Science of the Total Environment 613–614 (2018) 829–839

Contents lists available at ScienceDirect

Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Review

Environmentally friendly fertilizers: A review of materials used and their

effects on the environment
Jiao Chen, Shaoyu Lü ⁎, Zhe Zhang, Xuxia Zhao, Xinming Li, Piao Ning, Mingzhu Liu ⁎
State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Department of Chemistry, Lanzhou University,
Lanzhou 730000, People’s Republic of China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• New developments in environmentally

friendly fertilizers (EFFs) are discussed.
• EFFs are developed to improve yields
without compromising the environment.
• The effects of EFFs on the environment
are explored.
• Challenges and perspectives are provid-
ed on EFFs production and applications.

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

Article history: Fertilizer plays an important role in maintaining soil fertility, increasing yields and improving harvest quality.
Received 14 July 2017 However, a significant portion of fertilizers are lost, increasing agricultural cost, wasting energy and polluting
Received in revised form 18 September 2017 the environment, which are challenges for the sustainability of modern agriculture. To meet the demands of im-
Accepted 18 September 2017
proving yields without compromising the environment, environmentally friendly fertilizers (EFFs) have been de-
Available online 21 September 2017
veloped. EFFs are fertilizers that can reduce environmental pollution from nutrient loss by retarding, or even
Editor: D. Barcelo controlling, the release of nutrients into soil. Most of EFFs are employed in the form of coated fertilizers. The ap-
plication of degradable natural materials as a coating when amending soils is the focus of EFF research. Here, we
Keywords: review recent studies on materials used in EFFs and their effects on the environment. The major findings covered
Environmentally friendly fertilizer in this review are as follows: 1) EFF coatings can prevent urea exposure in water and soil by serving as a physical
Nutrient releases barrier, thereby reducing the urea hydrolysis rate and decreasing nitrogen oxide (NOx) and dinitrogen (N2) emis-
Soil sions, 2) EFFs can increase the soil organic matter content, 3) hydrogel/superabsorbent coated EFFs can buffer soil
Environment acidity or alkalinity and lead to an optimal pH for plants, and 4) hydrogel/superabsorbent coated EFFs can im-
Sustainable agriculture
prove water-retention and water-holding capacity of soil. In conclusion, EFFs play an important role in enhancing
nutrients efficiency and reducing environmental pollution.
© 2017 Elsevier B.V. All rights reserved.

⁎ Corresponding authors at: State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Lanzhou
University, Lanzhou 730000, People's Republic of China.
E-mail addresses: lshy@lzu.edu.cn (S. Lü), mzliu@lzu.edu.cn (M. Liu).

http://dx.doi.org/10.1016/j.scitotenv.2017.09.186
0048-9697/© 2017 Elsevier B.V. All rights reserved.
830 J. Chen et al. / Science of the Total Environment 613–614 (2018) 829–839

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 830
2. Natural materials used in EFFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 830
2.1. Chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 830
2.2. Sodium alginate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 831
2.3. Starch and its derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 832
2.4. Cellulose and their derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 833
2.5. Lignin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 833
2.6. Agricultural residues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 833
2.7. Biochar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 834
2.8. Polydopamine (Pdop) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 834
3. Effect of EFFs on the environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 835
3.1. Effect of EFFs on decreasing nitrogen oxide (NOx) and dinitrogen (N2) emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 835
3.2. Effect of EFFs on increasing soil organic matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 835
3.3. Effect of EFFs on adjusting soil pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 836
3.4. Effect of EFFs on improving water-retention and water-holding capacity of soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . 836
4. Challenges and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 836
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 837
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 837
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 837

1. Introduction dioxide, water, methane, inorganic compounds or microbial biomass.

Greater input of fertilizer, water and pesticides, along with new
technologies, have generated immense developments in modern agri-
culture over the past century. The crop production per unit of land has
increased greatly, which has allowed for increased populations and
has promoted economic development (Zhang et al., 2015). However,
while these developments have been significant, the environmental im-
pacts have typically gone unmeasured. Such costs associated with agri-
cultural development have resulted from the over-application of
fertilizers and pesticides, which have led to water eutrophication and
toxicity, groundwater pollution, air pollution, soil quality degradation,
and even the ecosystems change, raising questions about the sustain-
ability of modern agriculture (Tilman et al., 2002; Khan et al., 2008;
Wen et al., 2016).
Increasing crop production without compromising the environment
can be achieved by increasing fertilizer and water-use efficiency, mini-
mizing pesticide requirements, and using integrated management of
farming systems. This review mainly discusses research about the envi-
ronmental impacts associated with increasing fertilizer-use efficiency.
Intensive high-yield agriculture is dependent on fertilizer additions.
Increased food production cannot be achieved without increased fertil-
izer inputs. These inputs have helped to keep world crop productivity in
step with human population growth and have enhanced rural economic
development. However, mismanagement of fertilizer, applied in excess
of plant use, in conventional agriculture is a well-known inefficiency
that poses a threat to the environment. To avoid the negative environ-
mental consequences, fertilizer efficiency must be greatly increased
(Shaviv and Mikkelsen, 1993; Trenkel, 2010).
There are a variety of strategies that are used to increase fertilizer-
use efficiency to eliminate their negative impacts on the environment,
including improving fertilizer application methods, such as the use
of split or localized application, precision fertilization, fertigation-
fertilization via irrigation systems, and the use of environmentally
friendly fertilizers (EFFs) (Shaviv, 2005; Lü et al., 2016).
EFFs offer an effective way to improve nutrient efficiency, to mini-
mize leaching and volatilization losses of fertilizers, and to reduce envi-
ronmental hazards. They reduce environmental pollution from nutrient
losses by retarding or even controlling the release of nutrients into soil.
They are also referred to as “enhanced efficiency fertilizers” (EEFs)
(Chalk et al., 2015; Timilsena et al., 2015). Usually, EFFs are formulated
in such a way that nutrients are coated with environmentally friendly
materials, which can be degraded in soil and converted into carbon
This is the most common and commercially available formulation
(Naz and Sulaiman, 2016). However, other technologies have been
employed to develop EFFs; for example, using micro/nano networks to
entrap nutrients (Zhou et al., 2015a) or preparing nanocomposites
with the extrusion of a plastic mixture of polymer and fertilizer
(Pereira et al., 2015). This review mainly discusses coated EFFs, includ-
ing the materials most used in EFFs (Fig. 1) and the effect of EFFs on the
environment (Fig. 2).
2. Natural materials used in EFFs
Various materials have been used as coatings to retard nutrient re-
leases and to increase fertilizer-use efficiency. To develop EFFs, concen-
trated effort has been put into developing environmentally friendly
coating materials; most of these coatings derive from natural materials.
These natural materials display multiple advantages over synthetic
polymers due to their eco-friendly source: a low-cost, easy availability
and biodegradability (Wezel et al., 2014; Bao et al., 2015; Schneider
Teixeira et al., 2016). Table 1 shows the positive and negative character-
istics of the natural materials that are most used in EFFs.
2.1. Chitosan
Chitosan is a polysaccharide derived from the (partial) deacetylation
of chitin, which is a major constituent of the exoskeleton of crustaceous
water animals such as crab and shrimp (Rinaudo, 2006). This naturally
regenerating resource makes chitosan naturally abundant. Further-
more, it is nontoxic and degradable. Due to these properties, chitosan
has been extensively used in various applications, including agriculture
(Li et al., 1992; Rinaudo, 2006; Harish Prashanth and Tharanathan,
2007; Wang et al., 2014; Xing et al., 2014; Perez and Francois, 2016).
It should not generate pollution because it is naturally occurring and de-
gradable; therefore, it has been widely employed in EFFs (Jamnongkan
and Kaewpirom, 2010; Rattanamanee et al., 2014; Sabadini et al., 2015).
Chitosan-coated nitrogen, phosphorus and potassium compound
fertilizer has been developed (Wu and Liu, 2008). Water-soluble nitro-
gen, phosphorus and potassium fertilizer granule cores were coated
with chitosan as an inner coating, and poly(acrylic acid-co-acrylamide)
(P(AA-co-AM)) superabsorbent polymer was used as the outer coating.
The nutrient content included nitrogen (N) 8.06%, phosphorus
(P) 8.14%, and potassium (K) 7.98%. The percentages released were
79, 62, and 69% for N, P, and K on the 30th days, respectively. In addition
 J. Chen et al. / Science of the Total Environment 613–614 (2018) 829–839 831

Fig. 1. The structures or sources of natural materials that are most used in EFFs are as follows: chitosan, sodium alginate, starch and its derivatives, cellulose and its derivatives, lignin,
agricultural residues, biochar, and polydopamine (Pdop).

to the slow release behavior, the compound fertilizer exhibits water-
holding and water-retention properties in soil. Utilizing chitosan as a
coating material could reduce the production cost and make the fertiliz-
er more environmentally friendly. One potential limitation of this sys-
tem is that the chitosan was coated on the fertilizer cores using epoxy
dissolved in acetone. This method may cause environmental pollution
due to the emissions of organic solvent.
Another example of a chitosan-based fertilizer is chitosan-
montmorillonite clay microsphere fertilizer, which was developed
using a coagulation method and was then added to KNO3 fertilizer solu-
tions to obtain the potassium-containing fertilizers (dos Santos et al.,
2015). The addition of montmorillonite clay enhanced the adsorption
capacity of potassium due to its rough and porous surface. Moreover,
the clay is low cost, available, and environmentally friendly. The fertil-
izers were applied to the soil, and the potassium release was monitored
using time-domain reflectometry (TDR), which determined the electri-
cal conductivity of the soil. Higher fertilizer releases were identified dur-
ing the first three days, which were due to the KNO3 on the outsides of
the microspheres. Then, the concentration of potassium decreased until
a constant value was achieved. This work provides a useful technique of
using TDR to determine the real profile of fertilizer releases in the soil.
However, whether it is a sustainable fertilizer delivery system remains
unknown because the effect of the fertilizer on the environment was
not determined.
2.2. Sodium alginate
Sodium alginate (SA) is a linear polysaccharide extracted from
brown seaweed that consists of 1–4 linked α-L-guluronic and β-D-
mannuronic acid moieties in varying compositions (George and
Abraham, 2006). It can be ionically crosslinked with the addition of
Ca2 + in an aqueous solution. This mild gelation property causes it to
be widely used as a controlled release formulation of fertilizer (Guo
et al., 2006; Wu et al., 2011). However, the sodium alginate matrix has
a weak mechanical strength and is easily destructible in the presence
of monovalent cations. Furthermore, sodium alginate hydrogels do not

Fig. 2. The effect of EFFs on nitrogen oxide (NOx) emission, soil organic matter levels, soil pH, water retention and the water holding capacity of soil.
832 J. Chen et al. / Science of the Total Environment 613–614 (2018) 829–839

Table 1
Positive and negative characteristics of the natural materials most used in EFFs.

Materials Positive characteristics Negative characteristics Refs

Chitosan Naturally abundant, nontoxic and Only soluble in diluted acid. Water-soluble chitosan Perez and Francois, 2016; Sabadini et al., 2015; dos
degradable derivatives should be prepared; otherwise, chitosan Santos et al., 2015; Rattanamanee et al., 2014; Wang
is dissolved in organic solvents, which not only et al., 2014; Jamnongkan and Kaewpirom, 2010; Wu
increases the costs, but also causes adverse and Liu, 2008
environmental impacts.
Sodium alginate Mild gelation from the addition of Ca2+ Weak mechanical strength and easily destructible He et al., 2015; Córdoba et al., 2013; Wang et al., 2012;
in an aqueous solution, nontoxic and in the presence of monovalent cations; exhibits a Wu et al., 2011; Guo et al., 2006; Kenawy and Sakran,
degradable burst release of nutrients followed by a 1996
slow-release of the remaining nutrients.
Starch Easily modified, low-cost, nontoxic and Poor film-forming ability and water resistance, Chen et al., 2008b; Ge et al., 2002; Ito et al., 2005; Jin
degradable easily degraded in soil. et al., 2013; Lü et al., 2014; Riyajan et al., 2012; Qiao
et al., 2016; Zhong et al., 2013
Cellulose Renewable, degradable and film forming Strong hydrogen bonding. Cellulose derivatives, Li et al., 2016; Essawy et al., 2016; Bajpai et al., 2015;
ability such as cellulose ethers and cellulose esters are Li et al., 2015; Costa et al., 2013; Bortolin et al., 2013;
always prepared. Ethylene cellulose (EC) is used Davidson et al., 2013; Fernández-Pérez et al., 2008
most in fertilizer coating, which is often dissolved
in organic solvent, not only increasing costs, but
also causing adverse environmental impacts.
Lignin Low cost, readily available from plant The components of lignin are complex and its Fernández-Pérez et al., 2008; García et al., 1996;
derivatives fabrication is difficult. Lignin is non-soluble in Mulder et al., 2011; Peng and Chen, 2011; Sipponen
water and often dissolves in organic solvent, which et al., 2017
not only increases costs, but also causes adverse
environmental impacts.
Agricultural residues Abundantly available, cheap, Agricultural residues always need to be chemically Li et al., 2015; Liang et al., 2009; Ma et al., 2011; Xie
biodegradable, and renewable modified, and their utilization efficiency is low. et al., 2011; Yang et al., 2013; Zhang et al., 2014;
Holkar et al., 2016; Xia et al., 2017
Biochar Environmentally friendly, provides Nutrient content other than carbon is low. Its effect González et al., 2015; Yao et al., 2013; Zhou et al.,
organic matter and improves soil fertility on crops is dependent on its type. For example, 2015b; Cai et al., 2016; Wen et al., 2017
biochar with more volatile matter will inhibit the
growth of crops
Polydopamine Easily deposited on virtually all types of High cost Feng et al., 2015; Jia et al., 2013; Ma et al., 2013a; Ma
organic and inorganic substrates et al., 2013b

always exhibit controlled-release behavior and exhibit a burst release of
nutrients followed by a slow-release of the remaining nutrients
(Kenawy and Sakran, 1996; Córdoba et al., 2013).
To address this problem, sodium alginate coated fertilizers are en-
capsulated with another polymer or incorporated other materials into
the hydrogels. Wang et al. utilized a k-carrageenan-sodium alginate
(kC-SA) complex and cross-linked kC-g-poly(acrylic acid)/Celite (kC-g-
PAA/Celite) superabsorbent to coat urea granules as inner and outer
coating materials, respectively (Wang et al., 2012). The k-carrageenan
(kC) is a linear sulfate polysaccharide that is extracted from red seaweed
and has alternating α-1,3 and β-1,4 glycosidic linkages. The kC-SA com-
plex was produced by dropping kC and SA aqueous solutions into potas-
sium chloride and calcium chloride mixed solutions. The complex
formed through ionic crosslinking. Introduction of kC into SA hydrogel
improved its mechanical properties and reduced the brittleness of the
hydrogel (Mohamadnia et al., 2008). Furthermore, the kC-SA coating in-
corporated during fertilizer production made the products cheaper and
easier to biodegrade (Cassidy et al., 1995; Autio et al., 2002; Pourjavadi
et al., 2007; Pourjavadi et al., 2010). The kC-g-PAA/Celite superabsor-
bents used as the outer coating were applied to the surface of the gran-
ules while rotating. This process reduced the loss of fertilizer compared
to methods that blend or polymerize superabsorbents with fertilizers,
without altering their water-retention and water-holding properties.
The product contained 22.6% nitrogen, which exhibited slow-release
behavior; furthermore, 94.2% was released after being incubated in
the soil for 25 days.
A similar strategy has been described in a study evaluating a slow-
release microbial fertilizer (He et al., 2015). Raoultella planticola Rs-2
as a microbial fertilizer was encapsulated with sodium bentonite and al-
ginate composites. Bentonite is a type of sedimentary rock that is rich in
smectite that has a low cost and exhibits good adsorption of both water
and chemical compounds due to its unique crystal structure. The intro-
duction of bentonite to sodium alginates increases the solid content and
the porosity of alginate hydrogels. It also enhances the mechanical
strength because of increased viscosity and improved stability of
the clay. The Rs-2 encapsulation efficiency was almost 100%. After
6 months of storage at room temperature, as much as 88.9% of the Rs-
2 encapsulated in dried microcapsules of bentonite-alginate survived.
A bacteria release study in a sterile saline solution (0.9%) indicated an
initial burst release in the first 3 days, followed by a sustained release
between 3 and 30 days. The presence of bentonite minimized the corre-
sponding burst release effect and regulated the continuous release of
bacteria.
2.3. Starch and its derivatives
Starch is a polysaccharide composed of a large number of monosac-
charides or sugar (glucose) molecules that are joined together by α-1,4-
and/or α-1,6-glycosidic bonds (Sajilata et al., 2006). It is the most abun-
dant storage polysaccharide in plants and is the major dietary source of
carbohydrates (Ellis et al., 1998). The large number of available hydroxy
groups presents many options for starch derivatization. Due to this easy
modification property, the environmental friendliness and the afford-
ability, starch and its derivatives have been widely used in EFFs
(Ge et al., 2002; Jin et al., 2013; Zhong et al., 2013; Qiao et al., 2016).
Two types of starch derivatives, starch acetate and carboxymethyl
starch, have been synthesized to prepare double-coated fertilizers
(Lü et al., 2014). First, urea and natural attapulgite clay were mixed
and used as a fertilizer core. Then, starch acetate with a high-
substitution degree was synthesized and used as a hydrophobic inner
coating. Finally, carboxymethyl starch and xanthan gum were used to
prepare absorbent materials and to coat the outer surface of the fertiliz-
er granules. Nitrogen reached releasing equilibrium within 20 days for
the double-coated fertilizer. The introduction of natural polysaccharides
could induce biodegradability and provide full protection of the envi-
ronment. Double-coated urea granules were also evaluated by Ito
et al. (Ito et al., 2005). Poorly soluble isobutylidendiurea (IBDU) was
used as an inner coating, and starch with wax powder was used as an
 J. Chen et al. / Science of the Total Environment 613–614 (2018) 829–839
outer coating. A sigmoidal pattern (an initial slower release rate follow-
ed by consistent increases) of nutrient-controlled release behavior was
achieved.
Starch-based graft polymers were synthesized and developed as
fertilizer-coating materials. For example, starch was gelatinized with
water at 80 °C and then mixed with K2S2O8 at 60 °C for 45 min to obtain
K2S2O8 modified starch, which initiated the polymerization of natural
rubber to produce a natural rubber-g-starch graft polymer (Riyajan
et al., 2012). Then, urea granules were immersed into the graft polymer
blend to prepare coated fertilizers. The graft polymer is amphiphilic,
with a core–shell structure. The hydrophobic natural rubber is the
core and the hydrophilic grafted starch is the shell. Therefore, urea par-
ticles were encapsulated in the starch layer, and the hydrophobic natu-
ral rubber core formed as a barrier to reduce nitrogen releases. A urea
release study indicated that 21% of the nitrogen was released over
24 h in water. Starch was modified by polylactic acid (PLA) using an
in-situ graft-copolymerization technique and was then coated urea
with this composite (Chen et al., 2008b). A higher urea encapsulation ef-
ficiency of 70–81% was achieved for the starch-g-PLA/urea composite,
whereas it was 53% for the pure starch/urea composite. Hydrophobic
PLA reduced the hydrophilic quality of the starch matrix and retarded
the urea release from several hours to a maximum of 24 h.
2.4. Cellulose and their derivatives
Cellulose is the most abundant biopolymers on earth, found in cot-
ton, wood, hemp and other plant-based materials (Klemm et al.,
2005). It is a polysaccharide composed of a linear chain of several hun-
dred to many thousands of β(1-4) linked D-glucose units. Multiple hy-
droxyl groups are present on the glucose units, which can be partially
or fully reacted with various reagents to generate derivatives such as
cellulose ethers and cellulose esters (Siró and Plackett, 2010). The appli-
cation of cellulose and its derivatives as coating for fertilizers has gained
increasing attention due to their renewability, biodegradability and
film-forming ability (Bortolin et al., 2013; Davidson et al., 2013; Bajpai
et al., 2015; Li et al., 2015; Essawy et al., 2016; Li et al., 2016).
Ethylene cellulose (EC) is an inert, hydrophobic and biodegradable
cellulose derivative that is primarily used in fertilizer coating. Pérez
et al. mixed urea and lignin, then heated the mixture in a thermostatic
silicon oil bath to obtain a urea-lignin matrix (Fernández-Pérez et al.,
2008). The products were milled in a crusher to produce controlled-
release particles within a desired size range. Then, EC ethanol solution
(5%) was sprayed onto the products at 60 °C in a Wurster fluidized
bed, followed by air-drying at 70 °C. Different runs were made to obtain
products with different coating thicknesses. Water leaching experi-
ments were carried out to evaluate the nitrogen-release rates. The re-
sults demonstrated that EC coating can retard water diffusion and
slow nitrogen release.
However, another study indicated that urea releases occurred in
5 min with the coating of polyhydroxybutyrate (PHB) and EC, which
coated the urea granules through immersion and spraying with a pul-
verizer and triggler (Costa et al., 2013). The release rate was not in ac-
cordance with set standards for agricultural use. Furthermore, most
studies used the method that dissolved EC in organic solvent and then
sprayed it onto the fertilizer granules, which not only increases costs
due to the lean solvent and solvent recovery but also causes adverse en-
vironmental impacts due to hazardous emissions (Azeem et al., 2014).
2.5. Lignin
Lignin is the second most natural abundant biopolymer after cellu-
lose (Chowdhury, 2014). It is a copolymer of three different
phenylpropane monomer units, namely sinapyl alcohol, coniferyl alco-
hol and para-coumaryl alcohol (Pandey and Kim, 2011). It is typically
produced as a by-product of a chemical pulping process (Fernández-
Pérez et al., 1998) and during lignocellulosic biomass-based ethanol
833
production (Zakzeski et al., 2010). Due to its relatively low cost, biocom-
patibility, and availability from plant-derived sources, lignin has exten-
sive application in agriculture (García et al., 1996; Fellows et al., 2011;
Mulder et al., 2011; Sipponen et al., 2017).
Four types of commercially available lignin have been used to coat
urea granules, including soda flax lignin (Bioplast, Granit, Switzerland),
softwood kraft (Indulin. AT, Mead Westvaco, USA) and two lignosulfo-
nates (Wafex P and Borresperce, Borregaard/lignotech, Sweden)
(Mulder et al., 2011). Alkenyl succinic anhydride (ASA) has been used
to crosslink lignin. The lignin/ASA-coated urea granules have a smooth
surface, and the pinholes number was also low. However, urea
was completely released within 1 h in all formulations. In another
study, urea was coated with 10–20% kraft lignin and ethyl cellulose
(Fernández-Pérez et al., 2008). First, urea mixed with kraft lignin under
melting conditions was used to prepare the lignin matrixes. They were
crushed and sieved to obtain granules of a desired size. Then, an
ethanolic solution of ethyl cellulose was sprayed onto the matrixes
with a Wurster-type fluidized-bed equipment to obtain the coated
urea granules. Compared to the non-formulated urea, which completely
dissolved in less than 0.5 h, the urea release rate from the coated gran-
ules diminished. A total of 90% of the urea from the coated granules
was released within 48 h.
Lignin was also modified to improve its property. An acetic acid lig-
nin (AAL)-based hydrogel was prepared using isocyanate-terminated
polyurethane ionomers (IPUI) to crosslink (Peng and Chen, 2011). An
ammonium sulfate fertilizer core was coated with the hydrogel.
Controlled-release behavior was observed compared to the uncoated
ammonium sulfate. With the mass ratio of AAL to IPUI increasing from
0% to 35%, the ammonium sulfate release increased.
2.6. Agricultural residues
Agricultural residues are by-products of crops production and are
abundantly available, cheap, biodegradable, and renewable (Geng and
Henderson, 2012; Pittman et al., 2012). Agricultural residues, such as
wheat straw and corn stover, are comprised of cellulose, hemicellulose,
and lignin. They can provide organic matter and improve soil fertility
after degradation in soil (Johnson et al., 2010). However, approximately
half of them are disposed of through discarding and burning, which con-
tributes to severe environmental pollution (Bhatnagar and Sillanpää,
2010). To reduce this pollution and improve soil fertility, agricultural
residues have been utilized in EFFs (Ma et al., 2011; Yang et al., 2013;
Li et al., 2015; Holkar et al., 2016; Schneider Teixeira et al., 2016; Xia
et al., 2017).
An eco-friendly slow-release urea fertilizer (SRUF) was prepared
using mulberry branch-g-poly(acrylic acid-co-acrylamide) superabsor-
bent that was blended with urea, sodium alginate, and CaCl2 solution
(Zhang et al., 2014). The water-retention of the soil with SRUF improved
greatly compared to a treatment without SRUF. The water-retention
ratio of the soil (100 g) with 0.5 g of SRUF remained at 7.2 wt% after
25 d, whereas it was 2.0 wt% after 10 d in the control. However, the
urea released in deionized water and soil both exhibited fast release
rate, 85 wt% of the urea was released within 130 min in the water,
and nearly 100% of the urea was released after 10 d of incubation in
the soil. The reason may lie in the preparation process of SRUF, wherein
urea was blended with the superabsorbents, not coated with the super-
absorbents. The fast-absorbing rate of the superabsorbents led to con-
siderable urea releases from the fertilizer.
A coated fertilizer with a core/shell structure based on modified
wheat straw was prepared (Xie et al., 2011). The core was urea in an
attapulgite and alginate matrix, and the shell was a chemically modified
wheat straw-g-poly(acrylic acid)/attapulgite (CMWS-g-PAA/APT) su-
perabsorbent containing urea and borax, which provided nitrogen
(N) and boron (B), respectively. The contents of N and B were deter-
mined with an ammonia-selective electrode and inductively coupled
834 J. Chen et al. / Science of the Total Environment 613–614 (2018) 829–839
plasma; they were 23.3% and 0.65%, respectively. The product exhibited
slow-release and water-retention capacity.
Another example of agricultural-residue-based fertilizer used a
wheat straw-g-poly(acrylic acid) (WS/PAA) superabsorbent, which
was synthesized through graft polymerization with wheat straw and
acrylic acid in an aqueous solution (Liang et al., 2009). When 20% of
wheat straw was incorporated, the highest water absorbency was
achieved. Urea was loaded in the superabsorbent through the way
that superabsorbent was swollen in a urea aqueous solution. A total of
8% of the urea was loaded in the superabsorbent. Urea was released
completely within 60 min in water. However, in the soil, 16.3%, 60.2%
and 78.5% of the urea was released at 1, 5 and 10 days, respectively.
The difference in the release behavior in soil and water may be due to
the many types of ions that exist in the soil, which suppress the swelling
of WS/PAA in soil, resulting in urea diffusion becoming difficult and the
release rate of urea decreasing. Furthermore, the absorbing and desorp-
tion between urea molecule and soil particles also causes a slowing re-
lease rate of urea in soil.
2.7. Biochar
Biochar is a carbon-rich material that is obtained from the thermal
pyrolysis of agricultural residues or other lignocellulosic biomass at
moderately high temperature (González et al., 2015). Biochar has
been used as a biofertilizer or a support material for the controlled re-
lease of fertilizer due to its positive effects on the environment, such
as increased agricultural profitability, lower eutrophication risk to the
environment, sequestration of carbon from the atmosphere, and resto-
ration of degraded land (Yao et al., 2013; Cai et al., 2016).
A recent study introduced a polymer matrix composed of cotton
stalks (CSs), acrylic acid (AA), 2-acrylamide-2-methylpropanesulfonic
acid (AMPS), and bentonite (bent) into NH+ 4 -loaded biochar (N-BC),
and developed biochar-based slow-release nitrogen fertilizers (BSRFs)
(Wen et al., 2017). These fertilizers possessed high nitrogen-use effi-
ciency (64.27%), low nitrogen migrate-to-surface-loss amounts (7.4%),
and low nitrogen-leaching-loss amounts (10.3%). Furthermore, they ef-
fectively reduced the nitrogen-release rate (69.8% of nitrogen was re-
leased after 30 days), and consequently effectively promoted cotton
plant growth.
A controlled release fertilizer biochar may be considered an example
of biochar-based EFFs (González et al., 2015). Urea as an N source was
impregnated onto biochar in a batch reactor. Then, polysaccharide-
based polymers, including sodium alginate (SA), cellulose acetate (CA)
and ethyl cellulose (EC), were used to encapsulate the products, respec-
tively. The leaching potential was investigated in the soil columns with
and without wheat. The urea-N, ammonium, nitrite and nitrogen con-
centration were determined. The results indicated that the biochar
retarded the nutrient-release rate in soil, and the polysaccharide poly-
mers slowed down the urea hydrolysis from soil urease. However, the
crop yield was negatively affected by the developed formulations com-
pared with commercial N-CRF (ESN), although there was no significant
difference between the ESN- and EC-coated biochar-based fertilizer in
terms of nitrogen uptake in the grain of AC Barrie wheat after 90 days.
This may have been because the effectiveness of CRF depended on
crop, fertilization, soil characteristics and management factors (Chen
et al., 2008a).
A biochar-modified waterborne polyacrylate membrane coating was
prepared for use in fertilizer-controlled release (Zhou et al., 2015b). Wa-
terborne polyacrylate emulsion contained methyl methacrylate, butyl
acrylate, methyl acrylic acid, and the crosslinker aziridine. Then, biochar
(1%, w/w) was added into the emulsion to obtain membranes. The
effect of the membranes on the soil bacterial community profiles was
determined using Biolog EcoPlates and polymerase chain reaction-
denaturing gradient gel electrophoresis. The results indicated that
after incubation in paddy soil for 12 months, the membranes had no sig-
nificant impacts on the composition diversity of a soil dominant
bacterial community. During the early stages of incubation, the activity
and functional diversity of soil culturable microbial community de-
creased, which was because the membranes released small amounts
of soluble organic materials. However, it recovered after 12 months.
This study indicated that waterborne polyacrylate materials are envi-
ronmentally friendly and have potential in the development of coated
controlled-release fertilizers.
2.8. Polydopamine (Pdop)
Polydopamine is a primary pigment in naturally occurring melanin
(eumelanin) (Simon and Peles, 2010). Inspired by mussels, which can
strongly attach to diverse substrates with high binding strength, even
on wet surfaces, scientists have found that polydopamine can be easily
deposited on virtually all types of organic and inorganic substrates.
Therefore, it has a wide range of applications used as a coating material
(Liu et al., 2014; Xu et al., 2017).
Jia et al. coated double copper potassium pyrophosphate trihydrate
using Pdop through spontaneous oxidative polymerization of dopamine
(Jia et al., 2013). Slow release behavior of the nutrients was observed in
either water or soil, and the release rate of nutrients can be tailored by
using a multistep deposition technique. With an increasing number of
deposition cycles, the thickness of the Pdop coating increases, and the
release rate of nutrients trapped in the Pdop film decreases.
A “crosslinked coating-graft-polymer brush” structure was designed
to generate fertilizer with a pH-response and water-retention proper-
ties (Ma et al., 2013a). The fertilizer core was also a double-copper po-
tassium pyrophosphate trihydrate, which provides three essential
nutrients (P, K and Cu). Then, the Pdop layer was deposited on the fer-
tilizer core. Subsequently, a Pdop-based initiator was synthesized on the
surface of the fertilizer core, and the surface-initiated (SI)-ATRP tech-
nique was employed to graft poly(acrylic acid) on the Pdop layer. The
pH-responsive controlled release behavior was observed. P and Cu ex-
hibited the same release trend, wherein the release rate was slower in
the acid/neutral solution and faster in the basic solution. However, the
opposite trend was obtained for P. The charged/uncharged PAA layer
was the main reason for the pH-responsive release behavior. In the
basic solution, the layer was negatively charged and excludes anions
(P2O47 −) but let cations (K+ and Cu2 +) pass. At a low pH, the layer
remained uncharged and just served as a hindrance to reduce nutrient
releases.
Similarly, the researchers grafted poly(N-isopropylacrylamide)
onto the Pdop layer using the SI-ATRP technique, and prepared a
thermoresponsive release fertilizer (Ma et al., 2013b). Nutrient-release
studies were conducted at 25 °C and 37 °C. Faster nutrient release
rates were obtained at temperatures below a lower critical solution
temperature (LCST) (25 °C). This was due to the thermal switch behav-
ior of the PNIPAm layer. At 25 °C, the PNIPAm chains were stretching
and favored nutrients release. At 37 °C, the PNIPAm chains collapsed
and retarded nutrient permeability from the PNIPAm layer, thereby
slowing the release rate.
A “smart” fertilizer with poly(N,N-dimethylaminoethyl methacry-
late) (PDMAEMA) grafting from Pdop-coated ammonium zinc phos-
phate was developed (Feng et al., 2015). The nutrient releases
exhibited temperature- and pH-responsive behaviors according to the
ambient environment. In an acidic pH (below pKa of PDMAEMA) medi-
um, the nutrient-release rate accelerated due to the complete stretching
of the PDMAEMA brushes. In a medium pH, above the pKa of
PDMAEMA, the brushes gradually shrunk to hinder nutrient releases.
Furthermore, in a basic medium (pH above pKa of DMAEMA), the
nutrient-release rate was fast at temperature below the LCST of
PDMAEMA because of the extended PDMAEMA brushes, leading to a
high permeability of nutrients. However, at higher temperatures, such
as at noon or in summer, excessive nutrient release decreased and
avoided damage to plant roots. This “smart” fertilizer will improve
 J. Chen et al. / Science of the Total Environment 613–614 (2018) 829–839
nutrient availability, even when environmental conditions (tempera-
ture and pH) fluctuate.
3. Effect of EFFs on the environment
Fertilizer loss results in water pollution, air pollution, soil quality
degradation and other negative impacts. EFFs play an important role
in reducing such pollution, such as decreasing nitrogen oxide (NOx)
and dinitrogen (N2) emissions, increasing soil organic matter levels,
adjusting soil pH to an optimal pH, and improving water-retention
and water-holding capacity of soil.
3.1. Effect of EFFs on decreasing nitrogen oxide (NOx) and dinitrogen (N2)
emissions
Nitrogen fertilizer increases the gaseous emissions of ammonia, ni-
trogen oxides (NO and NO2), nitrous oxide (N2O) and dinitrogen (N2),
which play critical roles in air pollution and tropospheric and strato-
spheric chemistry. Generally, NOx and N2 gases are emitted in large
quantities to the atmosphere through soil biological and chemical pro-
cesses of denitrification/nitrification (Bremner, 1997; Kool et al.,
2011). Most of the atmospheric NOx and N2 is recycled into soil and
water to form acid depositions, leading to acidification, eutrophication,
shifts in species diversity, and effects on predator and parasite systems
(Galloway et al., 1995). NOx and N2 emissions can be reduced by chang-
ing the fertilizer type and amount, application methods and timing
(Harrison et al., 1995). Studies have shown that the application of
slow or controlled-release fertilizer can lead to lower NOx and N2 emis-
sions (Delgado and Mosier, 1996; Maggiotto et al., 2000; Halvorson
et al., 2014; Watts et al., 2015; Wei et al., 2017).
Nanocomposites were prepared by extrusion from a mixture of
montmorillonite, urea, and polymer (polyacrylamide hydrogel or
polycaprolactone) (Pereira et al., 2015). The urea release behavior was
studied in water. Pure urea was dissolved instantaneously. However,
the nanocomposites exhibited slower release behavior over 50 h, espe-
cially for the nanocomposites produced with polyacrylamide hydrogel.
The reason may lie in the polyacrylamide hydrogel competing with
water entering the pellets, preventing the fast solubilization of urea. A
field experiment was conducted to determine the N2O emissions from
the nanocomposites applied in soil that was seeded in winter wheat.
The highest N2O emissions were observed soon after nanocomposites
application during a substantial rain event. This was caused by a
combination effect of low oxygen levels and high amounts of available
N in soil, which favors denitrification activity (Hou et al., 2000;
Fernández-Luqueño et al., 2009; Díaz-Rojas et al., 2014). Over the 76-
day duration of the experiment, cumulative N2O fluxes of conventional
urea reached approximately 1850 g ha−1, whereas all nanocomposites
had lower N2O emissions, ranging from 99 to 560 g ha−1. The presence
of montmorillonite and polymers in the nanocomposites resulted in a
significant decrease in N2O emissions compared to urea, indicating
that their presence prevented urea exposure in water and soil as phys-
ical barriers, thereby reducing the urea hydrolysis rate. In addition to
acting as physical barriers, EFFs are expected to be designed to release
more N as the crop N demand increases, thereby reducing the quantity
of N available in the soil for nitrification and denitrification processes
and NOx formation.
A 3-year study was conducted to examine the N2O emissions for po-
tato production in a loamy sand in Minnesota (Hyatt et al., 2010). Single
pre-plant application of two different polymer-coated urea (PCU) was
compared with a conventional split application (CSA) using multiple
additions of soluble fertilizers. PCU-1 (42% N w/w) was a product
manufactured by Shandong Kingenta Ecological Engineering Co. Ltd.
(Linshu, China), and PCU-2 (44% N w/w) was a product (Environmen-
tally Smart Nitrogen) manufactured by Agrium Inc. (Calgary, AB,
Canada). Each treatment received 270 kg of fertilizer N ha−1 per season.
The results indicated that during 3 consecutive years, the mean
835
cumulative growing season N2O emissions were 1.36, 0.83, and
1.13 kg N ha−1 under CSA, PCU-1, and PCU-2, respectively. Furthermore,
the study found that tuber yields did not vary among fertilizer treat-
ments. These results revealed that single application strategies utilizing
EFFs can maintain potato yields, and can also reduce N2O emissions.
Compared with conventional split application using multiple additions
of soluble fertilizers, a single application of EFFs can reduce the costs
and equipment field time. However, an economic analysis is needed to
evaluate the high cost of EFFs (analyzed in Section 4).
3.2. Effect of EFFs on increasing soil organic matter
The loss of soil organic matter is a major concern in many regions.
Soil organic matter is a critical component in both natural and managed
ecosystems, providing organic substrate for nutrient release and playing
an important role in the maintenance of soil structure and water-
holding capacity, as well as in reducing erosion (Matson et al., 1997).
Furthermore, soil organic matter, as a substrate for soil decomposer or-
ganisms, supports divergent microbial communities. Fast-growing
plant species produce easily decomposable N-rich organic matter,
resulting in the dominance of bacterial-based soil communities, while
slow-growing plant species produce recalcitrant organic matter,
resulting in fungal-based microbial communities (Eskelinen et al.,
2009). It is evident that the use of green manure, animal manure or or-
ganic fertilizers can increase the soil organic matter levels (Shang et al.,
2014). However, there are limited reports on the long-term effect of
EFFs on soil organic matter content.
A 7-year field fertilization experiment was conducted by Geng et al.
to determine the effect of coated fertilizers on crop yields, and on the
mean nitrogen use efficiency (NUE), organic matter, soil N content,
available P and K content, and soil pH values (Geng et al., 2015). Coated
fertilizers are urea that is coated with hybrid coatings of sulfur and a
thin polymer, which are commercially available from Kingenta Ecologi-
cal Engineering Co. Ltd. in Shandong, China. The nitrogen content of the
coated fertilizer is 33%. Three application rates of 180 kg ha−1,
126 kg ha−1 and 90 kg ha−1 of the coated fertilizer was applied under
a rice (Oryza sativa L.)-oilseed rape (Brassica napus L.) rotation system
in Hubei province, China. The rice and oilseed rape yield increased by
6.1–8.2% and 6.3–15.5%, and the NUE was increased by 15.4–38.4%,
compared with the control, which applied urea at the same N rate. Fur-
−
thermore, the ammonium N (NH+ 4 -N) and nitrate N (NO3 -N) contents
of the coated fertilizer treatments were higher in the 0–40 cm soil layer,
but were lower in the 60–100 cm soil. The opposite trend was observed
for the urea treatments. This results indicated that the coated fertilizer
−
decreased the NH+ 4 -N and NO3 -N leaching into the deep soil. After
the harvest of rice, the total N and organic matter contents were in-
creased by 22.1% and 11.4%, respectively, in the 0–20 cm soil layer, by
applying the coated fertilizer after 7 years of fertilization. The corre-
sponding contents were increased by 21.0% and 14.8% after the harvest
of oilseed rape. The increase of the total N and organic matter contents is
because the coated fertilizer not only achieved a greater yield and bio-
mass, but also increased the amount residues, such as from roots, that
returned to the soil.
Although every type of fertilizer may increase organic matter returns
as crop residues into the soil by increasing crop yields, thereby raising
the soil organic matter content, EFFs have unique advantages in reduc-
ing the pollution of N by N leaching, maintaining soil fertility and de-
creasing the labor cost, compared with other fertilizers. However, the
application of EFFs to soil will influence the pH, ionic strength and
ionic composition of a soil solution, which will influence physico-
chemical processes (such as the dispersion or flocculation of clay parti-
cles) and thus soil aggregation, whereas aggregate stability is often
closely correlated with soil organic matter content (Haynes and Naidu,
1998). Long-term fertilizer experiments should be carried out to deter-
mine whether soil organic matter has been improved from the addition
of EFFs.
836 J. Chen et al. / Science of the Total Environment 613–614 (2018) 829–839
3.3. Effect of EFFs on adjusting soil pH
The soil pH is important to plants due to its effect on nutrient avail-
ability. For example, phosphorus is most available for plant uptake at a
pH from 6.0–6.8. Manganese and copper are uptaken easily by plants
when the pH decreases, and they become unavailable at a pH of 7.0 or
above. Furthermore, the soil pH is related to the toxicity of some ele-
ments. For example, aluminum, which is a component of most soil min-
erals but is not a nutrient, is increasingly soluble and toxic at a pH less
than 5. When the soil pH is in a range of 5.5–7.0, most nutrients are
available to plant roots, and the soil microbial biomass and microbial ac-
tivity stabilize (Wang et al., 2006).
The over-application of fertilizers, especially ammonium- or urea-
based nitrogen fertilizers, intensifies soil acidity, which affects microor-
ganism variety and activity, restricts nutrients cycling, and retards
water infiltration and plant root development (Goulding and Blake,
1998; Rasmussen et al., 1998). However, soil acidification can be slowed
from the application of EFFs (Geng et al., 2015). Recently, hydrogel/su-
perabsorbent coated EFFs have been developed to enhance the ability
of adjusting the soil pH.
A biomass-based multifunctional fertilizer has also been developed,
including urea granules, co-granulated with natural attapulgite and am-
monium zinc phosphate as a fertilizer core, cellulose acetate butyrate
(CAB) as an inner coating, and carboxymethyl chitosan-g-poly(acrylic
acid)/attapulgite (CMCS-g-PAA/ATP) hydrogel as an outer coating
(Wang et al., 2014). The hydrogel coating was crosslinked using N-
maleyl chitosan (N-MCS) to improve coating material degradation.
When the hydrogel coating was immersed in the soil solution, it
swelled, facilitating the interaction of polymers with soil microorganism
and resulting in hydrogel degradation. A nutrient-release study indicat-
ed that approximately 81.4% of N and 41.2% of Zn was released from the
double-coated fertilizer after 30 days, suggesting that the coated fertil-
izer can efficiently control nutrient release rates. When the hydrogel
coating was immersed in soil solutions with different pH values, it buff-
ered soil solution pH to approximately 7.0. This is because there are
large amounts of \\COOH and \\COO− groups in the hydrogel. In an
acidic medium, the\\COO− groups can react with H+, and in an alka-
line medium, the\\COOH groups can react with the OH− of the soil so-
lution. The results indicate that the hydrogel coating can buffer soil
acidity or alkalinity and develop an optimal pH for plants.
A similar strategy was employed in a study that developed a multi-
functional fertilizer based on natural attapulgite clay as a matrix, guar
gum (GG) as an inner coating, and guar gum-g-poly(itaconic acid-co-ac-
rylamide)/humic acid (GG-g-P(IA-co-AM)/HA) superabsorbent as an
outer coating (Ni et al., 2012). In addition to the N, P and K provided
by urea and KH2PO4, other nutrients elements can be provided to plants,
such as Ca, Mg, Fe, due to the abundant elements content of attapulgite.
A total of 80 ml of soil solution with pH values from 4.0 to 10.0 were
treated with 0.1 g of the superabsorbent for 90 min; then, the pH values
changed to 7.09–7.30. This resulted from large amounts of\\COOH and
\\COO− groups presented in the superabsorbent polymers, which
reacted with the OH− and H+ of the soil solution under basic and acidic
conditions, respectively. The results suggest that these fertilizers can be
used as a type of soil amendment.
3.4. Effect of EFFs on improving water-retention and water-holding capac-
ity of soil
A continued increase in agricultural production requires an in-
creased supply of irrigation water. It has been reported that irrigated ag-
ricultural lands in semiarid and arid regions are being degraded by
waterlogging and salinization (Matson et al., 1997). More salts and min-
erals are brought to the surface or groundwater during irrigation return-
flows due to evaporation and concentration, which affect downstream
agricultural and natural systems. Unless water-use efficiency increases,
greater agricultural production will require increased irrigation. On the
other hand, water is scarce in some regions, which currently or will soon
fail to have adequate water to maintain per capita food production from
irrigated land.
Application of superabsorbents to soil can improve the physical
properties of soil, including the structure, porosity, and water-holding
capacity (Andry et al., 2009; Snyder et al., 2009; Burke et al., 2010; Lü
et al., 2016). Johnson reported that the water-retention capacity in-
creased by 171–402% when superabsorbents were applied in coarse
sand (Johnson, 1984). Islam et al. found that the treatment of superab-
sorbents could conserve soil water, which is available for plants to in-
crease biomass accumulation and reduce oxidative stress, especially
under severe water stress (Islam et al., 2011). Furthermore, with the ap-
plication of superabsorbents, plant height, leaf area, and number of
grains, as well as starch, soluble sugar, and protein contents in the
grain also increased.
Based on previous studies, researchers have introduced superabsor-
bents into EFFs. Mikkelsen et al. reported that the addition of superab-
sorbent to fertilizer solutions reduced 45% of the N leaching compared
with N fertilizer alone during the first 4 weeks in heavily leached condi-
tions (Mikkelsen et al., 1993). Demitri et al. prepared cellulose-based
hydrogels and used them as a carrier for the controlled release of nutri-
ents (Demitri et al., 2013). The main advantage of the formulation is that
hydrogels may store water and release it slowly when the soil dries,
maintaining the soil humidity over a relatively long time.
Wang et al. prepared a coated fertilizer using a k-carrageenan-g-
poly(acrylic acid)/Celite (kC-g-PAA/Celite) superabsorbent as coating
materials (Wang et al., 2012). Application 0, 1, 2, and 3 wt% of the coated
fertilizer achieved 46%, 67%, 86%, and 113.5% of the water-retention ca-
pacity of the soil, respectively. After 10 days, the water-retention capac-
ity of the soil became 0, 22%, 40.5%, and 62% with 0, 1, 2, and 3 wt% of the
coated fertilizer, respectively. The water-holding capacity of the soil was
39%, 46.5%, 53.5%, and 59% for 0, 1, 2, and 3 wt% of the coated fertilizer,
respectively. The results indicated that the water flow rate through the
soil slowed from the addition of the coated fertilizer into the soil. There-
fore, if the coated fertilizer was applied to an agricultural field, it could
reduce water losses from infiltration and could supply moisture to
crops over time.
Polyurethane was synthesized using liquefied corn stover, isocya-
nate, and diethylenetriamine; it was then used as a coating material to
form polymer-coated urea (Yang et al., 2013). A superabsorbent com-
posite based on chicken feather protein (CFP) and acrylic acid was
also formulated and used as an outer-coating material. Nitrogen release
behaviors and water-retention capability of the double-layer polymer-
coated urea (DPCU) were determined in the water and soil. The
sustained release of nitrogen was achieved both in water and soil. The
water-holding capacity was 68.4% greater than the control (without
DPCU) when the addition of 4 g of DPCU into 200 g of soil. The water-
retention capacity of the soil is 28.1% and 34.5% on day 28 when 10 g
and 20 g of DPCU was applied, respectively, whereas without DPCU, it
was only 17.2%. The enhanced water-holding and water-retention
property from the application of the DPCU could be beneficial for
crops in arid regions. N-use efficiency and leaching losses, ear yields,
and dry-matter accumulation were investigated in a sweet corn soil-
plant system. The N-use efficiency of the plants with DPCU application
was 71.9% greater than the conventional urea treatment. Ear yields
and the total dry matter accumulation were enhanced compared to
the DPCU treatments with conventional urea fertilizer. The N leaching
loss rate of DPCU was ∼1/2–1/3 of the conventional urea for both irriga-
tion rates. These results revealed that DPCU application effectively in-
creased the soil water-retention capability, improved the N-use
efficiency, and reduced N-leaching losses.
4. Challenges and perspectives
The most prominent barrier to EFFs application is their high cost.
Generally, they are in the range of 2.5 to 8 times the cost of regular
 J. Chen et al. / Science of the Total Environment 613–614 (2018) 829–839
chemical fertilizers, which limits their use to high cash crops or to
specialties such as professional turf, landscaping and horticulture
(Davidson and Gu, 2012). The reasons for the high cost are as follows:
the coating materials are much more expensive than the fertilizer; the
production process is complicated; a size separation device is employed
to achieve a perfect coating; and the amounts of labor increases. There-
fore, EFFs have been, and continue to be, a relatively small market com-
pared to typical chemical fertilizers.
Another challenge is the degradation of the coating materials on
EFFs. Pure biodegradable natural polymers are susceptible to microbes
and enzymes and cannot effectively control fertilizer releases over a
longer period. For natural polymer/synthesis polymer blends or copoly-
mers, there are two concerns about their degradability. First, is the al-
lowable percentage ratio of the synthesis polymer in blends or
copolymers. Second, is the acceptable upper limit of degradability (%)
in claiming the degradability content of blends or copolymers (Majeed
et al., 2015).
Ideally, EFFs should meet the crop nutrient demand for the entire
season through a single application. Plants require more nutrients dur-
ing the growth period, whereas they do not need nutrients at all in the
earliest stages of plant growth or the mature period. However, most of
the EFFs do not respond directly to plants demands for nutrients.
Furthermore, there is no adequate study of the release behavior of
EFFs in various environmental conditions, such as in different tempera-
tures, ambient moisture, soil types, soil pH, soil bioactivity and so on. In
particular, for fertilizers coated with hydrogels/superabsorbents,
their release behavior is susceptible to water in the environment.
Hydrogels/superabsorbents swell during irrigation or rain, and nutri-
ents release is activated. In the intervals of irrigation or rain,
hydrogels/superabsorbents dry and nutrient release is retarded. This
may not be synchronous with the growth timeline or nutrient require-
ment of crops.
However, what is clear is that the environmental benefits of EFFs are
worth continued study, especially for high-value crops. Moreover, the
environmental benefits may be useful for governments in determining
cost-sharing to encourage producers to use EFFs in their crop produc-
tion systems.
In view of the above challenges, the authors offer a few suggestions:
Although various natural materials have been employed as coatings
to retard nutrients release and increase fertilizer use efficiency, they
need to be modified and manufactured in an ecological and cost ef-
fective way.
Plants need more nutrients in the growth period, whereas most of
the EFFs release nutrients fast in the earliest stages of plant growth.
This imbalance always caused by the inadequate hydrophobicity of
these natural-materials-based coating materials. Novel biodegrad-
able and renewable coating materials with superhydrophobicity
should be designed and developed to synchronize the nutrient re-
lease with the growth timeline or nutrient requirement of crops.
5. Conclusion
Fertilizer losses not only reduce nutrients efficiency, resulting in low
plant yields, but also create adverse impacts on the environment. Exten-
sive efforts to solve these problems have brought about a variety of
strategies. In particular, environmentally friendly fertilizers (EFFs) pro-
vide an effective way to improve nutrient-use efficiency, minimize
leaching and volatilization losses of fertilizers, and reduce environmen-
tal hazards by retarding or even controlling the release of nutrients into
soil. However, some challenges remain. The following aspects should be
considered. First, coating materials should be degradable and low cost.
Furthermore, the preparation process should be simple and economical
to encourage fertilizer production on a large scale. To this end, degrad-
able natural materials, which have generated increasing interest in
837
coated fertilizers, may be taken into consideration in designing new
types of EFFs. Second, ideal EFFs should meet crop nutrient demands
over the entire season through a single application. A further under-
standing of the effect of various environmental conditions, such as tem-
perature, ambient moisture, soil type, soil pH and soil bioactivity would
provide new opportunities for more efficient EFFs. However, the devel-
opment of sustainable modern agriculture has not been associated with
EFFs use, but their use accompanies advances in the sustainability of
water and pesticides use, energy input, manufacturing and other eco-
nomic sectors that also significantly impact the environment.
Acknowledgements
The authors gratefully acknowledge financial support from the Na-
tional Natural Science Foundation of China (grant no. 51503091,
51541304, 51273086), and the Fundamental Research Funds for the
Central Universities (grant no. lzujbky-2016-41, lzujbky-2016-ct05).
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