculture. Herein, we not
polymer, as well as the exploration of opportunities for the low- only give an overview of the role of lignin in these three
molecular-weight oligomers that are obtained via lignin application fields, but we also highlight the challenges and
depolymerization.5 problems that still need to be addressed and we provide a
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Table 2. Examples of Studies Where Lignin Was Incorporated into Biodegradable Polymers and the Effect of Lignin
Incorporation on Tensile Strength, Elongation at Break, Gas Barrier Properties, and Antioxidant and UV-Barrier Activity of
the Resulting Composite Films34−41

a
PLA = poly(lactic acid). bPVA = poly(vinyl alcohol). cPHB/PHA = poly(3-hydroxybutyrate)/polyhydroxyalkanoates.

Table 3. Examples of Studies Where Lignin Nanoparticles Were Incorporated into Biodegradable Polymers and the Effect of
Lignin Incorporation on the Tensile Strength, Elongation at Break, Gas Barrier Properties, and Antioxidant and UV-Barrier
Activity of the Resulting Films47−52

forward-looking perspective on the possible future develop- and not recycled. Food and food packaging currently are also
ments on this topic. responsible for almost half of the total municipal solid waste.27
Most of the polymers used for food packaging are non-
2. LIGNIN IN FOOD PACKAGING degradable oil-derived materials, such as poly(ethylene
Every year, 140 million tons of plastic are produced and terephthalate) (PET), polyethylene (PE), polypropylene
utilized as packaging materials.25,26 Around 40% of this is for (PP), polyvinyl chloride (PVC), and polystyrene (PS).28,29 A
food packaging, where it is mostly designed to be single-use number of strategies are possible to reduce the use of
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petroleum-based resources and prevent the accumulation of incorporated in a polymer film, the mechanical properties can
discarded materials in the environment. One possibility is the change in different ways. As Tables 2 and 3 highlight, the
implementation of food storage systems to prolong the food tensile strength and elongation at break can increase, decrease,
shelf life. Another approach is to substitute conventionally used or remain unchanged, depending on the polymer matrix and
polymers with biodegradable alternatives.30 Biodegradable the type of lignin. The effect of lignin incorporation is, thus,
polymers, which can be decomposed into CH4, CO2, and film specific, but the take home message from the literature is
H2O by microorganisms, can be classified according to their that, overall, the compatibility between the lignin filler and the
sources into natural, microbial, and synthetic polymers (Figure polymer matrix defines the mechanical properties of the film.13
2A). It is important to highlight that the end-of-life Generally, a more efficient lignin dispersion and compatibiliza-
management of these materials, such as industrial composting tion lead to better mechanical properties. Possible ways to
or home composting for some of them, remains as important improve the compatibility between lignin and the polymer
as in the case of the oil-derived ones.31−33 matrix and to avoid phase separation are lignin esterifica-
Although the polymers that are highlighted in Figure 2A can tion,53−58 the use of cross-linkers,59−61 and polymer surface
be used to substitute non-biodegradable plastics and reduce modification.45,46,62,63
the environmental impact, they generally have only moderate Lignin incorporation can reduce the oxygen and water vapor
mechanical and barrier properties, and often are more transmission, particularly when films are made from hydro-
expensive than the commonly utilized materials.28 For these philic materials, such as alginate37 and starch.38 This is not
reasons, they constitute only 1% of the plastics utilized for food only because of the overall hydrophobic nature of lignin but
packaging.30 To improve the market expansion of the materials also because of the interaction of lignin and film matrix. Once
shown in Figure 2A, the performance of these bioplastics needs incorporated in the film, lignin interacts with the hydrophilic
to be improved. The introduction of lignin as a filler for groups of the biopolymer, thereby reducing their affinity to
biodegradable plastics is one way to achieve this goal. Lignin water and oxygen molecules.13
incorporation can modify the mechanical and gas barrier Oxidation of lipids and proteins inside food is one of the
properties of food packaging films, and also provide the main reasons for food deterioration, and it affects food
packaging material with properties such as antioxidant and UV- appearance, taste, and smell and can lead to the generation of
barrier activity (Figure 2B). Lignin can be incorporated either toxic aldehydes.64 Antioxidant compounds, which act as radical
by blending free lignin with the polymer of interest or, scavengers and delay radical oxidative processes, can be
alternatively, by using lignin nanoparticles. Table 2 lists incorporated in packaging materials to prevent food oxidation.
examples of studies that have used lignin as a filler in Typical examples of antioxidants are butylated hydroxyanisole
biodegradable polymer films. and butylated hydroxytoluene.65 Although they are very
In addition to blending free lignin, this biopolymer can also efficient in hindering food oxidation, these compounds can
be incorporated in food packaging films in the form of generate benzoic acid, nitrates, and sulphites, which can cause
nanoparticles. Lignin nanoparticles can be synthesized by allergies and may have other side effects on human health.66,67
different methods, such as precipitation via solvent or pH Recently, the interest in greener and safer natural antioxidants
exchange, self-assembly, microwave assistance, ultrasonication, has, therefore, increased. Lignin is an efficient antioxidant and
and aerosol processing.42,43 These particles can be incorpo- a promising alternative for the mentioned synthetic com-
rated in a matrix to prepare nanocomposites.43,44 The main pounds.35,68,69 The antioxidant activity of lignin is due to the
advantage of using nanoparticles is that they present a high presence of phenols in its structure, which can act as radical
surface-area-to-volume ratio. There are some examples, in scavengers. A number of studies have verified that a higher
which lignin nanoparticles have been incorporated in a phenol content, lower molecular weight, and narrower
biodegradable polymer matrix to form nanocomposites that dispersities correlate with a higher antioxidant activity of
could potentially be used for food packaging (Table 3). As lignin.70−73
Table 3 indicates, typically only a small amount of lignin The presence of chromophores, such as carbonyl and
nanoparticles is incorporated in the polymer matrix (max 3%). conjugated phenol groups, inside the lignin structure enables
This is because, at higher nanoparticle contents, the nano- this polymer to absorb light in the UV range (200−400
particles aggregate to form larger clusters. This is caused by the nm).24,74 This is a further advantage of using lignin fillers in
poor compatibility between the aromatic cross-linked lignin food packaging because they help to protect food from UV
and the polymer matrix. This obstacle can be overcome by irradiation. It is important to consider that the UV protection
surface modification of the lignin nanoparticles in order to provided by lignin comes with a loss of visible transparency of
increase their compatibility with the surrounding matrix. In the polymer film because of the brown color of lignin. Visible
one example, this was accomplished by etherification of the transparency is an important factor for food packaging because
surface of lignin nanoparticles with citric acid. In this way, 10 customers generally desire to see the product inside the
wt % of lignin nanoparticles could be incorporated inside a packaging. It is, hence, always important to optimize the lignin
PVA film.45 Another approach involves grafting polymer chains content and distribution inside the polymer film in order to
from the particle surface. Ring-opening polymerization of find a material composition where the film is protecting the
lactide, for example, has been used to generate PLA-modified food from UV irradiation but also allowing the product to be
lignin nanoparticles that could be incorporated in a well- visually seen.
dispersed fashion to generate PLA films that contained up to Challenges and Future Perspectives for the Use of
10 wt % lignin nanoparticles.46 Lignin in Food Packaging Applications. Lignin can be
As mentioned above, the addition of lignin is attractive incorporated into biodegradable polymer films to improve
because it provides a way to improve mechanical and gas their performance in food packaging. The addition of lignin
barrier properties, as well as the antioxidant activity and UV- can enhance mechanical and gas barrier properties, two of the
barrier properties of food packaging materials. When lignin is main weaknesses of biodegradable polymers, and provide them
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with antioxidant and UV barrier properties, which are of major activity of lignin derives from its natural ability to protect a
importance for food preservation. Among the challenges for plant from pathogens.7 Inside the plant, lignin can preserve
the preparation of such blend materials is the compatibility carbohydrates from degradation by suppressing the attack of
between the polymer matrix, often made of linear aliphatic bacteria and fungi. 12 Technical lignins isolated from
polymer chains, and the aromatic cross-linked structure of lignocellulosic biomass have been involved in biological and
lignin. This leads to phase separation and heterogeneity inside medical studies as an antibacterial, antifungal, and antiviral
the film, which limits the performance of the final product. The agent (Figure 3). Table 4 presents several selected examples of
same applies for the preparation of nanocomposites where studies that have investigated the antimicrobial activity of
lignin nanoparticles are incorporated in the polymer film. Only various lignins in solution.
very small amounts of nanoparticles have been introduced into
such films, while a higher particle content could not be
achieved without aggregation and phase separation. The
functionalization of lignin and of lignin nanoparticles to
improve their affinity with the polymer matrix is, thus, key to
achieve an efficient dispersion of lignin in the final film.
Another important issue that still needs to be addressed
regarding the use of lignin in food packaging is safety. Studies
about the interaction of lignin with the packaged food, as well
as in vivo digestion, are to date very preliminary and will
require additional investigation.
The design of sustainable food packaging items must take
into consideration the end-of-life management of the final
product. Most of the food packaging items are disposed of by
landfilling, and are not recycled because of the presence of
additives, as well as food contamination that can be challenging
to separate. Landfilling results in the occupation of large
amounts of space and the production of greenhouse gases,
whereas composting is a valid alternative end-of-life treat-
ment.75 The American Society for Testing and Materials
(ASTM) defines a plastic as compostable when it “undergoes
degradation by biological processes during composting to yield
carbon dioxide, water, inorganic compounds, and biomass at a Figure 3. Antimicrobial activity of lignin.
rate consistent with other known compostable materials and
that leaves no visible, distinguishable, or toxic residue.”76 This The antibacterial activity of lignin is generally attributed to
is a subgroup of biodegradable plastics, which are instead the phenolic hydroxyl groups, which are able to damage the
defined as “plastic in which the degradation results from the bacterial cell membrane and lead to the bacteria lysis.94,95 The
action of naturally-occurring micro-organisms such as bacteria, antibacterial activity of phenols and polyphenols is generally
fungi, and algae.”76 Therefore, not all biodegradable plastics are known, but the precise mechanism of action is still unclear.
compostable. Lignin is efficiently biodegraded by white-rot The antibacterial performance varies with and depends on the
fungi and various types of bacteria,77,78 but the degradation of type of lignin and the bacterial strain. For instance, Dong et al.
lignin under composting conditions commonly used to dispose investigated and described a kraft lignin isolated from corn,
of food packaging items is incomplete and inefficient.79 which was able to efficiently inactivate Listeria monocytogenes
Moreover, the properties introduced by the addition of lignin and Staphylococcus aureus, two Gram-positive bacteria, but not
in a polymer matrix, such as improved gas barrier, decreased Gram-negative bacteria or bacteriophages.83 In another study,
water permeability, and increased hydrophobicity, can reduce Lourençon et al. reported that a kraft lignin extracted from
the material degradability in the composting conditions. eucalyptus can successfully inactivate both Gram-positive
Additional attention should be placed on studying how the bacteria, such as Bacillus cereus, Staphylococcus aureus, and
introduction of lignin influences the compostability of the final Pseudomonas aeruginosa, as well as Gram-negative bacteria,
product because this parameter is often not considered in the such as Escherichia coli and Salmonella enteritidis.81 In addition
published studies. to being used as a pure antibacterial agent, lignin can also be
blended with or incorporated into more complex systems. A
3. LIGNIN AS ANTIMICROBIAL AGENT very interesting example was provided by Ritcher et al., who
Some bioactive compounds extracted from plants can be used placed lignin around a silver nanoparticle core to achieve
as antimicrobial agents to inhibit the harmful activity of excellent antibacterial performance against Staphylococcus
bacteria, fungi, and viruses. Common examples are poly- aureus and Escherichia coli without production of environ-
phenols, amino acids, terpenoids, flavonoids, and tannins, mentally adverse silver ions.96 Some studies have also
which not only are very interesting for their biological activity examined the antibacterial activity of polymer films where
but also for their biocompatibility, renewability, and biode- lignin was used as a filler, prepared analogously to the polymer
gradability.12,80 Most of these compounds, however, are found blends described in the previous paragraph, which showed
in very small quantities in plants and typically require complex successful inactivation of various bacteria.97−99
extraction processes to be isolated. Lignin has recently Lignin can also inhibit specific species of fungi. The
attracted much attention since it is cheap and accessible and mechanism of fungal inhibition is currently unknown, but is
also shows interesting biological activities. The antimicrobial dependent both on the lignin source and extraction process.
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Table 4. Examples of Studies That Have Investigated the Antimicrobial Properties of Lignin in Solution
conc
lignin type solvent (mg/mL) inactivated pathogen reference
bacteria
kraft lignin DMSO 15 Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Salmonella enteritidis, 81
Bacillus cereus
pyrolytic lignin DMSO 5 Staphylococcus aureus, Escherichia coli 82
kraft lignin Bacto Tryptic Soy 100 Listeria monocytogenes, Staphylococcus aureus 83
Broth
fungi
organosolv/kraft DMSO 1−20 Aspergillus niger 84
lignin
organosolv lignin DMSO 0.48−0.025 Candida parapsilosis, Candida krusei, Candida guilliermondii, Candida albicans, 85
Aspergillus f lavus, Aspergillus f urmigatus
organosolv lignin DMSO 0.5, 5, 10 Aspergillus niger, Saccharomyces cerevisiae 86
viruses
lignin−carbohydrate 1% H2SO4 + organic 0.05 encephalomyocarditis virus (EMV) 87
complex solvents
DMEM 0.5 herpes simplex virus (HSV) 88
H2O 0.1, 2 EMV, HSV 89
lignosulfonate PBS 10 human immunodeficiency virus (HIV), HSV 90
cell culture medium 70 nM− HIV 91
236.6 μMa
cell culture medium 0−0.2 HIV 92
cell culture medium 0−0.5 HIV, HSV 93
a
In the article referenced, lignosulfonate concentration was expressed as the molar concentration of polymer.

Gordobil et al. compared the antifungal activity of lignin Challenges and Future Perspectives for the Applica-
extracted from both eucalyptus and spruce via organosolv and tion of Lignin as Antimicrobial Agent. Lignin has been
kraft processes against Aspergillus niger and verified that the proven to be an efficient agent for the inhibition of bacteria,
kraft lignin from eucalyptus exhibited the best antifungal fungi, and viruses. The main challenge for the application of
performance.84 Another example that is worth mentioning was lignin as an antimicrobial compound is its heterogeneity in
provided by de Melo et al., who tested a lignin isolated from terms of structure, reactive group content, and impurities.
Caesalpinia pulcherrima leaves against a wide number of fungi. Since lignin can be obtained from different natural sources by
The outcome of this study was that a very different amount of using various methods, its properties and activity against
the same lignin type can be necessary to inhibit different fungi pathogens can drastically vary. A fundamental mechanistic
species.85 understanding of the deactivation of bacteria, fungi, and viruses
The antiviral activity of lignin−carbohydrate complex and by lignin is, hence, required in order to define a structure−
lignosulfonate, both of which are water-soluble, has been activity dependency profile. Although lignin can be degraded in
studied in cell culture medium and aqueous solution against a the environment by specific fungi, bacteria, and enzymes, the
number of viruses. Even though some research groups have fate of this polymer inside the human body is still under
tried to establish a relationship between the lignin structure debate. Moreover, despite a large number of studies on the
and the antiviral effect, the well-defined antiviral mechanism biocompatibility of lignin, the consequences of lignin use for
has not been clarified yet. biomedical purposes on cells and genes are still mainly
Inside the plant wall, lignin is covalently bound to unknown and will require a detailed investigation. Regarding
carbohydrates and forms a lignin−carbohydrate complex, the studies about viral inactivation, besides the use of lignin as
which can be extracted from biomass via different methods, a macromolecule, it is noteworthy to mention that a number of
such as acidolysis, fractionation, and enzymatic hydrol- phenol monomers have been identified and extracted from
ysis.100,101 Lignin−carbohydrate complexes have shown lignin that displayed efficient antiviral activity against
efficient inactivation of encephalomyocarditis virus (EMV) encephalomyocarditis virus,102−104 which suggests the involve-
and herpes simplex virus (HSV).87−89 Their antiviral activity in ment of phenolic groups in the antiviral activity of lignin. For
aqueous solution was attributed to the inhibition of viral this application, only water-soluble lignosulfonates and lignin−
binding and penetration into the host cells. The specific role of carbohydrate complexes in solution have been tested. In a
lignin in the antiviral activity of the lignin−carbohydrate recent study, antiviral lignin surface coatings made of water
complex remains unclear. insoluble lignins were prepared, which showed very efficient
Lignosulfonate, the only water-soluble technical lignin type, inactivation of HSV-2 (>99% after 30 min). Particular
has shown antiviral activity against HSV and human attention has been focused on the mechanism behind the
immunodeficiency virus (HIV). The antiviral activity of antiviral activity of these coatings, which turned out to be
lignosulfonates was attributed to the structural similarity with strongly related to the lignin phenol content.105 The COVID-
heparan sulfate, a proteoglycan found in the proximity of the 19 outbreak has highlighted the importance of antiviral
cell wall where viruses can typically interact with cells. The surfaces. Lignin is a promising material to develop affordable
antiviral mechanism was not completely clarified but was and sustainable antiviral coatings on a large scale, which
proved to be influenced by sulfur content, molecular weight, deserves additional investigation. New methods to prepare
and counterion (Na+, Ca2+, NH4+).90−93 resistant coatings on any type of surface, such as spray and
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brush coatings, should be tested. The adhesive properties of Table 5. Overview of Selected Review Papers on Lignin-
the coating on different types of substrates, such as glass, wood, Based Fertilizers
or plastic, should also be examined in the future.
publication
review title year reference
4. LIGNIN FOR AGRICULTURAL APPLICATIONS Application of lignin in preparation of slow-release 2022 117
fertilizer: Current status and future perspectives
Lignin has been applied in several fields of agriculture, such as
Lignin-based controlled release fertilizers: A review 2022 118
fertilizer, pesticide, and plant growth regulator.23 Since lignin
Novel fertilizing products from lignin and its 2022 119
directly derives from plants and can be extracted from derivatives to enhance plant development and
agricultural residues, such as straw and husk, its use for increase the sustainability of crop production
agricultural applications is very attractive from the sustain- Can lignin be transformed into agrochemicals? 2021 23
Recent advances in the agricultural applications
ability and circular economy points of view. This Perspective of lignin
specifically focuses on lignin-based fertilizers, a field of primary Research Progress in Lignin-Based Slow/ 2020 120
importance, where this biopolymer has made a significant Controlled Release Fertilizer
contribution and has the potential to make further impact Lignin in Crop Cultivations and Bioremediation 2005 121
The use of fertilizers is essential to fulfill the continuously Nitrogenous Fertilizers From Lignins - a Review 2002 122
growing demand for food, which accompanies the increase of
global population. At the moment, 187 million metric tons of
fertilizer are applied every year to allow the production of more to lignin via ammoxidation and Mannich reactions, as shown in
than three billion metric tons of crops.106 In 2015, the United Figure 4A.
Nations established 17 sustainable development goals to be Ammoxidation involves the oxidation of an organic
accomplished by 2030, including eradicating hunger107 and compound using an oxidant (e.g., O2, H2O2, or H2SO4) in
making agriculture sustainable.108 With 800 million people the presence of ammonia.122 The amount of nitrogen that can
suffering from hunger nowadays and a growing global be incorporated into lignin depends on the reaction conditions,
population, it is imperative to further increase the efficiency which include temperature, pressure, time, and the type of
of crop production.109 To match this growing demand, oxidant.120 A nitrogen content of 13−14% was achieved using
technological innovations will be essential to increase the optimal conditions.124 Although this is a well-established
efficiency of fertilization and other agricultural practices, which method for the preparation of nitrogen-bearing lignin, some
are at the moment intrinsically inefficient. A significant portion drawbacks still need to be addressed, such as frequent damage
of the applied fertilizers do not reach the targeted plant and are of the equipment under the required harsh conditions and the
lost because of evaporation and wash off in the ground- easy leakage of ammonia.117
water.109−111 Not only is this a waste of nutrients and energy, The Mannich reaction allows the attachment of amine-
but it also is a huge environmental problem, which can lead to group-bearing molecules to lignin in the presence of
water eutrophication and dramatic changes in the ecosystems. formaldehyde and can be performed in basic, neutral, or acidic
The challenge of increasing crop production without conditions. This reaction modifies the aromatic rings of lignin,
compromising the environment can be addressed by better in particular the ortho and para position of the phenols,126 and
controlling nutrient release into the soil using slow- or displays higher yields on lower-molecular-weight lignins. To
controlled-release fertilizers.112−114 Among the starting materi- increase the efficiency of the reaction, lignin can be pretreated
als used for the development of such fertilizers, lignin is very via phenolation or mild depolymerization.138 Although this
attractive because of its biocompatibility and wide availability reaction is very efficient and straightforward, the use of
at low cost.115 Moreover, lignin has many reactive groups that formaldehyde is a serious drawback from a sustainability point
allow the chemical binding of a wide number of nutrient of view. A more environmentally friendly alternative should be
containing groups,21,116 which can then be gradually released considered in the future.
into the soil upon the biodegradation of lignin.115 Several Thanks to its aromatic structure and hydrophobic nature,
reviews have been published on this topic, which highlight the the incorporation of a fertilizer inside a lignin coating can
opportunities for lignin to contribute toward more sustainable reduce leaching in the environment and groundwater (see
agricultural practices (Table 5). Overall, these review articles Figure 4B). A number of papers have been published on urea
point out the high potential of lignin to produce agrochemicals incorporation inside lignin coatings prepared by mixing urea
with improved efficiency in nutrient release. However, the and lignin with a sealing agent, such as paraffin. For this
structural complexity and heterogeneity of lignin always process, lignin can be used as is or as previously modified. The
require an elaborated characterization of both reagents and nutrient inside the lignin coating can then be released by a
products. These reviews also highlight the lack of a uniform rupture mechanism, which means that water vapor enters the
and standardized evaluation of the produced fertilizers. coating and dissolves the fertilizers, thereby increasing the
Lignin-based slow/controlled release fertilizers can be osmotic pressure and breaking the coating. If the coating can
prepared via a number of approaches, where lignin can be resist the osmotic pressure increase, the nutrient is instead
(i) modified by chemical reaction and directly constitute the released via diffusion, which relies on the different concen-
nutrient, (ii) used as coating for the active ingredient, and (iii) tration of the nutrient inside and outside the coating.139−141
applied as a chelating agent for trace element release. These The elements necessary for the plant growth are in total 14,
three strategies are illustrated in Figure 4 and summarized in divided into major elements (N, P, K, Ca, Mg, and S) and trace
Table 6. elements (Cl, B, Fe, Mn, Cu, Zn, Ni, and Mo).142,143 Thanks
Most of the lignin-based slow-release fertilizers are prepared to the numerous hydroxyl and carbonyl groups in the lignin
by chemically binding nutrients to the reactive groups of lignin. structure, this polymer can be used to chelate a number of ions
In particular, nitrogen-containing groups are mainly attached for the preparation of trace element fertilizers (see Figure 4C).
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Figure 4. Methods to prepare lignin-based slow-release fertilizers: (A) chemical modification, (B) coating, and (C) chelation.

Table 6. Preparation of Lignin-Based Slow-Release Fertilizers

preparation method lignin type procedure active ingredient reference
ammoxidation kraft lignin O2, 150 °C, 50 min 12 N % content 123
kraft lignin O2, 150 °C, 90 min 13−14 N % content 124
straw pulping solid residue H2O2, 90 °C, 90 min 4.9 N % content 125
Mannich reaction soda lignin formaldehyde, NaOH, 60−80 °C, 3−5 h 5.4−10.2 N % content 126
soda lignin formaldehyde, ultrasound, 60−90 °C, 3 h 6.9−8.2 N % content 127
soda lignin formaldehyde, acetic acid, 60 °C, 4 h 3.4−4.2 N % content 128
soda lignin formaldehyde, NaOH, 60 °C, 3 h 12 N % content 129
coating kraft lignin drum coating urea 130
kraft lignin drum coating urea 131
acetylated lignosulfonates fluidized bed urea 132
soda lignin turning pan coater urea 133
chelation kraft lignin precipitation Ca2+ 134
aminated lignin mixing Fe3+ 135
lignosulfonates mixing Fe3+ 136
lignosulfonates mixing Fe3+ 137

The ability to create chelating bonds with metal ions depends main limitation is that the coating can often be uneven and
both on the lignin type and on the metal.144 present cracks, thereby making the nutrient release less
Challenges and Future Perspectives for the Applica- controllable than the products prepared via chemical
tion of Lignin as Fertilizer. Lignin is a very attractive modification. Improvements are, thus, needed to optimize
material for the preparation of slow-release fertilizers because the coating process and quality in order to achieve a more
of its biodegradability, low cost, and biocompatibility; hence, a stable slow-release effect. Another implementation could be
large number of articles have been published on this topic. made in regard to the delivered nutrient type. Overall, most of
However, several drawbacks currently limit the application of the developed lignin-based fertilizers bear nitrogen, while the
lignin as fertilizer. For the chemically modified lignin-based literature regarding fertilizers containing phosphorus, the
fertilizers, the ammoxidation process should be optimized in second most limiting nutrient in soil, is very limited.145−147
terms of temperature, pressure and choice of oxidant in order To achieve this, lignin could be simply phosphorylated,148 or
to increase the N % content in the final product. The recycling phosphorus cross-linkers and phosphorus-containing com-
of ammonia should also be considered. Regarding the Mannich pounds could be easily incorporated into a lignin carrier.149
reaction and chelation reaction, additional research work Another interesting perspective is the development of
should be invested to use sustainable reagents and avoid the nanosized lignin-based fertilizers. Nanofertilizers are known
generation of toxic byproducts. Considering the lignin-based to present many advantages over conventional fertil-
slow-release fertilizers prepared via the coating method, the izers,109,150−152 and lignin nanoparticles can be prepared with
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a wide number of methods.153−156 Finally, the slow- and controlled-release fertilizers, but some drawbacks need to be
controlled-release fertilizers developed so far simply slow down overcome to allow their large-scale use. On the one hand, the
the nutrient distribution in the soil, independent of proximity methods to prepare lignin-based fertilizers require improve-
to the target plant. A more efficient approach to diminish the ment. Ammoxidation and Mannich reactions are both efficient
waste of nutrients in the environment would be to develop to enrich lignin with nitrogen, but their sustainability should be
plant growth synchronized-release fertilizers that are able to optimized in terms of reagents, side products, and working
deliver the active principle only in the presence of the plant conditions. The same also applies to the use of lignin as a
roots. coating material to develop controlled-release fertilizers or as
depots for the release of essential elements. On the other hand,
5. CONCLUSIONS AND PERSPECTIVES lignin could be used to design new types of fertilizers. An
This Perspective has discussed the state-of-the-art methods interesting option to be examined is the use of lignin
and opportunities for the valorization of lignin for food nanoparticles, and of lignin modified with types of nutrients
packaging, antimicrobial, and agricultural applications. Lignin other than nitrogen, for instance, by modification with or
has the potential to be used in a range of applications, but the through the incorporation of phosphorus. The development of
use of this biopolymer can be challenging because of a number lignin-based nanofertilizers is another opportunity to imple-
of problems. Overall, the main complication is the structural ment the yield of crop production. In particular, a promising
and compositional heterogeneity of lignin, which depends on perspective is to develop systems that would allow the release
the plant source and extraction process and requires an of nutrients specifically in the proximity of the plant, thus
elaborate characterization of both the starting reagents and avoiding a waste of nutrients and helping to prevent or reduce
products. A consequence of the wide diversity in lignin types is environmental pollution.
that a well-defined structure−activity dependency should be Overall, the aim of this Perspective was to highlight the
established for most of the applications where this biopolymer potential of lignin, an underutilized natural source that holds a
is employed. lot of promise not only for food packaging, antimicrobial, and
For food packaging applications, lignin can be used as a agricultural applications, but also for a range of other
green additive not only to improve the mechanical and gas technological challenges that call for sustainable materials
barrier properties of polymer films but also to provide solutions.
antioxidant and anti-UV activity. The main challenge for the
incorporation of lignin into a polymer film is its compatibility
with the surrounding matrix. To avoid heterogeneity and phase
■ AUTHOR INFORMATION
Corresponding Author
separation, particular attention must be placed on the Harm-Anton Klok − Institut des Matériaux and Institut des
functionalization of the lignin or the lignin nanoparticles in Sciences et Ingénierie Chimiques, Laboratoire des Polymères,
order to improve their compatibility with and dispersion inside É cole Polytechnique Fédérale de Lausanne (EPFL), CH-1015
the polymer film. A deeper understanding of the interactions Lausanne, Switzerland; orcid.org/0000-0003-3365-
between lignin and the packaged products, as well as the 6543; Email: [email protected]
digestibility of the film, is also required. Since lignin is hardly
Author
degradable in composting conditions, additional attention
Alice Boarino − Institut des Matériaux and Institut des
should also be focused on evaluating the effect of the lignin
Sciences et Ingénierie Chimiques, Laboratoire des Polymères,
incorporation on the compostability and degradability of the
É cole Polytechnique Fédérale de Lausanne (EPFL), CH-1015
final product.
Lausanne, Switzerland
Regarding the use of lignin as an antimicrobial agent, the
precise mechanism of the interaction between lignin and Complete contact information is available at:
bacteria, fungi, and viruses is currently still unclear and under https://pubs.acs.org/10.1021/acs.biomac.2c01385
debate. The heterogeneity of lignin in terms of molecular
weight, impurities, and reactive group content opens the door Notes
to many applications in medicine and biology but also The authors declare no competing financial interest.
complicates the assessment of its activity and safety for the
human body. Despite a number of studies that have
investigated and demonstrated the antimicrobial activity of
■ ACKNOWLEDGMENTS
This work was financially supported by the Swiss National
lignin in solution, only very limited efforts have been made to Science Foundation (SNSF) Grant CRSII5_180258.
use lignin as a coating material to develop antimicrobial
surfaces. Since viruses and bacteria can transmit via contact
with contaminated surfaces, and the systematic disinfection of
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