See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/272399926

A comprehensive review on biodegradable polymers and their blends used in

controlled-release fertilizer processes

Article · February 2015

DOI: 10.1515/revce-2014-0021

CITATIONS READS

21 1,663

4 authors:

[email protected] Hussain Nur Kamila Ramli

Universiti Teknologi PETRONAS Universiti Teknologi PETRONAS, Tronoh, Perak Darul Ridzuan
19 PUBLICATIONS   45 CITATIONS    7 PUBLICATIONS   31 CITATIONS   

SEE PROFILE SEE PROFILE

Nurlidia Mansor Zakaria Man

PETRONAS Universiti Teknologi PETRONAS
37 PUBLICATIONS   89 CITATIONS    249 PUBLICATIONS   2,385 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Ionic Liquids View project

New thermally resistant adsorbents for wastewater treatment View project

All content following this page was uploaded by [email protected] Hussain on 01 June 2015.

The user has requested enhancement of the downloaded file.

 Rev Chem Eng 2015; 31(1): 69–95

Zahid Majeed, Nur Kamila Ramli, Nurlidia Mansor* and Zakaria Man

A comprehensive review on biodegradable

polymers and their blends used in controlled-
release fertilizer processes
Abstract: Biodegradable polymer-coated controlled-
release fertilizers (PC-CRFs) are essential means to reduce
1 Introduction
cost, improve marketability, conserve land fertility,
The world population is expected to grow by over 2.3 billion
achieve high crop yields and combat climate challenges.
people, between 2009 and 2050 (FAO 2009). To meet the
It is known that about 15–30% of any fertilizer packed
food demand of the world population and to tackle the
in a PC-CRF does not get released due to the concentra-
issues of food security through sustainable agriculture,
tion gradient difference across the polymer coatings. To
fertilizers have gained prime importance in the research
release the trapped fertilizer(s), it is desired that polymer-
and development of modern agriculture practices. On a
based coatings should biodegrade after the fertilizer is
global scale, applications of uncoated chemical fertilizers,
completely released into the soil. This review has aimed to
specifically nitrogen (N), phosphorus (P) and potassium
provide a comprehensive account for various biodegrad-
(K), are forecast to rise significantly around the world at a
able polymers/blends derived either from natural or syn-
rate of 2.5 million metric tons per year to meet the demand
thetic sources which are cited in the literature for PC-CRFs.
and supply gap (Zhang and Zhang 2007). However, most
In addition, this review covers the discussion on their
commercially uncoated fertilizers, so far, are well known
classification criteria, trends in the processes of fertilizer
for low efficiency of plant nutrients uptake due to losses
coatings, methodological issues for their biodegradation
on farmland by various reasons such as runoff, leaching
assessment, coating attributes that affect the biodegra-
and volatilization. These factors not only lead to financial
dability and an outlook into their biodegradation kinetic
losses but also pose risks to the environment and waste of
models that involve enzymes and microbial processes. It
energy (Entry and Sojka 2008). Therefore, the key impetus
also concludes that experimental as well as modeling data
of exploring into new biodegradable fertilizer coating
are insufficient to assess the biodegradation contribution
materials has been envisaged for effective nutrient encap-
of the overall nutrient release in PC-CRFs.
sulation in order to minimize nutrient losses and to cater
the specific plant nutrients demand at different plant
Keywords: biodegradation; controlled-release fertilizers;
growth stages to optimize the yield under specific soil
kinetic models.
conditions. To overcome this problem, plant nutrients are
either coated or chemically incorporated into a polymer
DOI 10.1515/revce-2014-0021 matrix, and are termed polymer-coated controlled-release
Received May 27, 2014; accepted December 19, 2014 fertilizers (PC-CRFs). PC-CRFs are the type of organic and
inorganic encapsulated fertilizers coated with various
types of polymeric materials that provide a better means
of targeted delivery of controlled-fertilizer supply for the
agricultural crops.
After Oertli and Lunt (1962), there has been increasing
research interests in the area of polymer resource utiliza-
tion for PC-CRFs. Meta-analysis has already shown that
*Corresponding author: Nurlidia Mansor, Department of PC-CRFs are a viable option as they reduced the environ-
Chemical Engineering, Universiti Teknologi PETRONAS, mental pollution by reducing the emission of nitrous oxide
Bandar Seri Iskandar, 31750 Tronoh, Perak, Malaysia,
and nitric oxide gases (Akiyama et al. 2010). According to
e-mail: [email protected]
Zahid Majeed, Nur Kamila Ramli and Zakaria Man: Department of
Shaviv (2005), in the past, non-biodegradable synthetic
Chemical Engineering, Universiti Teknologi PETRONAS, Bandar Seri coating materials also posed serious environment prob-
Iskandar, 31750 Tronoh, Perak, Malaysia lems such as polyolefin coatings’ lower biodegradation

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
70      Z. Majeed et al.: Controlled-release fertilizer biodegradation

rates than alkyd resins and polyurethane-like resins, as duration of their application. ASTM standard D-5488-
they decompose extremely slowly or not at all in the soil. 94d defines the term “biodegradation” for the materi-
Their use may thus lead to an undesirable accumulation als “capable of undergoing decomposition into carbon
of plastic residues up to 50 kg/ha/year (Trenkel 2010). dioxide, methane, water, inorganic compounds or micro-
According to the same author (Trenkel 2010), even if the bial biomass in which the predominant mechanism is
decomposition of such polymers takes a period of 10 the enzymatic action of microorganisms, which can be
years, the 500 kg/ha maximum accumulation would only measured by standard tests, in a specified period of time,
be 200 ppm of dry soil. Furthermore, if the polymer frag- reflecting available disposal conditions”.
ments decompose, smaller fragments than sand particles Indicators of polymer biodegradation assessment are
become part of the soil, and hence deteriorate the soil not limited but generally acceptable are those which are
quality. Therefore, research on PC-CRFs has alarmed the reported in the literature, such as surface roughness, loss
various concerns related to the non-biodegradable syn- of mechanical strength (Shogren et al. 2003, Karamanlio-
thetic polymer uses. It has motivated the focus of current glu and Robson 2013), assimilation by microorganisms
research towards replacing such polymers with biode- (Lucas et al. 2008), degradation by enzymes (Ignat et al.
gradable natural or synthetic polymers/blends derived 2011), backbone chain breakage and subsequent reduc-
from renewable natural resources. Such measures could tion in the molecular weight (MW) (Karamanlioglu and
be an effective way forward for the sustainable global Robson 2013, Shah et al. 2013). Therefore, biodegradable
carbon balance, as the CO2 evolved is recaptured into polymers, their blends, composites or their modifications
the plant biomass via the photosynthesis process. Use of that make them amenable to these defined and till-date-
biodegradable coatings adds additional advantages for known mechanisms are to be declared biodegradable
PC-CRF products as these are known for their hydrogel- polymers applied for PC-CRF processes. Inert polymers
forming properties which improve water holding capacity such as polyethylene and polypropylene are also known
(WHC) of soil, reduce oxidative stress and enhance particle to be attacked by selected microbial and fungi species
aggregation to minimize soil erosion (Andry et  al. 2009, (Sivan 2011) although biodegradation of these polymers
Snyder et  al. 2009, Burke et  al. 2010). PC-CRFs have also proceeds partially and slowly. Therefore, in such cases to
been exploited in the field of bioremediation where they use the term “non-biodegradable polymer” needs special
can stimulate the dormant microbial activity through the caution particularly when blends consist of biopolymers.
provision of necessary nutrients and prolong the period of Based upon the literature, a biopolymer promotes bio-
natural biodegraders in oil-spilled lands, aquifers, shore- degradation of synthetic polymers in blends, and such
lines and sediments (Lee et al. 1993, Xu and Obbard 2003). blend-based coatings have been claimed biodegradable.
Biodegradable coatings have made it further possible to However, our perception about biodegradation may be
encapsulate the specific natural or engineered microbial affected by the purpose of applications and natural envi-
strains as biofertilizer(s). The biodegradation of coatings ronmental conditions under which the test is performed.
facilitates the release of biofertilizers into the soil where The previous history of the environment, exposed to the
they actively solubilize the insoluble nutrients, particu- same substrate, may cause the specific biodegraders to
larly from mineral rocks to maintain the continuum of easily adopt and develop changes at the genomic level to
nutrient flux available to plant roots. express more specific enzymes. Such strategies help them
Although biodegradability has become a highly to successfully invade, grow and efficiently break the
subjective matter nowadays, the perceptions about the polymer chains into low-MW products that release into
biodegradability of a polymer are being changed with eve- the environment – could have either a benign or harmful
ryday development of new biodegradable polymers from role.
a variety of renewable natural resources. For example, As stated in ASTM standard D-5988-12, soil is an
nature-inspired synthetic polydopamine (Pdop), and syn- extremely species-rich source of inoculum for evaluation
thetic polylactic acid (PLA) and Poly(3-hydroxybutyrate) of the biodegradability. When maintained appropriately
(PHB) derived from renewable natural resources are now with regard to moisture content and oxygen availability,
acceptable as biodegradable polymers with their applica- the biological activity is quite considerable, although
tions in PC-CRFs (Costa et al. 2013, Jia et al. 2013). Accord- lower than other biologically active environment, such as
ing to Göpferich (1996), “biodegradable” polymers are activated sewage sludge. PC-CRFs tested under such soil
those polymers which biodegrade during their applica- conditions were attempted to evaluate the in situ nutrient
tion, while “non-biodegradable” polymers are those that release concomitantly when the material was in contact
require substantially longer time to biodegrade than the with soil microorganisms (Ge et al. 2002, Jia et al. 2013).

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
 Z. Majeed et al.: Controlled-release fertilizer biodegradation      71

Biodegradability tests of Pdop-coated multi-elements natural rubber-g-modified starch (Riyajan et al. 2012) and
(Jia et al. 2013) and urea-incorporated controlled-release starch-g-poly(l-lactide) (Chen et al. 2008), and blends of
starch/lignin matrix (Majeed et  al. 2014b) showed that biodegradable polymers with synthetic non-biodegrada-
materials biodegrade faster under sterilized soil as com- ble polymers such as starch with polysulfone (Tomasze-
pared to non-sterilized soil. The difference of biodegrada- wska and Jarosiewicz 2004) and starch with polyurethane
tion was due to the difference in the soil microorganism’s (PU) (Ge et  al. 2002). However, commercial scale-up of
activity. Biodegradation of PC-CRFs gives better assess- completely biodegradable PC-CRFs is yet to be realized
ment of the coating performance on the release of nutri- (Davidson and Gu 2012).
ents under soil conditions. There is general consensus that Keeping in view the importance of biodegradable
nutrient release is fast in soil compared to the aqueous polymers and their blends in PC-CRF research, this review
conditions for biodegradable coatings of fertilizers. It is has been aimed to critically analyze biodegradable poly-
understood that in addition to microorganisms, various mers, their modified forms and their blends with other
other factors such as pH, temperature and soil type could synthetic/natural polymers reported as biodegradable
also promote the overall outcome of the nutrient release PC-CRFs under in situ soil conditions. To address this
in a specified period of time. So far, limited techniques are issue, the classification criteria are re-examined for
applied for the complete characterization of the biodegra- PC-CRFs before classifying them into suitable two main
dation process involved in PC-CRFs in soil. Among these emerging coating processes which are hydrogel-forming
techniques, the most common is the weight loss (Majeed hydrophilic PC-CRFs and non-hydrogel-forming hydro-
et  al. 2015), but infrequently also cited are differential phobic PC-CRFs. The latter have been described quite fre-
scanning calorimetry (DSC) and Fourier transform infra- quently as slowly biodegradable PC-CRFs. As discussed
red spectroscopy (FTIR) (Ni et al. 2009, Lum et al. 2013). above, such coatings when mixed with biopolymers are
Natural biodegradable polymers, such as lignin, better exposed to the processes of biodegradation. This
starch, chitin, cellulose and other polysaccharides (e.g., fact has pushed us to also include biodegradable natural
k-carrageenan), cannot be used in natural pure form as and synthetic polymers and also their blends-based fer-
effective coating material due to their inherent properties tilizer coatings within the scope of this review. Different
which put some of technical limitations on their usage. methods are also discussed that have been reported by
For example, starch is hydrophilic in nature and has many researchers for the evaluation of PC-CRF biodegra-
poor mechanical properties. Lignin is more heterogene- dation. Microbial susceptibility, porosity, polymer blends/
ous, and has incompatibility with hydrophilic polymers, composites composition and type of cross-linkers have
complex chemistry and hydrophobic behavior. Cellulose been taken in length to provide these parameters effect
is also hydrophilic but its industrial demand is very high. on biodegradability of PC-CRFs. At the end of the review,
Chitin is a highly crystalline biopolymer, and has a very enzymes and microbial biomass-based biodegradation
low insolubility in common solvents due to α and β forms. kinetic models are also discussed especially to provide
To overcome these issues, still researchers have to do further insight into the biodegradability of PC-CRFs.
necessary chemical and physical modifications of such
biopolymers to improve their reactivity and biocompati­
bility with other classes of either natural or synthetic
polymers. For example, partial deacetylation of chitin
2 Biodegradable PC-CRF
under the alkaline condition produces a pseudonatural classification
cationic polymer named chitosan, which is soluble under
aqueous acidic media and has been known for casting So far there are no comprehensive guidelines that lay
film properties (Ravi Kumar 2000). In addition, cross- out the criteria for the classification of biodegradable
linkers, compatibilizers and fillers are usually selected to PC-CRFs. In the past, scientists have attempted to clas-
achieve processable, improved film-forming biodegrad- sify biodegradable PC-CRFs on the basis of their sources
able polymer blends towards green PC-CRF acquisition. such as natural or synthetic, modified blends, hydrogel-
Despite the above-mentioned challenges, researchers forming hydrophilic polymers (Mikkelsen 1994, Devass-
have tested various possibilities of biodegradable coatings ine et  al. 2002, Davidson and Gu 2012, Davidson et  al.
that consist of starch (Otey et al. 1984, Naz and Sulaiman 2013) and non-hydrogel-forming hydrophobic polymers
2014), lignin (Mulder et  al. 2011), blends of lignin with (Azeem et  al. 2014). There is general consensus that
ethyl cellulose (EC) (Fernández-Pérez et  al. 2008) and hydrogel coatings are more biodegradable compared to
starch with lignin (Ariyanti et  al. 2012), copolymers of non-hydrogel coatings due to the difference in the mode of

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
72      Z. Majeed et al.: Controlled-release fertilizer biodegradation

biodegradation and nutrient release mechanism. Hydro- resistance under environmental stresses due to soil mois-
gels can termed as “superabsorbents” when capacity of ture, temperature, pH and activity of invertebrates, there-
retaining water reached the extreme upper limit that is fore, purposely PC-CRFs are chemically, physically and
approximately 500 times of their own mass (30–60% of biologically modified.
the total volume). retain large amount of water and. It is A literature survey shows that PC-CRFs are coated
anticipated that hydrogels effectively impede the nutrient with 6 main sources of biodegradable polymeric materials
release before it biodegrades. Some criteria of classifica- that are under the current research and development:
tion for the coatings of fertilizers used earlier by different –– PC-CRFs coated with pure/modified natural polymers
researchers are listed in Table 1. In Figure 1 are classified –– PC-CRFs coated with mixed natural polymers
those polymers or blends that are reported for PC-CRFs –– PC-CRFs coated with nature-inspired/bioderived syn-
based on either hydrogel or non-hydrogel properties. thetic polymers
According to an ICL technology incubator (http:// –– PC-CRFs coated with mixed natural-bioderived syn-
www.icl-innovation.com/EEF, retrieved 14 August 2014), thetic polymers
commercialization for any biodegradable PC-CRFs in eco- –– PC-CRFs coated with mixed natural-hydrocarbon-
nomical agro terms should meet minimum 85 wt/wt% derived synthetic polymers
encapsulation efficiency of a fertilizer. In addition, the –– PC-CRFs coated with hydrocarbon-derived synthetic
fertilizer release profile should synchronize with rhizos- biodegradable polymers.
phere’s biology and coatings should be composed of bio-
degradable materials. To mitigate this challenge and to
revolutionize the agriculture crop productivity, explora- 2.1 P
 C-CRFs coated with pure/modified
tion of a suitable polymer coating scheme should involve natural polymers
comprehensive testing with natural microbial inoculum.
To reduce the cost, and achieve better time control over According to Sempeho et  al. (2014), there are three
the nutrient release, coatings should show reasonable basic types of natural polymers widely used in the
biodegradability, enough crushing strength to bear crack controlled-release delivery systems. These are neutral

Table 1 Criteria for the classification of biodegradable PC-CRFs.

Criteria Classification Reference

Biodegradability 1. Unmodified polymers: naturally susceptible to microbial-enzyme attack Platt (2006)

2. Synthetic polymers: primarily polyesters
3. Naturally biodegradable but modified polymers with additives and fillers
Hydrophilicity 1. Naturally occurring polymers: proteins, polysaccharides, lignins and Mikkelsen (1994)
rubber
2. Semi-synthetic polymers: primarily cellulose, which is reacted with
functional groups derived from petrochemicals
3. Synthetic polymers derived from polymerization of monomers from
petrochemicals
Nutrient release 1. Materials releasing nutrients through a low-solubility product due to a Trenkel (1997)
complex/high molecular weight of chemical structure following microbial
decomposition
2. Materials releasing nutrients through a coated surface (coated fertilizers)
3. Materials releasing nutrients through a membrane which may or may not
be soluble (encapsulation). Nutrient-releasing materials incorporated
into a matrix which itself may be coated
4. Materials releasing nutrients in delayed form due to a small surface-
to-volume ratio (supergranules, briquettes, tablets spikes, plant food
sticks, etc.)
Nutrient solubility 1. Compounds of low solubility Wang et al. (2012)
2. Coated or encapsulated water-soluble fertilizers
Water vapor permeability 1. Synthetic polymers, with a small water vapor permeability coefficient Devassine et al. (2002)
(K  ≤  3000 cm2 s-1 Pa-1) due to more hydrophobic structure
2. Non-modified polysaccharides, with a higher permeability coefficient
(K ≥ 4000 cm2 s-1 Pa-1) due to hydrophilic groups

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
 Z. Majeed et al.: Controlled-release fertilizer biodegradation      73

Biodegradable
polymers
Biodegradable Hydrogel Biodegradable Non-hydrogel
forming polymers forming polymers

Pure/mixed/ modified Natural-synthetic Monomers derived from Natural-synthetic Monomers derived from
Synthetic
renewable resources polymer blends natural renewable polymer blends petrochemical non-
polymers
from plants/animals/ resources renewable resources
microorganisms
Starch/Polylactic acid Poly (acrylic-acid) Poly(3-hydroxybutyrate) Polyethylene/ paraffin Polyurethanes
(Chen et al., 2008) (Liang and Liu 2006) (Costa et al., 2013, Yang wax (Ge et al., 1998)
Starch et al., 2012) (Al-Zahrani, 2000)
(Naz et al., 2014) Polyolefin
Starch/Acrylic Acid Polyvinyl alcohol Paraffin Wax/Rosin (Fujita et al., 1983)
(Anggoro, 2011) (PVA) Polylactic acid
Chitosan (Ibrahim and Jibril 2005)
(Alemzadeh and (Jintakanon et al., 2008) Polyethylene
(Jamnongkan and Vossoughi 2002) terephthalate
Kaewpirom 2010a) Poly-caprolactone/
Poly(3-hydroxybutyrate)/ (Devassine et al., 2002)
starch/clay Natural rubber ethylcellulose
Lignin (Wu et al., 2007) (Riyajan et al., 2012) (Costa et al., 2013) Polysulfone
(Mulder et al., 2011)
Wheat Gluten (Tomaszewska and
Lignin/polyurethane (Castro-Enríquez et al., Jarosiewicz 2002)
κ-Carrageenan-sodium (Peng et al., 2011) 2012) Polyacrylonitrile
alginate (Tomaszewska et al.,
(Wang et al., 2012) Starch/polyvinyl Polydopamine 2002)
alcohol (Jia et al., 2013)
Cellulose (Han et al., 2009) Polystyrene
(Davidson et al., 2013) (Yang et al., 2012)
Polysulfone/starch Cellulose acetate
Gelatin (Tomaszewska et al., butyrate/ Poly[N-Isopropyl
(Junejo et al., 2014) 2004) carboxymethyl acrylamide]-co-
chitosan-g- Polyurethane Copolymers
Polybutylene poly(acrylic (Mathews and Narine 2010)
succinate/starch acid)/attapulgite
(Chin-San, 2008) (Wang et al., 2014) Polyvinyl chloride
(Hanafi et al., 2000)

Figure 1 Classification of biodegradable polymers and their blends reported in the literature.

(hydroxypropylmethylcellulose), cationic (chitosan) and ammonium hydroxide along with boric acid were added
anionic (k-carrageenan and sodium alginate polymers) to form rubbery products with 80 wt% urea contents.
polymers with their excellent biocompatibility when Recently, Naz and Sulaiman (2014) used a dripping solu-
blended with other classes of polymers. These and many tion technique for coating urea granules. The thickness of
other alike biopolymers such as curdlan, carboxymethyl the coated urea was ranged from 0.15 to 0.70 mm. They
cellulose (CMC), starch, calcium alginate, PLA and pectin observed that the 100% urea release takes  < 3.60 min.
are attractive for their water retention, hydrogel forma- These researchers also noticed that the overall nutrient
tion, non-cytotoxicity and complete biodegradability. In release time of the starch-coated urea was three times
fact, these biopolymers are not yet technologically effi- higher than the uncoated urea. This was due to the
cient to be used for commercialized PC-CRFs (Davidson poor mechanical strength of coated urea which strongly
and Gu 2012). In an ideal situation, biodegradation events depends on the adhesive’s composition and coating thick-
of PC-CRFs should take place after complete release of ness. Garcia et al. (1996) selected pine lignin based on its
nutrients. However, the major problem of natural poly- insolubility in water over all pH values that may occur in
mer-based materials is related to their inherently poor soil. The lignin was mixed with various types of additives
resistance to microorganisms, which initiate early events to improvize the coating for urea. A mixture embodied with
of coating biodegradation and nutrient release which the additives, dimerized, esterified and natural rosins,
minimized their intended purpose of use over the months. as well as lignin, was the most efficient for the coating
Otey et al. (1984) were the first who provided the con- process of urea. The research findings of these authors
trolled granular urea as a starch-urea matrix. This matrix also demonstrated that the efficiency of the coating prod-
was obtained by two methods: an extrusion method ucts noticeably increased further by adding linseed oil as a
and a starch and flour borate method. In the extrusion sealing agent for lignin coatings. The crushing strength of
method, urea was dissolved in potassium hydroxide and the lignin-coated urea was 59% higher than the uncoated
mixed with starch before extrusion through 1  mm diam- fertilizer. Higher crushing strength facilitates the handling
eter die to simulate 2–3 mm pellets. In the starch and flour and transportation, and reduced the water absorption.
borate method, pre-gelatinized corn starch (CS) was dis- Mulder et  al. (2011) developed lignin-based controlled-
persed into the solution of urea. Water and concentrated release coatings for urea fertilizers. They coated urea with

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
74      Z. Majeed et al.: Controlled-release fertilizer biodegradation

commercially available four types of lignin, namely two increased with temperature ( > 20°C) tested under moist
lignosulfonates (Wafex P and Borresperce, Borregaard/ soil conditions up to 24 weeks. Natural rubber’s main
lignotech, Sweden), a softwood kraft (Indulin AT, Mead constituent is poly(cis-1,4-isoprene), in which the oxida-
Westvaco, USA) and soda flax lignin (Bioplast, Granit, tive cleavage of the double bond is the main route of its
Switzerland). The latter showed the best potential with biodegradation (Rose and Steinbüchel 2005).
respect to film-forming properties. Alkenyl succinic anhy-
dride (ASA) was added to lignin dispersion as cross-linker,
and it reduced the hydrophobicity of the lignin films. The 2.2 PC-CRFs coated with mixed natural
surface of the urea granules with a lignin/ASA coating polymers
was smooth, and the number of pinholes was also low.
However, complete urea was released after  < 1 h for all for- To overcome the problem of very high nitrogen release
mulations. This is due to the low reactivity of ASA towards with single natural polymer-coated PC-CRFs, differ-
lignin, too low percentages of applied coating or negative ent researchers’ published works have produced con-
effects of the selected compounds on the lignin film. In sensus that mixing of natural polymers improved their
other work, Fernández-Pérez et al. (2008) prepared a con- biocompatibility, strengthened structure and process-
trolled-release fertilizer by mixing urea with kraft lignin ing properties. Ariyanti et  al. (2012) chemically modi-
under melting conditions. The mixture was then crushed fied the tapioca starch-urea-borate (SUB) complex
and sieved to obtain urea granules between 0.5–1, 1–2, 2–3 as a slow-release fertilizer (SRF) matrix. They added
and 3–5 mm. They reported that urea release diminished 10% kraft lignin into this matrix to improve the starch
in  < 0.5 h for all sizes of urea granules. hydrophilicity and to reduce the urea release in water. It
Chitosan, a natural polysaccharide, produced by dea- was found that lignin addition retards the urea release
cetylation of chitin, has a repeating structural unit of β- from the starch film which stayed intact for one month
(1-4)-2-amino-deoxy-β-d-glucan. In a chitosan hydrogel, after immersing in water. The starch modified with
Jamnongkan and Kaewpirom (2010a) reported potassium lignin shows high potential as a biopolymer blends for
cumulative release of 80%, which become steady in  < 10 PC-CRF applications. Another research group conducted
days. They found that the total cumulative potassium experiments on sodium alginate as an inner coating
release was lower at pH 4.1 than at 7.3 due to pH-depend- and sodium alginate-g-poly(acrylic acid-co-acrylamide)/
ent protonation of the unreacted NH2 groups of chitosan humic acid superabsorbent as an outer coating for the
during its degradation in soil. Roshanravan et  al. (2014) controlled release of organic-inorganic compound fer-
mixed urea with chitosan as a binder and found that tilizers. In these coatings, fertilizer release reached the
after 30 days, the nitrogen release decreased from 77.31% plateau in a  < 10-day period after application in soil
to 59.29% with increase in the chitosan contents. It was (Ni et  al. 2010). Fernández-Pérez et  al. (2008) reported
found that chitosan improved the crushing strength of a very high urea encapsulation efficiency of 97.18% by
urea granules. Pérez-García et  al. (2007) discussed the kraft lignin, 97.02% by EC+10% kraft lignin and 95.12%
time taken for 50% of the active ammonium nitrate release by EC+20% kraft lignin. Cumulative release percentage
into water (T50) from coated granules. They found that the was  < 4 h in uncoated urea while EC+10–20% kraft lignin
formulations which contain higher percentage of EC and prolonged it to 50  h in coated urea. Wang et  al. (2014)
bigger granule diameter (d) retard more better the nutri- successfully coated co-granulated ammonium zinc phos-
ent release. In granules (1 mm < d < 2 mm) coated with 10% phate and urea as central core with cellulose acetate
of EC without plasticizers, T50 was 7.47 h. In granules (2 butyrate as an inner coating and a carboxymethyl chi-
mm < d < 3 mm) coated with 20% of EC, T50 was high up tosan-g-poly(acrylic acid)/attapulgite superabsorbent
to 24.06 h. Plasticizers have also shown a positive effect composite as an outer coating. This material has the
on nutrient retardation due to a lower permeability of benefit that it effectively reduces N leaching and runoff
the coating. For granules prepared with dibutyl sebacate losses, improves soil moisture-retention capacity, ame-
as plasticizer, T50 was 22.80 h. For granules coated with liorates soil acidity and alkalinity while at the same time
dibutyl phthalate as plasticizer, T50 was 35.74 h. In soil, T50 biodegradability occurs in the soil solution. Wang et al.
showed a high value of 10.24 h for 1 mm < d < 2 mm gran- (2012) produced urea coated with two different polymer
ules coated with 10% of EC and 38.80 h for 1 mm < d < 2 mm coating layers. The inner coating layer was made up of
granules containing plasticizer dibutyl sebacate. In other k-carrageenan-sodium alginate, while the outer coating
studies, Hassan et  al. (1990) reported the biodegrad- composed of cross-linked kC-g-poly(acrylic acid)/celite
able urea-rubber matrix in which the release of nitrogen superabsorbent. Elemental analysis showed 22.6% urea

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
 Z. Majeed et al.: Controlled-release fertilizer biodegradation      75

encapsulation efficiency based on nitrogen contents. In compared to the pure starch/urea composite with a low
addition, the coated urea had a higher average crushing encapsulation efficiency of 53%. The grafting efficiency
strength in comparison with uncoated urea. of hydrophobic PLA could reduce the swelling proper-
ties of the starch matrix. This matrix has been found
to effectively modulate the urea release from several
2.3 P
 C-CRFs coated with nature-inspired/ hours to maximum 24 h. Peng and Chen (2011) reported
bioderived synthetic polymers a hydrogel which was synthesized after chemical
cross-linking of acetic acid lignin (AAL) with reactive
Nature-inspired synthetic polymers are composed of pre- isocyanate-terminated polyurethane ionomers (IPUI).
cursor monomers and have self-polymerization capability. Thermal stability of the hydrogel was improved after
Pdop is one of such polymers and has been very recently the introduction of lignin. Hydrogel-coated ammonium
reported in PC-CRF applications. Pdop has the excellent sulfate confirms the properties of controlled release in
capability of forming a thin, surface-adherent and multi- comparison with uncoated ammonium sulfate. When
functional layer due to a self-assembled trimer of dopa- the mass ratio of AAL to IPUI was incremented from
mine, 2/5,6-dihydroxyindole, in an aqueous solution. The 0% to 35%, it further enhanced the ammonium sulfate
repeated cycles of deposition provide better control over release.
the thickness and tuning of the biodegradation by chang-
ing the ratio of the dopamine in the film. Pioneer research
work of Jia et al. (2013) has reported a Pdop-coated double 2.5 PC-CRFs coated with mixed natural-
copper potassium pyrophosphate trihydrate fertilizer, for hydrocarbon-derived synthetic polymers
three essential plant nutrients (Cu, K and P) by sponta-
neous oxidative polymerization of dopamine. Thermo- The synthetic polymers derived from hydrocarbons,
gravimetric weight loss of Pdop linearly increased with mainly the polyalkenes, are technologically more
an increase in the number of deposition cycles, negatively advanced type of materials for coating commercial fertiliz-
correlated with the linear nutrient release both in water ers (e.g., Nutricote®, Chisso-Asahi Fertilizer Corporation,
and soil. Japan). Researchers are now more focused on replacing
PLA is a completely biodegradable, hydrophobic PC-CRFs, purely made up of synthetic polymers, with
polymer which is synthesized from the condensation natural polymers (Mulder et  al. 2011). Although natural
of two lactic acid monomers, i.e., lactic acid and lactide polymer blends with hydrocarbon-derived synthetic
(cyclic di-ester), derived from natural renewable resources polymers have been claimed biodegradable coatings for
such as CS, tapioca roots and sugarcane. Hanafi et  al. fertilizers (Ge et  al. 2002), such blends have two serious
(2000) used PLA for coating compound fertilizers (N, P, concerns. First is about the acceptable upper limit of bio-
K, Ca, Mg, Cu) with thicknesses of 2.54–2.63 mm. Polym- degradability (%) to claim the permissible extent of the
erization history, inherent properties and structure of PLA blend’s biodegradability. Second is the about the allow-
have been attributed to variation in the coated fertilizer able percentage ratio of mixing two or more polymers in a
thickness. Devassine et al. (2002) coated ammonium chlo- case where the intention is to minimize the relative propor-
ride with PLA in a fluidized bed and found that the optical tion of synthetic polymers in natural-synthetic polymer
activity of PLA does not influence the circulation of water blends to achieve the more benign biodegradability in soil
vapors through the membrane. However, PLA’s higher environment. These two problems caused delusion of the
permeability coefficient (K ≥ 4000 cm2 s-1 Pa-1) was mainly biodegradability concept when it was applied to blends
due to attached hydrophilic groups. consisting of natural and synthetic polymers.
According to the research findings of Salman (1988),
pure synthetic polymer-based coatings of polymers such
2.4 P
 C-CRFs coated with mixed natural-­ as polystyrene, polycarbonate, a copolymer of vinyl chlo-
bioderived synthetic polymers ride and vinyl acetate, poly(vinyl acetate), showed high
urea dissolution (95%) due to formation of large pin-
Chen et al. (2008) prepared encapsulated urea with the holes and film’s non-uniformity. To tackle this problem,
starch matrix modified by PLA by an in situ graft-copol- hydrocarbon-derived synthetic polymers were mixed
ymerization technique. The grafting efficiency of PLA in with natural polymers to reduce their porosity, hydro-
the starch-g-PLA/urea composite demonstrates higher phobicity and environmental destruction by microorgan-
urea encapsulation efficiency ranging from 70% to 81% isms and their enzyme-specific activities (Ge et al. 2002,

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
76      Z. Majeed et al.: Controlled-release fertilizer biodegradation

­ omaszewska and Jarosiewicz 2004). Han et  al. (2009)

T 2.6 P
 C-CRFs coated with hydrocarbon-derived
reported that the permeability of NH 4+ ions increases after synthetic biodegradable polymers
adding 10–50% of polyvinyl alcohol (PVA) in starch/PVA
blends. According to their findings, PVA has more -OH Tyliszczak et al. (2009) synthesized biodegradable supera-
groups than starch which can increase the polarity, crys- bsorbent matrices from N,N′-methylene bisacrylamide
tallinity and hydrophilicity of starch/PVA blends, mean- cross-linked acrylic acid for a slow release of a water-solu-
while the decrease of starch may affect the compatibility ble granular phosphorus fertilizer (KH2PO4). Based on the
of the blends. Tomaszewska and Jarosiewicz (2004) added fertilizer diffusion, a new concept of controlling release of
starch (0.2–2 wt%) to polysulfone (18 wt%) and applied nutrients from a biodegradable macromolecular matrix was
it as coating for water-soluble NPK fertilizers. The incre- introduced. These authors found that water-soluble nutri-
ment of starch wt% positively increased the porosity of the ents left the super absorbent matrices by diffusion through
polysulfone and its nutrient release by means of changing the formation of three distinct zones. Zone 1 referred to a
porosity. These authors did not test the starch effect on transparent gel which contained a concentrated solution
biodegradability but argued that starch addition to poly- of nutrients; Zone 2 consisted of undissolved fertilizer par-
sulfone facilitates the destruction of the polymeric coat- ticles dispersed in a gel. Zone 3 was called the dry zone.
ings in soil. Single and triple layers of polysulfone with The superabsorbent matrices showed good water-retention
0.5% starch were tested for nutrient release. Single-layer capacity, which is expected to be non-toxic in soil. Dow
polysulfone releases 65% of the ammonium ions, 48.3% Chemical Company and a partner, OPX Biotechnologies,
of phosphates and 40.3% of the potassium ions, whereas are together investigating the fermented sugars that can
triple-coating polysulfone releases only 16% of the NH 4+ produce 3-hydroxypropionic acid, an acrylic acid precur-
ions, 11.8% of phosphates and 9.3% of the potassium sor, to replace the current acrylic acid synthetic precursor
ions. Ge et  al. (2002) prepared biodegradable PU from a molecule “propene”, which is a byproduct of ethylene (en.
four-component system consisting of diisocyanate, poly- wikipedia.org/wiki/Acrylic_acid, accessed 10 Oct. 2014).
ester, Acacia mearnsii bark (BK) and CS. Ammonium Al-Zahrani (2000) produced different types of fertilizers
­
sulfate was coated with PU, and the effect of BK and CS coated either with paraffin wax or polyethylene wax, namely
amendments was tested on its release properties. When monoammonium phosphate, diammonium phosphate, NP,
CS was replaced with 10% BK in PU, the release ratio was NPK-4 and NPK-14 grades and granular triple superphos-
decreased. However, when CS was partly replaced with BK phate. It was observed in all types of these coated fertilizers
(15% BK and 15% CS), the release ratio was more effec- that the release time was almost affected double compared
tively controlled. Their findings suggested that the release to the uncoated fertilizers. Nevertheless, the polyethylene
ratio difference was due to the CS component that reduced wax was observed with longer release time than the paraffin
the opening of the cells in the PU structure during the syn- wax due to complete biodegradation of the latter in soil.
thesis. Jamnongkan and Kaewpirom (2010b) found a PVA/
CS hydrogel encapsulation efficiency of 99.96% for potas-
sium. Costa et al. (2013) coated the urea granules with PHB
and EC. The PHB and EC solution was used for coating 3 Environmental parameters
urea granules. In case of coated urea, initial dissolution
rates were found to be similar to those for uncoated urea as
affecting the biodegradability in
they were observed for only 30 s; urea dissolution was  > 50 PC-CRFs
wt% due to irregular surface morphology. Surface defects
were arisen due to the lack of interaction between the fer- Ge et  al. (2002) reported that coating disintegration is
tilizer and the polymer materials. To remove this defect, required for the release of about 15–30% of the fertilizer
PHB and cetyltrimethylammonium bromide (CTAB) were that remained unreleased from PC-CRFs due to the con-
mixed and applied as urea coating before immersion in centration gradient difference across the polymer coat-
EC solution. They found that CTAB enhanced the interac- ings. Biodegradation of PC-CRFs is a complex process that
tion between the polymers and promoted the formation of involves cascade events controlled by abiotic and biotic
more regular coatings. Therefore, CTAB effectively mini- stimuli in the environment. Macroscopic and microscopic
mized the rates of urea release in the coated granule. Like observations collectively have supported the natural
other coatings discussed above, nutrient release was not occurrence of such a chain of events in the biodegrada-
more than 5  min when urea was coated with 1.38–1.79% tion of both hydrogel-forming hydrophilic PC-CRFs and
polymer coating solution. non-hydrogel-forming hydrophobic PC-CRFs. Initial

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
 Z. Majeed et al.: Controlled-release fertilizer biodegradation      77

polymer losses could involve macroscopic changes, i.e., of polymer chains (e.g., starch). Coating polymers carrying
bulk erosion and surface erosion, that were later taken ionic functional groups more easily swell due to absorbance
over with microscopic activity of microorganisms and of water (Mikkelsen 1994). Based upon ester bond hydrolysis
their relevant machinery of biocatalysts (enzymes) for in various synthetic biodegradable polymers, Burkersroda
complete decomposition of PC-CRFs in the environment. et  al. (2002) developed a theoretical model to calculate
These events are shown in Figure 2, and the details are the values of a critical thickness (Lcritical) for a polymer that
discussed in the following sections. it must exceed in order to undergo surface erosion. If Lcriti-
In a bulk erosion, fragments are lost from the entire cal
 < 10-1 mm, a polymer shows bulk erosion mechanism, e.g.,
polymer network homogeneously as a result of MW changes polyanhydrides, polyketals, poly(orthoesters), polyacetals
due to the bond cleavage mediated by abiotic factors such and polyesters, in the range of pH 2–7.
as water, acids, bases, transition metals or by radiations In the surface erosion process, a polymer matrix over
(Burkersroda et  al. 2002, Pepic et  al. 2008). The polymer the time slowly becomes smaller and smaller but retains its
matrix size remains constant over the application time original geometric shape (Göpferich 1996) with no change
(Göpferich 1996). Bulk erosion is facilitated by ester, amide in the MW of the polymer. The absence of oxidizing groups
and anhydride bonds that are prone to slow hydrolysis but (such as -COO-, -OH and -NH2) makes the polymer surface
fast enzymatic degradation. In the process, the polymer more hydrophobic and slows down its biodegradation due
chains appeared to be degrading across the whole polymer to non-accessible carbon for microorganisms. The bacte-
matrix. As a result, degradation products accumulate and rial surface has been known to become more hydrophobic
exert osmotic pressure inside the matrix. Suddenly, it starts under such conditions that facilitate their attack on the
with many random breaks and ends with the collapse of the hydrophobic polymer surfaces (Sakharovskii et al. 1999).
whole matrix. PC-CRFs coated with starch, CMC, chitosan The examples of this phenomenon have been observed in
and PLA are expected to behave in this way. Water absorb- the biodegradation of polystyrene by the bacterium Rho-
ance coupled with hydrolytic degradation involves the dococcus ruber (C208) (Mor and Sivan 2008), polyethylene
activity of hydroxyl radicals that initiates the disintegration by R. ruber (Sivan et al. 2006) and have also assumed to

Porous Enlarged
polymer pores
Fertilizer
coating

Hollow
inner
core
Non-
CO2, H2O,
porous
Microbial
polymer
biomass
Non-hydrogel forming coating
biodegradable
PC-CRF
Functional
Swollen hydrogel Chemical
groups
network Disintegration Large pores Linkages
Pores CH4, H2O,
CO2, H2, H2S
Microbial
biomass

Swelling
Oligomers

Hydrogel forming Water Microbes Depolymerases Dimers

biodegradable Urea, NPK
PC-CRF Soil
Monomers
Lapse time
Biodeterioration
Biofragmentation
Assimilation
Mineralization

Figure 2 Hydrogel and non-hydrogel-type PC-CRF biodegradation processes in soil.

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
78      Z. Majeed et al.: Controlled-release fertilizer biodegradation

be true for cellulose-PVC blends and starch-PVC blends The details of these events involving PC-CRFs are shown
by fungus Phanaerochaete chrysosporium PV1 (Ali et  al. in Figure 2.
2009, 2014). PC-CRFs with non-hydrogel hydrophobic
surfaces have shown surface erosion, e.g., polyethylene
terephthalate-coated mineral fertilizer (N15P15K15) (Anghel 3.1 Biodeterioration
et al. 2012), PHB-coated urea (Costa et al. 2013) and poly-
anhydrides (Natarajan et al. 2014). During lapse time, PC-CRFs passed through the events
Non-hydrogel-forming hydrophobic PC-CRF surfaces of either bulk or surface erosion that creates suitable
could be porous or non-porous. According to Shaviv morphological changes and microenvironment on the
(2005), non-porous hydrophobic coatings are based on polymer surface. Such events are immediately overlapped
alkyd-type resins and thermoplastic polymers. In such with the process of biodeterioration. In biodeterioration,
coatings, water vapors penetrate through the microscopic soil microbial biomass secretes polysaccharides and pro-
pores of the coating and condense on the fertilizer core. teins that help them to adhere more firmly and penetrate
Osmotic pressure builds up inside the coating, conse- the polymer surface (Capitelli et al. 2006) of PC-CRFs. This
quently stretching the coating can enlarge the micro-pore process is eased when the pore size of a polymer coating
size. The process further facilitates the fertilizer release by is increased, which facilitates the contact of microorgan-
diffusion driven by a concentration gradient or mass flow isms with the polymer surface area. Fungi are known for
driven by a pressure gradient, or by a combination of the the formation of filamentous growth on the biodegraded
two. To increase the permeability of these coatings, ethyl- polymers especially due to their unique morphology.
ene-vinyl acetate and other types of surfactants are also Hyphae-like structures develop a mycelia network, which
added into polyolefin-coated CRF (Nutricote®) (Jacobs penetrates into the polymer structure, changes it into
et al. 2003). For porous hydrophobic coatings such as EC, more brittle character and provokes cracks or fragmenta-
Gurny et  al. (1982) described that dissolution and diffu- tion (Bonhomme et al. 2003). After physical contact with a
sion are the two prevailing mechanisms of solute release polymer, chemical processes start to take over the polymer
into the water-filled pores. In a dissolution phase, solute surface. The extracellular moieties are produced by micro-
concentration becomes low enough so that it can dissolve organisms that act as biosurfactants, and play the main
in the water-filled pores below its saturation concentra- role in facilitating the exchange between hydrophilic and
tion. Further release is diffusion controlled. Finally, as hydrophobic phases. Palmitate iron carboxylate-Fe(III)
the solute is almost totally depleted, major changes of hydroxide is a surfactant that has increased the biodeg-
the void fraction and porosity may lead to a considerable radation of polyethylene under the soil environment
increase in the release rate. The swelling and shrinking (Karlsson et  al. 1988). Each kind of microbial flora that
events can produce cracks or interstices that promote the has been developed on the polymer surface can contrib-
surface erosion event on the surface of PC-CRFs. At the ute to the specific chemical reaction of biodeterioration.
end of nutrient release, coatings are left behind in the soil Progressive biodegradation changes the microstructure of
with some low concentration of nutrients due to the differ- the polymer that coincides with the event of pore forma-
ence in the concentration gradient, which release through tion. pH inside these pores is modified by the degradation
the biochemical disintegration process. products, which normally have some acid-base character-
Erosion events driven by abiotic factors (pH, water, istics (­Göpferich 1996).
and photo-oxidation, etc.) could further prepare the
polymer surface for fast attack of microorganisms. Lucas
et al. (2008) described three stages involved in the biodeg- 3.2 Biofragmentation
radation of biodegradable polymers: (a) biodeterioration,
(b) biofragmentation (disintegration) and (c) assimila- During biofragmentation, chemical bonds present within
tion. These authors, however, did not give attention to the polymer chain are hydrolyzed by depolymerases
the fourth stage (d) mineralization as it corresponds to either naturally present in soil or secreted freshly by living
aerobic or anaerobic microorganisms maximum activity. microorganisms or the product of their cell lysis. High-MW
These four steps together constitute “microscopic” epi- polymer chains are converted into low-MW byproducts.
sodes that are the sole outcome of microorganisms’ action Endopeptidase and endoesterases accomplish the cata-
and their enzyme activities in soil. This understanding lytic action along the polymer chain, whereas exoenzymes
can be extended to explain biodegradation of the materi- catalyze reactions principally working at either end of
als used in PC-CRF that are already discussed in Section 2. each chain. Bacillus sp. PG01 as a phosphate-solubilizing

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
 Z. Majeed et al.: Controlled-release fertilizer biodegradation      79

bacterium was coated with poly butylene succinate) 3.4 Mineralization

(PBSU)/starch and acrylic acid grafted PBSU/starch
(PBSU-g-AA)/starch. These blends could be hydrolyzed by Mineralization of polymers is the outcome of microbial
Rhizopus delemar lipase in addition to the endo- and exo- respiration activity on the polymer and yields carbon
hydrolysis action of amylases and lysozyme (Bikiaris et al. dioxide and water under aerobic conditions, and methane
2006, Chin-San 2008). Starch-g-PLA-coated urea (Chen and carbon dioxide under anaerobic conditions as the
et al. 2008) could be susceptible to amylases and protein- major end products of the process. Polymers are rich
ase K. Chitosan is another modified biopolymer that could source of carbon that could itself act as a strong ­electron
be biodegraded by endochitinase, N-acetyglucosamini- donor (Sutton-Grier et  al. 2011) to a variety of electron
dase (Rodriguez-Kabana et  al. 1983, Parham and Deng acceptors which facilitates the microorganisms to gain
2000, Wu and Liu 2008, Jamnongkan and Kaewpirom energy at the cellular level from the mineralization of a
2010b). polymer. If the anaerobic microorganisms have the appro-
Biodegradation was observed for the superabsorbent priate enzyme systems, only then they can use either elec-
type of cross-linked water-insoluble polymers composed tron acceptor (Stevens 2002) to acquire energy during the
of polyacrylate and its copolymer with polyacrylamide polymer biodegradation. Under anaerobic soil conditions,
after buried under the soil. The soil microbes cooperate mineralization of SRF matrix showed that increase of kraft
with each other for the complete decomposition of the lignin from 5 to 20 wt% reduced the percentage minerali-
superabsorbent. It is known that fungi solubilized the zation over the period of 63 days (Majeed et al. 2015).
poly­mer while microbes stimulated the polymer’s min- In Figure 3, the details of the microbial and enzyme-
eralization. However, soil microbes were able to signifi- driven processes of PC-CRF biodegradation and nutrient
cantly mineralize both polymers once solubilization was release are given in the perspective of aerobic and anaer-
completed by fungal peroxidase or cellobiose dehydro- obic soil conditions where they are applied in practice.
genase secreted by white rot fungus, P. chrysosporium, PC-CRFs are more easily biodegraded in aerobic soil as O2
in addition to the action of a photochemically generated is the strong terminal electron acceptor. Under anaerobic
Fenton reagent (solution of hydrogen peroxide and iron) conditions, the rate of biodegradation is usually limited by
(Stahl et al. 2000). Poly[(R,S)-3-hydroxybutyrate], a-PHB, weak terminal electron acceptors such as nitrate ( NO3- ),
form binary blends with natural PHB (n-PHB) and poly-(l- ferric iron (Fe3+), manganese (Mn3+ and Mn4+), bicarbonate
lactic acid) (PLLA). The biodegradation of a-PHB-con- ( HCO3- ) and sulfate ( SO42-). Under a natural environment,
taining binary blends proceeded faster than that of plain PC-CRFs can also serve as a complete and balanced source
n-PHB and PLLA in natural soil. The decrease of MW in of carbon, nitrogen and other encapsulated nutrients that
the n-PHB component was high (Rychter et al. 2006). could activate the dormant microbial community during
the period of nutrient deficiency. Constitutive enzymes are
synthesized by microorganisms during their whole cellular
3.3 Assimilation life mainly for the purpose of maintaining the cell process
or structure. Such enzymes do not n ­ ecessarily contribute
The assimilation represents the process where low-MW to the degradation of a particular substrate, but specific
products of polymer biodegradation are taken up by the enough to catalyze the degradation of its target substrate
microorganisms from the outer environment as an organic in a mixture of different substrate matrices. Soil microbial
source of energy to maintain their growth and also to biomass also produces inducible enzymes only when a
reproduce new microbial biomass. The assimilation initi- specific biodegradable substrate is added into the environ-
ated parallel during the early phases of biodeterioration ment. Such enzyme activity degrades the polymeric sub-
would have now become more pronounced as the biof- strate and then soil microorganisms obtain food and energy
ragmentation gradually taken over the biodeterioration for their growth and reproduction. Recently, Allison et al.
(Figure 2). At the end of biofragmention, microbial assimi- (2014) mixed seven polymeric substrates, including starch,
lation regression is assumed to follow resource allocation lignin, cellulose, chitin and xylan, into the soil and studied
hypothesis which posits that decomposition rates should the constrain imposed by these the single and mixed sub-
increase once substrate concentrations are sufficient to strate concentration on microbial decomposition in soil.
overcome biochemical investment costs and opposite is Their finding showed that the cost of biochemical machin-
true that the costs of biochemical machinery limit micro- ery limits microbial decomposition of a substrate at low
bial decomposition of substrates at low concentration concentration. The presence of enzymes with low substrate
(Allison et al. 2014). specificity was not sufficient to overcome this constraint

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
80      Z. Majeed et al.: Controlled-release fertilizer biodegradation

Terminal electron acceptors

SO42-, NO3-, Mn4+, O2
HCO3-, Fe3+ (Aerobic soil) NH3 N2O, N2
(Anaerobic soil)
Co-metabolism
Nitrogen NH4+ Plants
Soil Substrate sensing
Microorganisms

coated polymer
Controlled by

Controlled by
nitrification inhibitor
EEs (Natural or synthetic)
+/- feedback
mechanism 1. Constitutive
2. Inducible NO2-
3. Cell bound Biodegradable O2-
Lysis PC-CRF
4. Clay
adsorbed NO3-
Controlled by
denitrification inhibitor
(Natural or synthetic)
O2 deficient condition
Low Mw
Unfavorable products
environment
Carbon Leaching,
run off
SOM = Soil organic matter
EEs Degrade,
DOM = Dissolved organic matter
EEs= Extracellular enzymes Denature,
Inactivate SOM DOM

Figure 3 In situ PC-CRF biodegradation interactive dynamic pathways in soil.

for some substrates. The activities of β-glucosidase and inherently more stable in harsh environment as they are
N-acetyl-glucosaminidase that target cellulose and chitin, glycosylated and have disulfide bond, which provide ther-
respectively, were found significantly low under modest mostability, a broad pH range for activity and some resist-
concentrations of their target substrates. Some enzymes, ance against protease (Burns 2010). Non-desorbed enzymes
such as β-xylosidase, were consistent with specialist strate- which are soluble in soil aqueous phase biodegrade more
gies because they showed the highest activity in the presence easily, despite the fact that they stabilize through interac-
of their target substrate. Other enzymes such as polyphenol tion with the clay mineral and humic acid (Allison 2006).
oxidase, peroxidase, α-1,4-glucosidase, cellobiohydrolase, EEs can also be inactivated or denatured during the natural
acid phosphatase and leucine amino peptidase were more decomposition process. Ultimately, PC-CRF biodegradation
generalist, as their activity was observed across multiple increases the soil fertility by increasing soil organic carbon
substrates. In fact, cellular metabolism of microorganisms pool while 15–30% trapped fertilizer could also be released.
and extracellular depolymerization by enzymes normally After soil contact, biodegradation of PC-CRFs and
operate simultaneously in soil but are difficult to separate release of nutrients are fully controlled by a synergistic
with currently available assays (Blankinship et  al. 2014). triad as highlighted in Figure 4. Many physical, chemical
According to Burns et al. (2013), soil extracellular enzymes and biological factors of the soil govern the final fate of
(EEs) could exist either on the outer surface of alive micro- PC-CRFs. Nie et al. (2004) showed that biodegradability of
bial cells, or attached to the entire dead microbial cells a CMC hydrogel in sandy, damp and viscous soil is a func-
or their debris or disperse free in soil water. Absorption, tion of the difference in soil properties like water holding
entrapment and copolymerization of EEs on organic matter capacity (WHC), aeration and particle size. The bigger
or other organic substrates in soil and adsorption to the holes in sandy soil were assumed to favor high oxygen
external and internal surfaces of the clay minerals are few circulation and enhanced the activities of microorganisms
of the natural pathways that determine their role in natural against CMC. According to Karamanlioglu and Robson
substrate biodegradation events. When these EEs come in (2013) observations, PLA biodegradation rates were much
contact with PC-CRFs, low-MW compounds are released as faster in microorganism-rich compost and soil conditions
oligomers, dimers and monomers that are easily taken up than in sterile water at two temperatures 45 and 50°C. The
by microorganisms. As the substrate biodegrades, it sends decrease in both tensile strength and MW was faster after
signal positive or negative to microorganisms for the feed- 30 and 36 days in microorganism-rich compost and soil,
back to modulate the synthesis of EEs. Adsorbed EEs on respectively. However, the change in these parameters was
the soil clay particle may longer their availability. EEs are slow in sterile compost and soil extract and took 57 and 54

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
 Z. Majeed et al.: Controlled-release fertilizer biodegradation      81

that ultimately determine the biochemical hydrolysis are

the functional groups attached to the polymer backbone,
position and type of chemical linkages. In these perspec-
tives, the current literature review presents the great vari-
ation in design and choice of the polymer with different

Ph il tex re
structural properties that impart variation in the PC-CRF
s
tor

ysi
al
nti

So
fac

ity

ca ure
biodegradation. In Table 2, various coating polymers and

Te
ote

ac

l fa
mp
al
xp

ap
c

Mo
their modifications are cited from the literature which

c to
era

t
ec
i
do

PH
em

ist
ng

t
Re

rs
u
Ch

provide comprehensive comparison of the conditions

ure
ha
xc

PC-CRF
ne

and techniques applied for the assessment of PC-CRFs

tio
Ca

biodegradation in the environment. Few of the important

Inhibitory substrates material properties affecting the biodegradation critically
Enzymes
discussed in the following sections.
Microorganisms

Biological factors

Figure 4 A synergistic triad of environmental control of PC-CRF 4.1 Microbial susceptibility
biodegradation in soil (the order of the parameters does not present
any specific priority). According to the “Probabio” concept, biodegradability is
not an intrinsic property of a material but actually is deter-
days, respectively. Another study, using CO2 as a measure mined by the specific degrader activity on the substrates
of starch removal from films [40% starch, 25% polyethyl- in the testing environment (Thouand et al. 2011) reflected
ene, 25% poly(ethylene-co-acrylic acid) mixed with 10% by the chemical bonds or functional groups susceptibil-
urea], showed the fastest removal of starch in sandy soil ity and hence the actual mode of biodegradation. PU-like
compared to clay loam soil (Wool and Cole 1988). coating fertilizers (Multicote product of Haifa Chemical
Ltd., Israel) (Du et al. 2006) are biodegraded by different
species of fungi and bacteria that secrete specific enzyme

4 M
 aterial properties affecting the “polyurethanase” that are efficient to attack polyester
segment and cleavage of ester bonds (Nakajima-Kambe
biodegradability in PC-CRFs et al. 1999). After the 4-week soil burial test, the polydis-
persity index of biodegraded PU was increased from 1.369
Since 1994, many new materials from natural renew- (control) to 1.760 (sample) whereas MW decreased from
able resources have been mixed with synthetic polymers 50,161 g/mol (control) to 49,684 g/mol (sample) with the
to make coatings more acceptable as biodegradable (Ge release of non-toxic byproducts, 1,4-butandiol and adipic
et al. 1998, Tomaszewska and Jarosiewicz 2004, Han et al. acid Shah et al. (2013). In recent work, a fungus, Pestaloti-
2009). Many physical, chemical and biological modifica- opsis microspora, has been identified that secretes serine
tions of PC-CRFs are responsible for predicting the process hydrolase which is an extracellular, diffusible enzyme
of biodegradation. These properties ultimately influence capable of biodegrading PU under both aerobic and anaer-
the controlled release of nutrients in soil. Physical prop- obic conditions over a short period of 1  h (Russell et  al.
erties include the coating thickness (Shogren et al. 2003, 2011). One disadvantage of PU-based coatings is that they
Majeed et al. 2014b), polymer concentration and porosity release ammonia after decomposition of ureathane units.
(Tomaszewska and Jarosiewicz 2002), type of organic/ Basidiomycota fungi species, Lentinus edodes, Naemato-
inorganic/natural or synthetic fillers (Majeed et al. 2014a), loma sublateritium, Pleurotus ostreatus and Flammulina
source of coating materials (Salman 1988, Devassine et al. velutipes, degrades the lignin-glutaraldehyde (GA) gel
2002), type and parentages of grafted polymers (Nikolic completely into liquid after 11 months. It was anticipated
et al. 2014), mass ratio of cross-link molecules (Nie et al. that fungus secreted lignin peroxidases specifically recog-
2004), and amount and type of fertilizers (particle size nized the lignin-GA gels as substrates and digest the β-O-4
and charge) (Tomaszewska et al. 2002, Nie et al. 2004). The linkage of the aryl ether or the methylene bridge between
chemical modifications affecting the biodegradable poly- free phenolic groups, or the cross-linking bridge devel-
mers are the ionic charges (Nikolic et al. 2014), chemical oped between hydroxyl groups of GA units (Yamamoto
linkages dispersed within the backbone of polymer, degree et  al. 2000). Guo et  al. (2006) studied the biodegrada-
of polymerization and crystallinity. Biological attributes tion process of urea-formaldehyde (UF) coated with a

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
 Table 2 PC-CRF biodegradation in different media and techniques for assessment.

Coating polymer type Polymer class Biodegr-adability Conditions Technique/Criteria Reported results Reference

Polyurethane (PU) Synthetic Partial Soil and water, Fourier transform infrared Soil microorganisms caused more fast Wu (2011)
28 days (FTIR) degradation in soil compared to water
Polydopamine (Pdop) Synthetic Complete Soil 30% WHC, % weight loss Faster biodegradation in non-sterilized Jia et al. (2013)
18 days than in sterilized soil. Film collapse, metal
ions and microorganisms promoted the
biodegradation
Biodegradable PU Synthetic/ Partial Soil, FTIR, scanning electron CS increased biodegradation of PU. Ge et al. (2002)
(diisocyanate, polyester, natural (mixed) humidity (37–92%), microscopy (SEM), Bonds, C-O-C and C-O-H, in both hard
Acacia mearnsi bark (BK) 20–35°C, % weight loss and soft segments showed changes for
and corn starch (CS) 6–12 months damaged PU due to soil microorganisms
Natural rubber-g-modified Natural Complete Specimen (2 × 2 cm) was % weight loss Biodegradation of NR-g-ST dramatically Riyajan et al.
starch (NR-g-ST) buried under soil (100 increased with the increase of the ST (2012)
g) at 7 cm from top soil, contents. ST was greatly degraded by
ambient conditions, 3 bacteria and fungi in soil activated by
weeks moisture and heat
Alginate microbeads Natural Complete Samples buried 5 cm Stereoscopic microscopy Presence of bacterium, Azospirillum Bashan et al.
below the soil surface brasilense and skim milk in the alginate (2002)
in the natural soil, 30°C, microbeads caused degradation index
15 days above 1.0
82      Z. Majeed et al.: Controlled-release fertilizer biodegradation

Angemeldet
0 = no biodegradation; 1 = little
biodegradation with small holes and
deformations in the bead structure
2 = completely biodegraded

Bereitgestellt von | De Gruyter / TCS

Heruntergeladen am | 10.02.15 18:11

Polycaprolactone (PCL) Synthetic Partial Saline solution (0.85% Time course growth After 60 days, weight loss in PCL (30%) Wu et al. (2007)
and its composites (with NaCl), 30°C, 60 days analysis by SEM images was found to be low in comparison to
starch and/or clay) PCL/starch composite (60%). Addition of
clay reduced the biodegradation in the
following order: PCL/starch > PCL/starch/
clay > PCL > PCL/clay
Chitosan Synthetic Complete Moisture content ∼50%, Time course, weight loss, Chitosan 0.1–0.3% loading increased Hamid et al.
(modified from ambient conditions, 20 FTIR, differential scanning biodegradation. Samples become brittle (2013)
chitin) days calorimetry (DSC), visual and reduce in size. Melting temperature
observations (Tm) and total enthalpy (ΔH) decreased
due to the degradation of the amorphous
phase but the difference in these values
was non-significant among different
chitosan loading percentages
 (Table 2 Continued)

Coating polymer type Polymer class Biodegr-adability Conditions Technique/Criteria Reported results Reference

Ethylcellulose (EC) Synthetic Partial, slow Thickness 25–45 μm, DSC EC glass transition temperature decreased Ni et al. (2009)
(modified from buried 100 mm beneath from 140.8°C on the 30th day, to 139.5°C
cellulose) the surface of the on the 60th day and finally to 136.0°C on
soil, 30 wt% water the 90th day, respectively; decrease of
holding capacity, room the softening point at about 180°C. Partial
temperature. Incubated destruction of intra- and intermolecular
for 0, 30, 60 and 90 days hydrogen bonds in the crystal zone of EC
by the action of soil microorganisms
Starch/ Synthetic/ Partial Films (3 × 3 cm) buried in % weight loss Specimens appeared brittle, fragile and Han et al. (2009)
PVA natural (mixed) an agricultural soil in a diminished in size when weight loss
pot, ambient conditions, exceeded 50%
50 days
Starch/PVA/ Synthetic/ Partial Diameter 10 mm and Visual observation,% Films appeared brittle, fragile and Lum et al. (2013)
glycerol natural (mixed) 5±1 thickness buried weight loss, DSC diminished in size rapidly in the initial
in agricultural soil in 20 days; the composite film showed less
a beaker, ambient biodegradation. Composites showed
conditions, 30 days 13–47% weight loss. The greater the
concentration of PVA in a composite
film, the higher the resistance against
biodegradation

Angemeldet
Polyethylene/paraffin Synthetic/ Partial, slow – – – Al-Zahrani (2000)
natural (mixed)
Polyethylene Synthetic Very slow Sandy and wet soil, Visual observations The coating film for PCU is quite stable Salman et al.
temperature 25°C and and is not affected by temperature or (1989)

Bereitgestellt von | De Gruyter / TCS

Heruntergeladen am | 10.02.15 18:11

45°C, 7–9 weeks microbial activity
Poly(butylene succinate Synthetic Complete, fast Burkholderia cepacia, Time course recording of PBSA surface erosion, cracking, 45% Wu (2010)
adipate) grafted maleic (mixed) sterile saline colony-forming units (CFU), weight loss in 60 days. In PBSA-g-MA
anhydride (PBSA-g-MA) solution (0.85% NaCl) gel permeation more abundant growth, large pores, 82%
with an initial pH of 7.0 chromatography (GPC) weight loss after 60 days
and incubated at 37°C,
60 days
Soy protein isolate/ Natural/ Complete, fast ASTM D-6400-04 % weight loss, SEM Decrease in the residual mass as a Calabria et al.
poly(lactic acid) blends synthetic standard (6400-04-99, function of time was faster for unloaded (2012)
plasticized with triacetin (mixed) 1993). 0.3 × 10 × 10 matrix SPI/PLA-TA than for composite
(SPI/PLA-TA) mm, maintained at material SPI/PLA-TA-NPK, suggesting that
32±2°C and 80% relative the NPK salts delay the biodegradation
humidity in soil, 45 days process; SEM showed NPK-containing
samples featuring a more eroded/
degraded surface
Z. Majeed et al.: Controlled-release fertilizer biodegradation      83
84      Z. Majeed et al.: Controlled-release fertilizer biodegradation

UF granule In a polysulfone-coated NPK fertilizer, the release

rate of nutrients from coated granules was observed to
decrease with the decrease of the coating porosity. Surface
of PC-CRFs with 38.5% porosity, prepared from 13.5% poly­
Soil UF+U+A sulfone solution showed release of 100% of NH 4+ in water
micro-organism solution
after 5  h test, whereas only 19.0% of NH 4+ was released
after the same time for the coating bear 11% porosity
UF+U+A
(Tomaszewska and ­Jarosiewicz 2002). Afterward, these
U: urea authors (Tomaszewska and Jarosiewicz 2004) mixed poly-
Coating materials A: Ammonia
sulfone with starch (0.2–2 wt%) filler with the intention
Soil of affecting its biodegradability in natural environments.
Polysulfone solutions with higher starch concentration
Figure 5 Microorganism-assisted release of insoluble part of
became more porous, namely the porosity changed from
urea-formaldehyde. [Adopted from Guo et al. (2006), with copyright
permission 2014 from John Wiley and Sons.]
46.7% to 63.7%. The structure of a triple coating was more
compact and the porosity decreased almost twofold in
comparison with the single coating (Tomaszewska and
superabsorbent polymer [poly(ammonium-acrylate)] in
Jarosiewicz 2004). However, direct studies of the poros-
soil. Soil microorganisms penetrate through the outer
ity effect on PC-CRF biodegradation are missing, but
swollen coatings and assembled around the central core
evidence from the PHB membrane showed that higher
of UF. Microorganisms initiate biodegradation of UF and
porosity is linked to its faster degradation (Liu et al. 2014).
therefore urea and ammonia compounds are released into
the soil (Figure 5).

4.3 Polymer blend/composite composition

4.2 Porosity
Additives such as starch, cellulose and lignin enhanced
The porosity is a unique property of a polymer and its the biodegradability of both natural-natural and natural-
process to coat the PC-CRFs. It has been reported for synthetic PC-CRFs (Ge et  al. 1998, Liang and Liu 2006,
completely biodegradable rosin-paraffin wax-modified Majeed et  al. 2014a). In mixed blends of starch/poly­
PC-CRFs that the concentration of fertilizer, contents sulfone (Tomaszewska and Jarosiewicz 2004), starch/PVA
of the modified rosins (wt%) and particle size (μm) are (Han et al. 2009), starch/PU (Ge et al. 2002) and EC/PHB
inversely related to the coating pore size (Kakoulides and (Costa et al. 2013), the biodegradability of more resistant
Valkanas 1994). Earlier, an ammonium sulfate fertilizer synthetic counterpart was improved. For example, lignin
coated by PU mixed with BK showed the expansion of the improved the biodegradability of a PU-based hydrogel,
multicell structure of PU and its damage after contact with while the PU chain enhanced the strength of a lignin-
soil microorganisms as shown in Figure 6 (Ge et al. 2002). based hydrogel for coating of ammonium sulfate (Peng

A B C

Figure 6 SEM photographs of BK-PU after different periods of soil microorganism treatment: (A) 0 months (100 × ), (B) 6 months (100 × ) and
(C) 12 months (100 × ). [Adopted from Ge et al. (2002), with copyright permission 2014 from John Wiley and Sons.]

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
 Z. Majeed et al.: Controlled-release fertilizer biodegradation      85

and Chen 2011). In polystyrene-g-starch samples, 37% cepacia isolate) encapsulated in maleic anhydride (MA)
degradation was reported over 160 days after incubation was grafted onto Poly(butylene succinate adipate) (PBSA).
with soil media (Singh and Sharma 2007). The longevity of PBSA amalgamated with 20 wt% starch enhanced the bio-
nutrient release for lignin, cellulose or starch-coated fer- degradability of the composite and facilitated the release
tilizers is too short, normally  < 30 days (Jamnongkan and of the entrapped cells into the environment (Wu 2010).
Kaewpirom 2010a, Mulder et al. 2011). Different polymer Nikolic et al. (2014) figured out a significant negative cor-
blends/composites prepared from natural and synthetic relation between the share of polystyrene in its copolymer
sources (Section 3) showed an obvious difference in their with starch and the degree of biodegradation. Grafting of
biodegradation due to the variation of microbial suscep- polystyrene on starch (55–93%) prevented the latter com-
tibility, new chemical linkages and structural configura- plete biodegradation, while the addition of polystyrene
tions. In PC-CRFs, coating with different combinations of (37–77%) retarded the biodegradation of the degradable
polymers is another way to achieve desired control over part of copolymers in different soil samples.
the process of biodegradation. In starch/PVA/glycerol- In polymeric composites, natural fillers are usually
encapsulated urea, mixing of PVA 0.5 g, 0.75 g and 1.0 g used to reduce the cost and increase the strength
reduced the composite weigh loss in the soil burial test (­
Teegarden 2004). This trend is also very common to
(Lum et  al. 2013). For these composites, enthalpy was modify the compositions prior to the coating of PC-CRFs.
decreased and the loss of amorphous phase also disrupted Peanut shell powder (PSP) and coconut shell powder
the crystalline regions. From the detailed mechanistic (CSP) at 10 and 40 phr (parts per hundred part of rubber)
study, these authors showed that the hydrolysis of starch were investigated for the effect of filler’s chemical treat-
takes place first, together with consumption of a part of ment, particle size and loading percentages on the bio-
the amorphous phase of PVA. The crystalline regions of degradation of natural rubber composites (Sareena et al.
PVA after biodegradation, in fact, contributed to a higher 2014). Chemical treatment with 10% NaOH reduced the
value of enthalpy. Kim and Lee (2002) conducted research availability of the hydrophilic center of CSP and PSP. The
on biodegradation of starch-filled low-density polyethyl- rubber matrix consisting of these fillers attributed more
ene (LDPE) and observed cross-linked starch distributed resistance of the composites to decomposition in soil
homogeneously throughout the LDPE. The starch distri- environment. An untreated filler in the range of 0–45 μm
bution improved the LDPE contact with microorganisms and 45–90 μm showed the higher percentage loss for
and reduced the hydrophobicity that favored more partial the parameters; weight loss, elongation at break, tensile
biodegradation. strength and hardness compared to pure natural rubber
When PLA and PLA-co-PET copolymer (polylactic over 6 months’ contact with soil. The SRF matrix com-
acid copolymerized polyethylene terephthalate) were posed of SUB was blended with 10% kraft lignin and it
used as separate coatings, the release was single step showed improvement in hydrophilicity of SUB matrix (Ari-
mainly by hydrolytic degradation. When coating was yanti et  al. 2012). Majeed et  al. (2014a) findings showed
made up of PLA/PLA-co-PET blends, in the first step, the kraft lignin with 5, 10, 15 and 20% reduced the SRF weight
initial release of urea was due to pore formation and after loss ∼20–80% compared to the SRF received no lignin
that, in the second step, the encapsulating structure was (control) with high weight loss ∼70–90% over the initial
collapsed as a result of hydrolytic degradation (Kordach period of 10  days under wet soil microcosm (Figure 7).
2009). Esterases and cutinases are two enzymes that also They concluded that lignin hydrophobic and recalcitrant
biodegrade the PET (Shah et al. 2014). Mousavioun et al. properties supposedly reduced the starch hydrophilic
(2012) provided evidence of biodegradation inhibition character in SRF that protected it from soil microorgan-
in PHB after mixing the bagasse lignin during the in situ isms. Figure 8 shows that filler BK increased the weight
biodegradation test performed in soil. They observed sig- loss of PU-coated urea, but change was more significant
nificant surface roughness in PHB films with the growth of when BK and CS were used together.
both loosely and strongly associated microorganisms. The
presence of lignin inhibited the colonization of microor-
ganisms due to more resistance of blends towards micro- 4.4 Types of cross-linkers
bial attack. FTIR analysis suggested that lignin formed
strong hydrogen bonds with PHB in the buried samples In hydrogel-forming hydrophilic PC-CRFs, the type and
and it was likely that the rate of breakdown of PHB was extent of cross-linking are very important in the forma-
reduced, and also prevented rapid degradation of the tion of a uniform network structure, increasing MW,
blends. A phosphate-solubilizing bacterium (Burkholderia and improving chemical structure, polymer–polymer

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
86      Z. Majeed et al.: Controlled-release fertilizer biodegradation

100 0% lignin 5% lignin 10% lignin 15% lignin 20% lignin

90
80
Weight loss (%)

70
60
50 SRF
40 SRF 5% lignin Before biodegradation
30 SRF 10% lignin
20 SRF 15% lignin
10 SRF 20% lignin
0
1 2 4 10 14 21 28
Time (days) After biodegradation

Figure 7 Effect of different lignin percentages on biodegradability of slow release fertilizer (SRF) matrix evaluated by weight loss (left) and
visual observations (right) after 28 days in wet soil (60% WHC) under ambient soil conditions. [Adopted from Majeed et al., 2014a, with
copyright permission 2014 from Trans Tech Publications).]

20 oxide showed the lowest weight loss compared with for-

E maldehyde and epichlorohydrin (Maiti et al. 2012). Table 3
D
15 C shows the comparison of cross-linker properties for the
polymers that have been reported for PC-CRFs.
Weight loss (%)

10 B

5 Biodegradation kinetic models

5
Most common and well-studied models for microbial
growth and substrate decomposition are based on fre-
A
0
0 2 4 6 quently applied two fundamental empirical models. One
Time (months) is Monod model which specifically described the micro-
bial growth on a substrate and other is Michaelis-Menten
Figure 8 Effect of the soil microorganism treatment on the weight
loss of PU foams: (A) 0% BK in PU (with 20% trimethyl-olpropane), (M-M) model to predict the enzyme-substrate kinetics.
(B) 10% BK in PU, (C) 20% BK in PU, (D) 30% BK in PU and (E) 15% During polymer biodegradation, microbial growth and
BK and 15% CS in PU. [Adopted from Ge et al. (2002), with copyright enzymes activities are two mutually exclusive but inter-
permission 2014 from John Wiley and Sons.] dependent essential processes that should be considered
together in any biodegradation kinetic analysis. In the lit-
compatibility, thermal properties, rigidity, water vapor erature, rarely both types of kinetic approaches are taken
permeation and moisture absorption (Dušek and into account for the detailed findings of the impact of
Dušková-Smrčková 2000, Zhao et  al. 2010). These modi- biodegradation on polymer coating in PC-CRFs. In Monod
fications ultimately vary the degree of biodegradation of and M-M models, maximum rate change and the substrate
coated polymers. In starch/PVA films (Han et  al. 2009), saturation constants are derived from biodegradable sub-
10 wt% formaldehyde as cross-linker showed 50% weight strate concentration by non-linear curve fitting. Due to
loss of film after 50  days of biodegradation test under these two kinetic models interrelationship, here are dis-
composting conditions. Junejo et al. (2011) coated the urea cussed below Monod model together with M-M model.
with the gelatin. Chiou et al. (2008) cross-linked gelatin,
derived from animal resources (pollock and salmon), with
0, 0.25, 0.5 and 0.75 wt% GA for its effect on film biodegra- 5.1 Michaelis-Menten kinetics
dation. Biodegradation of cross-linked film with 0.50 and
0.75 wt% GA was faster than other samples. Starch/PVA Mukai et al. (1993) applied the M-M model for the study of
film cross-linked with borax, zinc oxide, formaldehyde the mechanism of degradation kinetics on the surface of
and epichlorohydrin showed that weight loss decreased poly[(R)-3-hydroxybutyrate] [P(R)-3HB] film by extracellular
initially fast and later it slows down for all types of cross- poly(hydroxyalkanoate) (PHA) depolymerase from various
linkers. However, cross-linked film with borax and zinc microorganisms, Alcaligenes faecalis, Pseudomonas pickettii

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
 Z. Majeed et al.: Controlled-release fertilizer biodegradation      87

Table 3 Type of cross-linkers for PC-CRFs and their environment hazards.

Cross-linker Source Coating system Remarks Reference

Formaldehyde Synthetic Starch/PVA Biodegradable, toxic Han et al. (2009)

Glutaraldehyde Synthetic Gelatin Biodegradable, toxic Chiou et al. (2008)
Calcium chloride (CaCl2) Natural/ Sodium alginate Environmental Guo et al. (2005)
synthetic friendly, non-toxic
N,N′-methylene Synthetic Wheat straw-g- Biodegradable, Abraham et al. (1996),
bisacrylamide (NNMBA) poly(acrylic acid)/ less toxic Liang and Liu (2006),
attapulgite (CMWS-g- Tyliszczak et al. (2009),
PAA/APT) Xie et al. (2011)
Divinylbenzene (DVB)/ Synthetic Acrylamide Slowly biodegrade in Abraham et al. (1996)
tetraethyleneglycol diacrylate copolymers environment, harmful
(TTEGDA) or pentaerythritol
triacrylate (PETA)
Aziridine Synthetic Acrylate latex Irritant, toxic and Zhao et al. (2010)
mutagen
Genipin Natural Chitosan Natural, less cytotoxic Hussain et al. (2012)
than glutaraldehyde

and Comamonas testosteroni, in potassium phosphate buffer Modelli et al. (1999) also maintained the view that bio-
(pH 7.4). The enzyme kinetic data were accounted for a het- degradation products (low-mass polymer fragment) were
erogeneous enzymatic reaction on the surface of P[(R)-3HB] rapidly and irreversibly oxidized to CO2 by microorgan-
film via two steps of adsorption and hydrolysis, which cata- isms, and this was assumed to be the fourth step of the
lyzed by PHA depolymerase binding and catalytic domains. M-M equation but could not be expressed in the M-M equa-
According to their findings, the properties of the enzyme’s tion. Polymer biodegradation systems were independent
catalytic domains were very similar among the three PHA of initial rates and the substrate concentration [S] (active
depolymerases, but those of the binding domains were sites of the polymer per unit surface) that remained con-
strongly dependent on the sources of depolymerases. stant during the course of reaction if the enzyme concen-
According to Modelli et al. (1999), until 1999, detailed kinetic tration ϑ (mol A-1 t-1) on the polymer surface also remained
studies for a heterogeneous complex system like polymer- constant as shown in the following equations:
soil microorganisms were not reported. In our view, appli-
d [ CO2 ] k [E] [S]
cations of such studies are still limited for polymers, but ϑ( mol A-1t -1 ) = =  k2 [ ES ] =   2   o (3)
dt K +  [S] 
almost none are reported for PC-CRFs. These authors used
ASTM D-5988-96 test method to determine the aerobic bio-
degradation kinetics of natural poly(3-hydroxybutyrate) V ( mol t -1 ) =  ϑ  x  A = const.x  A (4)
(PHB) and synthetic polycaprolactone (PCL) in contact with
soil. They found that CO2 data of polymer degradation are where V is the degradation rate experimentally observed
satisfactorily described in soil by an M-M-type mechanism and mainly the outcome of the polymer surface area. K is
according to the following equations: the derived adsorption factor and k2 the hydrolysis rate.
Scandola et al. (1998) studied the enzymatic degradation
k1 k2 k3
of PHB film and PHB powder; they showed that rate con-
S + E  ES ES  EP EP  → P + E
(1) stants for film (1.48 μg cm-2 min-1) versus powder suspen-
k-1 k-2 fast sion (1.42 μg cm-2 min-1) yield analogous hydrolysis derived

from Eq. (5). High Vmax of the PHB powder, compared to the
k1 k2 k3 PHB film, was correlated with the large surface area, but
S + E  ES ES + S  ESS ESS  → ES + E in fact the crystallinity difference was the same after PHB
(2) depolymerase attacked on the polymers as a substrate:
k-1 k-2 fast

Vmax =   k2 Aϑ ′ =  k2 A[ KCe /( 1+ KCe )] (5)
where S is the substrate, ES a substrate-enzyme complex,
EP a product-enzyme complex, P the product and k the where Vmax is the enzyme hydrolysis rate on the polymer
step-specific rate constants. surface area, ϑ′ the fraction of the substrate surface

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
88      Z. Majeed et al.: Controlled-release fertilizer biodegradation

occupied by the ES complex, Ce the initial enzyme while the K2 value could give a rough indication of the
concentration. efficiency of the biological system involved in TPS degra-
Bikiaris et al. (2006) studied the M-M kinetic param- dation. These constants were correlated with the mean-
eters of the three aliphatic polyesters by enzymatic hydrol- ings of Vmax = K1, the maximum enzyme reaction velocity,
ysis with Rhizopus delemar lipase by kinetic Eq. (6). For and Km = K2, the substrate saturation constant for the M-M
poly(ethylene succinate), poly(propylene succinate) and equation.
poly(butylene succinate) (PBSu), the kinetic constant (k-1) Jarrell and Boersma (1979) formulated Eqs. (8) and (9)
decreased from 0.036, 0.028 and 0.009 day-1, respectively. to describe the rate at which soil microorganisms removed
As spacing increased between ester groups of these poly- coatings from sulfur-coated urea when it was initially
mers, susceptibility to enzymatic attack also increased: undamaged granules. Biodegradation was predicted on
the basis of percentage of damaged granules as a function
kC
θ=   1 E { 1-exp[-( k1CE   + k-1 ) t ] } (6) of the amount of coating material removed. The effect of
k1CE + k-1
 temperature and soil water content on the soil microbial
growth coefficient (K) in the presence of sulfur-coated
where θ is the fraction of a substrate occupied by the ES
urea granules was depicted by the following equation:
complex and CE is the enzyme concentration, t is the time.
Biodegradation of PLA/starch/coir biocomposites ()
K =  Kmax f ( T ) g ϕ . (8)
was assessed under controlled composting conditions by
following an M-M-like equation (Iovino et al. 2008), used The growth coefficient K depends on the soil temperature
for enzyme-catalyzed reactions: T and water contents g(ϕ), whereas Kmax is the growth rate
at optimum f (T) and g(ϕ):
( K 1t )
%CO2 =
( K 2+ t ) (7)  ∆H * 
 CT exp  - 
 RT 
where K1 = 100 and K2 = 14 at time t. K1 indicated a very long f ( T ) =  (9)
 ∆S ∆H 
incubation time required for the complete mineralization 1 + exp  -
 R RT  
of thermoplastic starch (TPS) with 100% CO2 production,

Table 4 Comparison of Monod and M-M kinetic model parameters for the polymers applied in PC-CRFs.

Biopolymer Enzyme Km Vmax Reference

Michaelis–Menten (M-M) kinetics

 Chitosan Chitin deacetylase 532–750 mg/l 0.477–0.786 l/min Jaworska (2012)
 Cassava starch Amylase 0.2243 g/l 0.739 g/l/min Osaribie et al. (2013)
 Syringic acid (lignin Laccase 43–50 μm 841–962 μm/s
model compound)
 Alginate and Lipase 3.1–4.17 μm 11.11–12.5 μm/min Abdulla et al. (2013)
k-carrageenan hybrid
matrix
 Cellulose Cellulose 1.719–9.844 g/l 0.016–0.304 g/l/min Yeh et al. (2010)
 Poly(β- PHBase 1.0–1.1 cm2/ml 60–94 nEq/min
hydroxybutyrate)
 Poly(ethylene Cutinase 0.41–0.76 μm-1 0.62–0.09 μmol/cm2/h Ronkvist et al. (2009b)
terephthalate)
 Poly(vinyl acetate) Cutinase 20–125 m2/ml 3–11 μmol/ml/h Ronkvist et al. (2009a)

Microorganism μmax Ks

Monod kinetics
 Polyhydroxy butyrate Cupriavidus necator 4.08 day-1 86 g/l Baei et al. (2011)
 Cellulose – 0.48 day-1 0.34 mg/l Cited in Lübken et al. (2010)
 Starch – 37.5 day-1 527 mg/l Cited in Lübken et al. (2010)
 Fly ash-chitosan Funalia trogii – 91.51 mg/l Lin et al. (2013)
 Polyacrylates – 0.066 gC/g biomass-day 0.11 gC/m3 Rittmann et al. (1991)
 Polyurethane Pseudomonas chlororaphis 1.09–1.54 doubling/h 0.649–0.917 mg/ml Howard (2011a)

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
 Z. Majeed et al.: Controlled-release fertilizer biodegradation      89

where C = 0.003,612 exp(24.04), T is the absolute tempera- on a specific substrate at a particular time. Monod intro-
ture in kelvin, ΔH is the enthalpy in cal/mol, R is the uni- duced its fundamental model that described the substrate-
versal gas constant, ΔH* is the enthalpy of an activated dependent microbial growth under the assumption of
enzyme-substrate complex (cal/mol) and ΔS is the entropy. non-inhibitory effect of a substrate or its product. From the
Starch-based PC-CRFs treated with α-amylase showed literature, it was found that biodegradation models provide
that the half-saturation constant (Ks) reduced with the reasonable flexibility to be used according to the experi-
increase in pH from 4 to 10 when data fitted into the M-M mental conditions, either aerobic and/or anaerobic (Cho
model (Rahman et  al. 2013). PC-CRFs being insoluble et al. 2011). The Haldane (Andrews 1968) model introduced
polymers are difficult to mix homogeneously with soil in Monod’s model a self-inhibitory constant to recognize
and challenge the applicability of in situ enzyme activ- inhibition of the reaction due to the inhibition effect of
ity assays in accurate assessment of kinetic parameters. products in biodegradable substrate kinetics.
Alternatively, surrogate synthetic substrates used in The constants of the Monod and M-M kinetic models
enzyme assays are some key issues for the realistic esti- are influenced by substrate concentration but inde-
mation of kinetic parameters in the M-M-type model. pendent of small change in the time course. However,
Recently, an in situ enzyme assay in soil (Spohn et al. 2013) we can see from the comparison of the above equations
was developed using gelatin and starch as the substrate. that different researchers have also used the time course
This method can be extended to PC-CRFs to measure the data of CO2 to calculate the parameters of these models.
better estimate of M-M kinetic parameters in soil. But due These models are quite flexible to meet and fulfill the
to cost and limited substrates, it still needs more research requirement of the research objectives for PC-CRF micro-
for various enzymes especially with low turnover rate, bial and enzyme degradation kinetics. Polymers may
e.g., laccase, a lignin-degrading enzyme. not further support the growth or enzyme hydrolysis due
Any polymer degradation is a trade-off between popu- to recalcitrant or crystalline segments of polymers over
lation density of specific degraders and their growth rate the course of biodegradation which should be critically

Table 5 Microbial growth kinetic models of biodegradable polymers reported for PC-CRFs.

Polymer/monomer Model Equation Reference

Polyurethane Monod µmax  S Howard (2011b)

µs =  
K s +  S

– Monod ∆CO2 µmax MBC0 S0 Wang et al. (2003)

=
∆t S0 + K s

Polycaprolactone-starch blends Gompertz   R⋅e   Cho et al. (2011)

and polybutylene succinate model M = P ⋅exp -exp  ( λ-t )+ 1 
  P  
Poly(lactic acid) (PLA) Boltzmann A -A Arrieta et al. (2013)
Y =   [1x − x2 ] + A2
1 + e 0 )/dx
Polycaprolactone-starch blends First-order B Cho et al. (2011)
= (1 −e-k ,t )
decay model B0

Wheat, native corn and modified corn First-order q = Qmax(1-e-Kt) Shi et al. (2010)
starch, protein, wheat gluten, soy protein decay model
- kmt n
Poly(hydroxy ester ether) Logistic model Pt =  P0 (1-bexp )   Rick et al. (1998)

Polyhydroxyalkanoate Hill model  t  n

Arcos-Hernandez
y = ymax  n n  + y0
 k +t  et al. (2012)

μs, specific growth rate; μmax, maximum growth rate; Ks, half-saturation constant; S, substrate utilized or removed; MBC0, microbial biomass
carbon; M, cumulative methane generation; P, ultimate methane generation; R, the methane generation rate; e, Euler’s number; λ, the lag-
phase period; t, time; A1, the nadir of the sigmoid curve and expresses the initial point in the biodegradation; A2, the vertex of the sigmoid
curve and shows the final point of the biodegradation; dx, the time constant; x0, half time; B, the cumulative oxygen consumption; B0,
ultimate oxygen consumption; K, the biodegradation first-order rate constant; Qmax, total gases generated during the material biodegrada-
tion; Pt, the cumulative percentage of theoretical CO2 at time t; b, a coordinate scaling factor associated with constant of integration; P0, the
theoretical maximum CO2; km, the first-order mineralization rate constant; n, an empirical constant; y, the biodegradation rate at time t; ymax,
the maximum biodegradation; k and n, kinetic parameters of degradation.

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
90      Z. Majeed et al.: Controlled-release fertilizer biodegradation

considered in biodegradation models. Monod kinetics granules to predict their biodegradation impact on the
is very infrequently being cited to record the microbial release of nutrients. These models for PC-CRFs could
activities against applied PC-CRF degradation which provide a better indirect idea about the changes on the
needs further research on the growth response for envi- polymer surface by considering appropriate experimen-
ronment characterization of biodegradation of such tal control and techniques reported in Table 2.
newly developed modified polymer blends.
Table 4 lists the kinetic parameters of the M-M and
Monod models for different biodegradable natural and
synthetic polymers, which, so far, have been applied or 6 C
 onclusion, challenges and
are under trial as polymer coating for PC-CRFs. Still these recommendations
model parameter data are rare and limited to a few classes
of polymers applied in PC-CRFs. Further, in these models, Polymer blends in various combinations with natural
a comparison of the calculated parameters units showed polymers, especially with lignin, starch, chitosan, algi-
a great variation due to variable experimental conditions, nate, cellulose or their modified forms have shown to be
sources of substrate and research objectives. All of these a promising inducer of biodegradation in the more hydro-
together have made the comparison of inter- and intra- phobic synthetic polymers such as polyethylene, polysul-
studies more difficult. Further, M-M parameter values fone and PU in PC-CRFs. Fertilizer release could induce
are not easily retrievable under in situ polymer biodeg- in situ microorganisms growth that compete for the take
radation due to the surrogate synthetic substrates for the up of the nutrients released, and meanwhile grow on the
model verification. In addition, in environment prospects, surface of PC-CRFs and start the events of depolymeriza-
the gap between the field of microbial enzymology and tion. However, studies are lacking which elaborate the role
polymer sciences needs to be abridged further. of microbes and enzymes in the PC-CRF biodegradability
and its effect on the rates of nutrient releases. Such studies
are important to evaluate the effectiveness of the coating
5.2 Microbial growth kinetic models in natural microcosm. The impact of microbial susceptibil-
ity, type and degree of cross-linking, porosity and polymer
Table 5 shows the reported microbial growth models composites composition are few of the coating material
that are practiced to assess the biodegradability of the properties whose understanding could help to engineer the
polymer. In these microbial growth models, parameters desired biodegradation in the coatings of fertilizers to gain
are estimated from the response of the microbial growth better control over current problems of the nutrient release
or substrate mineralization products (CO2 or CO2+CH4) with these materials. Use of microbial growth kinetics in
produced over the initial to the final time of substrate combination with enzyme assays under in situ conditions
incubation in hours, days and months. Model para­ remained unexplored in PC-CRFs to assess the role of these
meters derived from non-linear regression curves very parameters on the biodegradation drivers in addition to
much depend on the shape of the curve, initial substrate the routine testing of weight loss, SEM, DSC and FTIR tech-
concentration and substrate liability to biodegradation. niques. Use of pure biodegradable natural polymers as the
These models, however, provide more detailed changes effective coating material is still a great challenge not only
derived from the growth curve that could provide more because of their high susceptibility to natural biodegrada-
detailed characterization of the polymer biodegradation tion but also because of their poor strength to stay longer
as perceived for coating of PC-CRFs. However, it is up to as PC-CRFs. Synthetic polymers, e.g., PLA and Pdop are
the researchers to choose the model of their choice to best based, or natural monomers are although biodegradable
answer the question. These models are also advantageous and effective in controlled-release formulations, their com-
that they provide good estimate for the mixed microbial mercial synthesis also increases the cost of PC-CRFs produc-
culture in a natural state. They are quite theoretical and tion. The combination of alginate and k-carrageenan with
based upon the experimental data. Fitting the data in other synthetic polymers is yet another area of interest for
either model although made the interpretation justifiable, their application in biodegradable PC-CRFs. To compete
there may be reasons or factors that cause the deviation and replace the current state-of-the-art commercially avail-
within the model and need to be considered before apply- able polyolefin- and PU-based non-environmental friendly
ing these models. To the best of our research survey, there PC-CRF technologies, it is required to find new methods
are very limited studies that could provide an application to harness natural renewable biomass to meet challenge
of these models for polymers once coated onto fertilizer ahead to establish synchrony between the growing plant

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
 Z. Majeed et al.: Controlled-release fertilizer biodegradation      91

growth dynamic nutrient requirement and nutrient release Anghel A, Lacatusu A-R, Lacatusu R, Iancu S, Lungu M, Lazar R,
from PC-CRFs. Vrinceanu A. The effect of prolonged release mineral fertilizers
coated with co-polyester films from pet waste recycling on
maize plants. Scientific Papers. Series A. Agronomy 2012;
Acknowledgments: We are grateful to Ministry of Higher LV-2012: 123–128.
Anggoro DD. Producing slow release urea by coating with starch/
Education (MOHE), Malaysia, for research funding
acrylic acid in fluid bed spraying. Int J Eng Tech 2011; 11: 77–80.
through Long Term Research Grant Scheme (LRGS) and Arcos-Hernandez MV, Laycock B, Pratt S, Donose BC, Nikolić MAL,
Universiti Teknologi PETRONAS for providing graduate Luckman P, Werker A, Lant PA. Biodegradation in a soil
assistantship to complete this research successfully. We environment of activated sludge derived polyhydroxyalkanoate
are also grateful to all anonymous reviewers for their use- (PHBV). Polym Degrad Stabil 2012; 97: 2301.
ful comments and suggestions to improve this manuscript Ariyanti S, Man Z, Azmi BM. Improvement of hydrophobicity of
urea modified tapioca starch film with lignin for slow release
for the publication.
fertilizer. Adv Mater Res 2012; 626: 350–354.
Arrieta MP, Parres F, López J, Jiménez A. Development of a novel
Funding: Ministry of Higher Education (MOHE), Malay- pyrolysis-gas chromatography/mass spectrometry method for
sia through Long Term Research Grant Scheme (LRGS), the analysis of poly (lactic acid) thermal degradation products.
(Grant/Award Number: ‘0153AB-C71-4’). J Anal Appl Pyrol 2013; 101: 150–155.
Azeem B, Kushaari K, Man ZB, Basit A, Thanh TH. Review on
materials & methods to produce controlled release coated urea
fertilizer. J Control Release 2014; 181: 11–21.
References Baei SM, Najafpour G, Younesi H, Tabandeh F, Issazadeh H,
Khodabandeh M. Growth kinetic parameters and biosynthesis
Abdulla R, Ravindra P. Characterization of cross linked Burkholderia of polyhydroxybutyrate in Cupriavidus necator DSMZ 545
cepacia lipase in alginate and κ-carrageenan hybrid matrix. on selected substrates. Chemical Industry and Chemical
J Taiwan Inst Chem Eng 2013; 44: 545. Engineering Quarterly/CICEQ 2011; 17: 1–8.
Abraham J, Rajasekharan Pillai V. Membrane-encapsulated Bashan Y, Hernandez J-P, Leyva L, Bacilio M. Alginate microbeads
controlled-release urea fertilizers based on acrylamide as inoculant carriers for plant growth-promoting bacteria. Biol
copolymers. J Appl Polym Sci 1996; 60: 2347–2351. Fert Soils 2002; 35: 359–368.
Akiyama H, Yan X, Yagi K. Evaluation of effectiveness of enhanced- Bikiaris DN, Papageorgiou GZ, Achilias DS. Synthesis and
efficiency fertilizers as mitigation options for N2O and NO comparative biodegradability studies of three poly(alkylene
emissions from agricultural soils: meta-analysis. Global succinate)s. Polym Deg Stab 2006; 91: 31–43.
Change Biol 2010; 16: 1837–1846. Blankinship JC, Becerra CA, Schaeffer SM, Schimel JP. Separating
Alemzadeh I, Vossoughi M. Controlled release of paraquat from poly cellular metabolism from exoenzyme activity in soil organic
vinyl alcohol hydrogel. Chemical Engineering and Processing: matter decomposition. Soil Biol Biochem 2014; 71: 68–75.
Process Intensification, 2002; 41: 707–710. Bonhomme S, Cuer A, Delort A, Lemaire J, Sancelme M, Scott G.
Ali MI, Perveen Q, Ahmad B, Javed I, Razi-Ul-Hussnain R, Andleeb Environmental biodegradation of polyethylene. Polym Deg Stab
S, Atique N, Ghumro PB, Ahmed S, Hameed A. Studies on 2003 81: 441–452.
biodegradation of cellulose blended polyvinyl chloride films. Burke D, Akay G, Bilsborrow P. Development of novel polymeric
Int J Agric Biol 2009; 11: 577–580. materials for agroprocess intensification. J Appl Polymer Sci
Ali M, Ahmed S, Javed I, Ali N, Atiq N, Hameed A, Robson G. 2010; 118: 3292–3299.
Biodegradation of starch blended polyvinyl chloride films by Burkersroda FV, Schedl L, Göpferich A. Why degradable polymers
isolated Phanerochaete chrysosporium PV1. Int J Environ Sci undergo surface erosion or bulk erosion. Biomaterials 2002;
Technol 2014; 11: 339–348. 23: 4221–4231.
Allison SD. Soil minerals and humic acids alter enzyme stability: Burns R. How do microbial extracellular enzymes locate and
implications for ecosystem processes. Biogeochemistry 2006; degrade natural and synthetic polymers in soil. In: Xu J,
81: 361–373. Huang P, editors. Molecular environmental soil science at
Allison SD, Chacon SS, German DP. Substrate concentration the interfaces in the earth’s critical zone: Berlin, Heidelberg:
constraints on microbial decomposition. Soil Biol Biochem Springer, 2010. p. 294–297.
2014; 79: 43–49. Burns RG, Deforest JL, Marxsen J, Sinsabaugh RL, Stromberger ME,
Al-Zahrani S. Utilization of polyethylene and paraffin waxes as Wallenstein MD, Weintraub MN, Zoppini A. Soil enzymes
controlled delivery systems for different fertilizers. Ind Eng in a changing environment: current knowledge and future
Chem Res 2000; 39: 367–371. directions. Soil Biol Biochem 2013; 58: 216–234.
Andrews J. A mathematical model for the continuous culture of Calabria L, Vieceli N, Bianchi O, Boff de Oliveira RV, do Nascimento
microorganisms utilizing inhibitory substance. Biotechnol Filho I, Schmidt V. Soy protein isolate/poly (lactic acid)
Bioeng 1968; 10; 707–723. injection-molded biodegradable blends for slow release of
Andry H, Yamamoto T, Irie T, Moritani S, Inoue M, Fujiyama H. Water fertilizers. Ind Crop Prod 2012; 36: 41–46.
retention, hydraulic conductivity of hydrophilic polymers Capitelli F, Principi P, Sorlini C. Biodeterioration of modern materials
in sandy soil as affected by temperature and water quality. in contemporary collections: can biotechnology help? Trends
J Hydrol 2009; 373: 177–183. Biotechnol 2006; 24: 350–354.

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
92      Z. Majeed et al.: Controlled-release fertilizer biodegradation

Castro-Enríquez DD, Rodríguez-Félix F, Ramírez-Wong B, controlled-release fertilizer. J Appl Polym Sci 2002; 86:
Torres-Chávez PI, Castillo-Ortega MM, Rodríguez-Félix 2948–2952.
DE, Armenta-Villegas L, Ledesma-Osuna AI. Preparation, Göpferich A. Mechanisms of polymer degradation and erosion.
characterization and release of urea from wheat gluten Biomaterials 1996; 17: 103–114.
electrospun membranes. Materials 2012; 5: 2903–2916. Guo M, Liu M, Zhan F, Wu L. Preparation and properties of a
Chen L, Xie Z, Zhuang X, Chen X, Jing X. Controlled release of urea slow-release membrane-encapsulated urea fertilizer with
encapsulated by starch-g-poly(l-lactide). Carbohyd Polym superabsorbent and moisture preservation. Ind Eng Chem Res
2008; 72: 342–348. 2005; 44: 4206–4211.
Chin-San W. Controlled release evaluation of bacterial fertilizer Guo M, Liu M, Liang R, Niu A. Granular urea-formaldehyde
using polymer composites as matrix. J Control Release 2008; slow-release fertilizer with superabsorbent and moisture
132: 42–48. preservation. J Appl Polym Sci 2006; 99: 3230–3235.
Chiou B-S, Avena-Bustillos RJ, Bechtel PJ, Jafri H, Narayan R, Gurny R, Doelker E, Peppas N. Modelling of sustained release of
Imam SH, Glenn GM, Orts WJ. Cold water fish gelatin films: water-soluble drugs from porous, hydrophobic polymers.
effects of cross-linking on thermal, mechanical, barrier, and Biomaterials 1982 3: 27–32.
biodegradation properties. Eur Polym J 2008; 44: 3748–3753. Hamid NNA, Mohamad N, Hing LY, Dimin MF, Azam MA, Hassan
Cho HS, Moon HS, Kim M, Nam K, Kim JY. Biodegradability and MHC, Mustaq MKS, Ahmad AS. The effect of chitosan content
biodegradation rate of poly(caprolactone)-starch blend and to physical and degradation properties of biodegradable urea
poly(butylene succinate) biodegradable polymer under aerobic fertilizer. J Scie Innov Res 2013; 2: 893–902.
and anaerobic environment. Waste Manag 2011; 31: 475–480. Han X, Chen S, Hu X. Controlled-release fertilizer encapsulated by
Costa MM, Cabral-Albuquerque EC, Alves TL, Pinto JC, Fialho RL. Use starch/polyvinyl alcohol coating. Desalination 2009; 240:
of polyhydroxybutyrate and ethyl cellulose for coating of urea 21–26.
granules. J Agric Food Chem 2013; 61: 9984–9991. Hanafi M, Eltaib S, Ahmad M. Physical and chemical characteristics
Davidson D, Gu FX. Materials for sustained and controlled release of of controlled release compound fertiliser. Eur Polymer J 2000;
nutrients and molecules to support plant growth. J Agric Food 36: 2081–2088.
Chem 2012; 60: 870–876. Hassan Z, Young S, Hepburn C, Arizal R. An evaluation of
Davidson DW, Verma MS, Gu FX. Controlled root targeted delivery urea-rubber matrices as slow-release fertilizers. Fert Res 1990;
of fertilizer using an ionically crosslinked carboxymethyl 22: 63–70.
cellulose hydrogel matrix. SpringerPlus 2013; 2: 4–9. Howard GT. Microbial biodegradation of polyurethane. Recent
Devassine M, Henry F, Guerin P, Briand X. Coating of fertilizers by Developments in Polymer Recycling 2011a; 215: 238.
degradable polymers. Int J Pharm 2002; 242: 399–404. Howard GT. Polyurethane biodegradation. In: Signh SN, editor.
Du C-W, Zhou J-M, Shaviv A. Release characteristics of nutrients Microbial Degradation of Xenobiotics Environmental Science
from polymer-coated compound controlled release fertilizers. and Engineering. Berlin: Springer, 2011b; 2012: 371–394.
J Polym Environ 2006; 14: 223–230. Hussain MR, Devi RR, Maji TK. Controlled release of urea from
Dušek K, Dušková-Smrčková M. Network structure formation during chitosan microspheres prepared by emulsification and
crosslinking of organic coating systems. Prog Polym Sci 2000; cross-linking method. Iran Polym J 2012; 21: 473–479.
25: 1215–1260. Ibrahim AA, Jibril BY. Controlled release of paraffin wax/rosin-coated
Entry JA, Sojka R. Matrix based fertilizers reduce nitrogen and fertilizers. Ind Eng Chem Res 2005; 44: 2288–2291.
phosphorus leaching in three soils. J Environ Manage 2008; Ignat L, Ignat M, Ciobanu C, Doroftei F, Popa V. Effects of flax lignin
87: 364–372. addition on enzymatic oxidation of poly(ethylene adipate)
FAO. Global agriculture towards 2050 in high level expert urethanes. Ind Crops Prod 2011; 34: 1017–1028.
forum – how to feed the world in 2050. Viale delle Terme di Iovino R, Zullo R, Rao M, Cassar L, Gianfreda L. Biodegradation of
Caracalla, 00153 Rome, Italy: Office of the director, agricultural poly(lactic acid)/starch/coir biocomposites under controlled
development economics division economic and social composting conditions. Polym Deg Stab 2008; 93: 147–157.
development department 2009. Jacobs DF, Rose R, Haase DL. Incorporating controlled-release
Fernández-Pérez M, Garrido-Herrera FJ, González-Pradas E, fertilizer technology into outplanting. In: Riley LE, Dumroese
Villafranca-Sánchez M, Flores-Céspedes F. Lignin and RK, Landis TD, editors. National Proceedings: Forest and
ethylcellulose as polymers in controlled release formulations Conservation Nursery Associations-2002. US Department of
of urea. J Appl Polym Sci 2008; 108: 3796–3803. Agriculture Forest Service Rocky Mountain Research Station
Fujita T, Takahashi C, Ushioda T, Shimizu H. Coated granular Proc. RMRS-P-28, 2003: 37–42.
fertilizer capable of controlling the effects of temperature upon Jamnongkan T, Kaewpirom S. Controlled-release fertilizer based
dissolution-out rate. United States Patent, No. 4, 881,963, 1983. on chitosan hydrogel: phosphorus release kinetics. Sci J UBU
Garcia MC, Dãez JA, Vallejo A, Garcãa L, Cartagena MC. Use of kraft 2010a; 1: 43–50.
pine lignin in controlled-release fertilizer formulations. Ind Eng Jamnongkan T, Kaewpirom S. Potassium release kinetics and water
Chem Res 1996; 35: 245–249. retention of controlled-release fertilizers based on chitosan
Ge J, Yu H, Zhong W, Li W, Yu T. Study on the utilization of hydrogels. J Polym Environ 2010b; 18: 413–421.
biodegradable polyurethane material from the bark of Acacia Jarrell WM, Boersma L. Model for the release of urea by granules of
mearnsii (I). Coating material of controlled slow-release sulfur-coated urea applied to soil. Soil Sci Soc Am J 1979; 43:
fertilizer. J Funct Polym 1998; 11: 478–482. 1044–1050.
Ge J, Wu R, Shi X, Yu H, Wang M, Li W. Biodegradable polyurethane Jaworska MM. Kinetics of enzymatic deacetylation of chitosan.
materials from bark and starch: II. Coating material for Cellulose 2012; 19: 363.

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
 Z. Majeed et al.: Controlled-release fertilizer biodegradation      93

Jia X, Ma Z-Y, Zhang G-X, Hu J-M, Liu Z-Y, Wang H-Y, Zhou F. Majeed Z, Ramli NK, Mansor N, Man Z. Lignin loading effect on
Polydopamine film coated controlled-release multielement biodegradability and nitrogen release properties of urea modified
compound fertilizer based on mussel-inspired chemistry. tapioca starch in wet soil. Key Eng Mater 2014a; 594: 798–802.
J Agric Food Chem 2013; 61: 2919–2924. Majeed Z, Ramli NK, Mansor N, Man Z. Starch biodegradation in a
Jintakanon N, Opaprakasit P, Petchsuk A, Opaprakasit M. Controlled lignin modified slow release fertilizer: effect of thickness. Appl
release materials for fertilizer based on lactic acid polymers. Mech Mater 2014b; 625: 830–833.
Adv Mater Res 2008; 905–908. Majeed Z, Ramli NK, Mansor N, Man Z. Lignin modified urea fertilizer
Junejo N, Khanif MY, Hanfi MM, Dharejo KA, Wan ZWY. Reduced loss biodegradation and nitrogen release under reduced soil
of NH3 by coating urea with biodegradable polymers, palm conditions. Appl Mech Mater 2015; 699: 981–987.
stearin and selected micronutrients. Afr J Biotechnol 2011; 10: Mathews AS, Narine S. Poly [N-isopropyl acrylamide]-co-
10618–10625. polyurethane copolymers for controlled release of urea. J Polym
Junejo N, Khanif M, Dharejo K, Abdu A, Abdul-Hamid H. A field Sci A1 2010; 48: 3236–3243.
evaluation of coated urea with biodegradable materials and Mikkelsen RL. Using hydrophilic polymers to control nutrient
selected urease inhibitors. Afr J Biotechn 2014; 10: 19729– release. Fert Res 1994; 38: 53–59.
19736. Modelli A, Calcagno B, Scandola M, Kinetics of aerobic polymer
Kakoulides EP, Valkanas GN. Modified rosin-paraffin wax resins degradation in soil by means of the ASTM D 5988-96 standard
as controlled delivery systems for fertilizers: 1. Fabrication method. J Environ Polym Degrad 1999; 7: 109–116.
parameters governing fertilizer release in water. Ind Eng Chem Mor R, Sivan A. Biofilm formation and partial biodegradation
Res 1994; 33: 1623–1630. of polystyrene by the actinomycete Rhodococcus ruber.
Karamanlioglu M, Robson GD. The influence of biotic and abiotic Biodegradation 2008; 19: 851–858.
factors on the rate of degradation of poly(lactic) acid (PLA) Mousavioun P, George GA, Doherty WOS. Environmental
coupons buried in compost and soil. Polym Degrad. Stab 2013; degradation of lignin/poly(hydroxybutyrate) blends. Polym
98: 2063–2071. Degrad Stab 2012; 97: 1114–1122.
Karlsson S, Ljungquist O, Albertsson A-C. Biodegradation of Mukai K, Yamada K, Doi Y. Kinetics and mechanism of
polyethylene and the influence of surfactants. Polym Degrad heterogeneous hydrolysis of poly[(R)-3-hydroxybutyrate] film
Stab 1988; 21: 237–250. by PHA depolymerases. Int J Biol Macromol 1993; 15: 361–366.
Kim M, Lee S-J. Characteristics of crosslinked potato starch and Mulder WJ, Gosselink RJA, Vingerhoeds MH, Harmsen PFH,
starch-filled linear low-density polyethylene films. Carbohyd Eastham D. Lignin based controlled release coatings. Ind Crops
Polym 2002; 50: 331–337. Prod 2011; 34: 915–920.
Kordach A. Preparation and characterization of controlled-release Nakajima-Kambe T, Shigeno-Akutsu Y, Nomura N, Onuma F,
materials for urea fertilizer from copolyester and its blend. Nakahara T. Microbial degradation of polyurethane, polyester
Sirindhorn International Institute of Technology Thammasat polyurethanes and polyether polyurethanes. Appl Microbiol
University, Thailand, 2009. Biotechnol 1999; 51: 134–140.
Lee K, Tremblay GH, Levy E. Bioremediation: application of Natarajan J, Rattan S, Singh U, Madras G, Chatterjee K.
slow-release fertilizers on low-energy shorelines. International Polyanhydrides of castor oil-sebacic acid for controlled release
Oil Spill Conference. American Petroleum Institute, 1993; 1993: applications. Ind Eng Chem Res 2014; 53: 7891–7901.
449–454. Naz M, Sulaiman S. Testing of starch-based carbohydrate polymer
Liang R, Liu M. Preparation and properties of a double-coated coatings for enhanced urea performance. J Coat Technol Res
slow-release and water-retention urea fertilizer. J Agric Food 2014; 11: 747–756.
Chem 2006; 54: 1392–1398. Ni B, Liu M, Lü S. Multifunctional slow-release urea fertilizer from
Lin Y-H, Lin W-F, Jhang K-N, Lin P-Y, Lee M-C. Adsorption with ethylcellulose and superabsorbent coated formulations. Chem
biodegradation for decolorization of reactive black 5 by Funalia Eng J 2009; 155: 892–898.
trogii 200800 on a fly ash-chitosan medium in a fluidized Ni B, Liu M, Lü S, Xie L, Wang Y. Multifunctional slow-release
bed bioreactor-kinetic model and reactor performance. organic-inorganic compound fertilizer. J Agric Food Chem 2010;
Biodegradation 2013; 24: 137–152. 58: 12373–12378.
Liu Y, Yin S, Wang Y, Cai D, Zhang X, Zhang W. Effect of high Nie H, Liu M, Zhan F, Guo M. Factors on the preparation of
porosity on biodegradation of poly(4-hydroxybutyrate) in vivo. carboxymethylcellulose hydrogel and its degradation behavior
J Biomater Appl 2014; 28: 1105–1112. in soil. Carbohyd Polym 2004; 58: 185–189.
Lübken M, Gehring T, Wichern M. Microbiological fermentation Nikolic V, Velickovic S, Popovic A. Biodegradation of polystyrene-
of lignocellulosic biomass: current state and prospects of graft-starch copolymers in three different types of soil. Environ
mathematical modeling. Appl Microbiol Biot 2010; 85: 1643. Sci Pollut Res 2014; 21: 9877–9886.
Lucas N, Bienaime C, Belloy C, Queneudec M, Silvestre F, Oertli J, Lunt O. Controlled release of fertilizer minerals by
Nava-Saucedo JE. Polymer biodegradation: mechanisms and incapsulating membranes: I. Factors influencing the rate of
estimation techniques. Chemosphere 2008; 73: 429–442. release. Soil Sci Soc Am J 1962; 26: 579–583.
Lum YH, Shaaban A, Mitan NMM, Dimin MF, Mohamad N, Hamid N, Osaribie NA, Okonkwo PC, Aderemi BO. Investigating the effect
Se SM. Characterization of urea encapsulated by biodegradable of Aspergillus niger on starch degradation: process variable
starch-PVA-glycerol. J Polym Environ 2013; 21: 1083–1087. optimization and kinetics. Afr J Biotechnol 2013; 12: 4490.
Maiti S, Ray D, Mitra D. Role of crosslinker on the biodegradation Otey FH, Trimnell D, Westhoff RP, Shasha BS. Starch matrix for
behavior of starch/polyvinylalcohol blend films. J Polym controlled release of urea fertilizer. J Agric Food Chem 1984;
Environ 2012; 20: 749–759. 32: 1095–1098.

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
94      Z. Majeed et al.: Controlled-release fertilizer biodegradation

Parham JA, Deng SP. Detection, quantification and characterization Salman OA, Hovakeemian G, Khraishi N. Polyethylene-coated urea.
of b-glucosaminidase activity in soil. Soil Biol Biochem 2000; 2. Urea release as affected by coating material, soil type and
32: 1183–1190. temperature. Ind Eng Chem Res 1989; 28: 633–638.
Peng Z, Chen F. Synthesis and properties of lignin-based Sareena C, Sreejith M, Ramesan M, Purushothaman E.
polyurethane hydrogels. Int J Polym Mater 2011; 60: 674–683. Biodegradation behaviour of natural rubber composites
Pepic D, Zagar E, Zigon M, Krzan A, Kunaver M, Djonlagic J. reinforced with natural resource fillers – monitoring by soil
Synthesis and characterization of biodegradable aliphatic burial test. J Reinf Plast Comp 2014; 33: 412–429.
copolyesters with poly(ethylene oxide) soft segments. Eur Scandola M, Focarete ML, Frisoni G. Simple kinetic model for
Polym J 2008; 44: 904–917. the heterogeneous enzymatic hydrolysis of natural poly(3-
Pérez-García S, Fernández-Pérez M, Villafranca-Sánchez M, hydroxybutyrate). Macromolecules 1998; 31: 3846–3851.
González-Pradas E, Flores-Céspedes F. Controlled release of Sempeho SI, Kim HT, Mubofu E, Hilonga A. Meticulous overview
ammonium nitrate from ethylcellulose coated formulations. Ind on the controlled release fertilizers. Adv Chem 2014; 2014:
Eng Chem Res 2007; 46: 3304–3311. (Article ID 363071) 1–16.
Rahman A, Haniza N, Mansor N, Razali R. The study of biodegradation Shah Z, Krumholz L, Aktas DF, Hasan F, Khattak M, Shah AA.
kinetics of starch based on coating in Controlled Released Degradation of polyester polyurethane by a newly isolated soil
Fertilizer (CRF). Appl Mech Mat 2013; 295: 240. bacterium, Bacillus subtilis strain MZA-75. Biodegradation
Ravi Kumar MN. A review of chitin and chitosan applications. React 2013; 24: 865–877.
Funct Polym 2000; 46: 1–27. Shah AA, Kato S, Shintani N, Kamini NR, Nakajima-Kambe T. Microbial
Rick DL, Davis JW, Kram SL, Mang MN, Lickly TD. Biodegradation of degradation of aliphatic and aliphatic-aromatic co-polyesters.
an epoxy-based thermoplastic polyester, poly (hydroxy ester Appl Microbiol Biotechnol 2014; 98: 3437–3447.
ether) in a laboratory-scale compost system. J Environ Polym Shaviv A. Controlled release fertilizers. IFA International Workshop
Degr 1998; 6: 143–157. on Enhanced-Efficiency Fertilizers, Frankfurt. International
Rittmann BE, Sutfin JA, Henry B. Biodegradation and sorption Fertilizer Industry Association Paris, France, 28–30, 2005.
properties of polydisperse acrylate polymers. Biodegradation Shi B, Bunyard C, Palfery D. Plant polymer biodegradation in
1991; 2: 181–191. relation to global carbon management. Carbohyd Polym 2010;
Riyajan S-A, Sasithornsonti Y, Phinyocheep P. Green natural rubber- 82: 401–404.
g-modified starch for controlling urea release. Carbohyd Polym Shogren RL, Doane WM, Garlotta D, Lawton JW,
2012; 89: 251–258. Willett JL. Biodegradation of starch/polylactic acid/
Rodriguez-Kabana R, Godoy G, Morgan-Jones G, Shelby RA. The poly(hydroxyester-ether) composite bars in soil. Polym Degrad
determination of soil chitinase activity: conditions for assay Stab 2003; 79: 405–411.
and ecological studies. Plant Soil 1983; 75: 95–106. Singh B, Sharma N. Optimized synthesis and characterization of
Ronkvist ÅM, Lu W, Feder D, Gross RA. Cutinase-catalyzed deacetylation polystyrene graft copolymers and preliminary assessment
of poly (vinyl acetate). Macromolecules 2009a; 42: 6086–6097. of their biodegradability and application in water pollution
Ronkvist ÅM, Xie W, Lu W, Gross RA. Cutinase-catalyzed hydrolysis alleviation technologies. Polym Degrad Stab 2007; 92:
of poly (ethylene terephthalate). Macromolecules 2009b; 42: 876–885.
5128–5138. Sivan A. New perspectives in plastic biodegradation. Curr Opin
Rose K, Steinbüchel A. Biodegradation of natural rubber and related Biotechnol 2011; 22: 422–426.
compounds: recent insights into a hardly understood catabolic Sivan A, Szanto M, Pavlov V. Biofilm development of the
capability of microorganisms. Appl Environ Microbiol 2005; 71: polyethylene-degrading bacterium Rhodococcus ruber. Appl
2803–2812. Microbiol Biotechnol 2006; 72: 346–352.
Roshanravan B, Mahdavi F, Rashid SA. Nitrogen release properties Snyder C, Bruulsema T, Jensen T, Fixen P, Review of greenhouse
of urea-kaolinite controlled release fertilizer with chitosan gas emissions from crop production systems and fertilizer
binder. In: Aris AZ et al., editors. From sources to solution: management effects. Agric Ecosyst Environ 2009; 133: 247–266.
Proceedings of the international conference on environmental Spohn M, Carminati A, Kuzyakov Y. Soil zymography–A novel in situ
forensics 2013. Berlin: Springer, 2014. method for mapping distribution of enzyme activity in soil. Soil
Russell JR, Huang J, Anand P, Kucera K, Sandoval AG, Dantzler KW, Biol Biochem 2013; 58: 275–280.
Hickman D, Jee J, Kimovec FM, Koppstein D. Biodegradation Stahl JD, Cameron MD, Haselbach J, Aust SD. Biodegradation of
of polyester polyurethane by endophytic fungi. Appl Environ superabsorbent polymers in soil. Environ Sci Pollut Res 2000;
Microbiol 2011; 77: 6076–6084. 7: 83–88.
Rychter P, Biczak R, Herman B, Smylla A, Kurcok P, Adamus G, Stevens ES. Green plastics: an introduction to the new science of
Kowalczuk M. Environmental degradation of polyester blends biodegradable plastics. USA: Princeton University Press, 2002.
containing atactic poly(3-hydroxybutyrate). Biodegradation in Sutton-Grier AE, Keller JK, Koch R, Gilmour C, Megonigal JP. Electron
soil and ecotoxicological impact. Biomacromolecules 2006; 7: donors and acceptors influence anaerobic soil organic matter
3125–3131. mineralization in tidal marshes. Soil Biol Biochem 2011; 43:
Sakharovskii VV, Nikitin DI, Sakharovskii VG. Physiological 1576–1583.
characterization of the survival of some Gram-negative bacteria Teegarden DM. Polymer chemistry: introduction to an indispensable
under conditions of carbon deficiency. Appl Biochem Microbiol science, Virginia: NSTA Press, 2004.
1999; 35: 380–388. Tomaszewska M. Jarosiewicz A. Use of polysulfone in controlled-
Salman OA. Polymer coating on urea prills to reduce dissolution release NPK fertilizer formulations. J Agric Food Chem 2002;
rate. J Agric Food Chem 1988; 36: 616–621. 50: 4634–4639.

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
 Z. Majeed et al.: Controlled-release fertilizer biodegradation      95

Tomaszewska M, Jarosiewicz A. Polysulfone coating with starch Yeh A-I, Huang Y-C, Chen SH. Effect of particle size on the rate of
addition in CRF formulation. Desalination 2004; 163: 247–252. enzymatic hydrolysis of cellulose. Carbohyd Polym 2010; 79:
Tomaszewska M, Jarosiewicz A, Karakulski K. Physical and chemical 192.
characteristics of polymer coatings in CRF formulation. Zhang W, Zhang X. A forecast analysis on fertilizers consumption
Desalination 2002; 146: 319–323. worldwide. Environ Monitor Assess 2007; 133: 427–434.
Thouand G, Durand MJ, Maul A, Gancet C, Blok H. New concepts in the Zhao C, Shen YZ, Du CW, Zhou JM, Wang HY, Chen XY. Evaluation
evaluation of biodegradation/persistence of chemical substances of waterborne coating for controlled-release fertilizer using
using a microbial inoculum. Front Microbiol 2011; 2: 1–6. Wurster fluidized bed. Ind Eng Chem Res 2010; 49: 9644–9647.
Trenkel ME. Slow- and controlled-release and stabilized fertilizers:
an option for enhancing nutrient use efficiency in agriculture.
Paris: International Fertilizer Industry Association, 2010.
Tyliszczak B, Polaczek J, Pielichowski,J, Pielichowski K.
Preparation and properties of biodegradable slow-release
Bionotes
PAA superabsorbent matrixes for phosphorus fertilizers.
Zahid Majeed
Macromolecular symposia, Wiley Online Library 2009: 236–242.
Department of Chemical Engineering,
Wang WJ, Dalal RC, Moody PW, Smith CJ. Relationships of soil
Universiti Teknologi PETRONAS, Bandar
respiration to microbial biomass, substrate availability and
Seri Iskandar, 31750 Tronoh, Perak,
clay content. Soil Biol Biochem 2003; 35: 273.
Malaysia
Wang Y, Liu M, Ni B, Xie L. κ-Carrageenan-sodium alginate
beads and superabsorbent coated nitrogen fertilizer with
slow-release, water-retention, and anticompaction properties.
Ind Eng Chem Res 2012; 51: 1413–1422.
Wang X, Lü S, Gao C, Xu X, Wei Y, Bai X, Feng C, Gao N, Liu M, Wu L. Zahid Majeed obtained his Master of Philosophy degree in Biochem-
Biomass-based multifunctional fertilizer system featuring istry from Quaid-i-Azam University (QAU), Islamabad, Pakistan, in
controlled-release nutrient, water-retention and amelioration 2008. After that he joined the Ministry of National Food Security &
of soil. RSC Adv 2014; 4: 18382–18390. Research, Islamabad, Pakistan where he served as a manager until
Wool RP, Cole MA. Microbial degradation. ASM engineering 2011. In the same year, he went to Malaysia where he continued his
materials handbook Vol. 2: Engineering plastics. New York: PhD under the supervision of Dr Nurlidia Mansor and co-supervision
Plenum Publishing, 1988: 783–787. of Dr Zakaria Man at the Department of Chemical Engineering,
Wu K-J, Wu C-S, Chang J-S. Biodegradability and mechanical Universiti Teknologi PETRONAS (UTP), Perak, Malaysia. Currently,
properties of polycaprolactone composites encapsulating he is working on the biodegradable biomaterial’s development
phosphate-solubilizing bacterium Bacillus sp. PG01. Proc from low-cost waste resources for the application of slow drug
Biochem 2007; 42: 669–675. delivery technologies. Both theoretical and applied aspects are of
Wu C-S. Promoting fertilizer use via controlled release of a special interest that involve microbial and enzymatic transformation
bacteria-encapsulated film bag. J Agric Food Chem 2010; 58: through their reaction kinetic studies in these materials.
6300–6305.
Wu L, Liu M. Preparation and properties of chitosan-coated Nur Kamila Ramli
NPK compound fertilizer with controlled-release and Department of Chemical Engineering,
water-retention. Carbohyd Polym 2008; 72: 240–247. Universiti Teknologi PETRONAS, Bandar
Wu S. FTIR spectra study on the film of polyurethane coated urea Seri Iskandar, 31750 Tronoh, Perak,
controlled-release fertilizer. Spectroscopy and Spectral Malaysia
Analysis 2011; 31: 630–634.
Xie L, Liu M, Ni B, Zhang X, Wang Y. Slow-release nitrogen and
boron fertilizer from a functional superabsorbent formulation
based on wheat straw and attapulgite. Chem Eng J 2011; 167: Nur Kamila Ramli is currently doing her PhD in Chemical Engi-
342–348. neering at the Department of Chemical Engineering, Universiti
Xu R, Obbard JP. Effect of nutrient amendments on indigenous Teknologi PETRONAS (UTP), Tronoh, Perak, Malaysia. She obtained
hydrocarbon biodegradation in oil-contaminated beach her Bachelor’s degree in Environmental Technology from Universiti
sediments. J Environ Qual 2003; 32: 1234–1243. Sains Malaysia (USM), Penang, in 2009 and was involved with
Yamamoto H, Amaike M, Saitoh H, Sano Y. Gel formation of lignin wastewater analysis as the final project. In 2010, she obtained
and biodegradation of the lignin gels by microorganisms. her Master’s degree (course work mode) in Environmental Studies
Mater Sci Eng C 2000; 7: 143–147. (final project: water quality analysis) from Universiti Putra Malaysia
Yang Y-C, Zhang M, Li Y, Fan X-H, Geng Y-Q. Improving the quality of (UPM), Serdang, Malaysia. Her current research focuses on natural
polymer-coated urea with recycled plastic, proper additives, compounds such as urease bioinhibitors for controlled-release
and large tablets. J Agr Food Chem 2012; 60: 11229–11237. fertilizer application.

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
 96      Z. Majeed et al.: Controlled-release fertilizer biodegradation

Nurlidia Mansor
Department of Chemical Engineering,
Universiti Teknologi PETRONAS, Bandar
Seri Iskandar, 31750 Tronoh, Perak,
Malaysia
[email protected]

Nurlidia Mansor is a senior lecturer at the Department of Chemical

Engineering, Universiti Teknologi PETRONAS, Malaysia. She holds
degrees in Biotechnology and Environmental Engineering from
Universiti Putra Malaysia and a PhD in Environmental Chemistry
from Glasgow University, UK. Her research interest lies in the areas
of biomonitoring, bioremediation and phytoremediation as well as
microalgae biosorbents. She is also part of a research group that
studies alternative green materials for improvements in agricultural
technology.

Zakaria Man
Department of Chemical Engineering,
Universiti Teknologi PETRONAS, Bandar
Seri Iskandar, 31750 Tronoh, Perak,
Malaysia

Zakaria Man is a lecturer of polymer- and petrochemical-related

subjects at the Department of Chemical Engineering, Universiti
Teknologi PETRONAS (UTP), Malaysia. He started his career in 1985
with PETRONAS Research Institute. In 1994, he took up work at
Polyethylene Malaysia Sdn. Berhad (PEMSB) and was appointed as
a polymer technologist. In 1997, he joined UTP and pursued his PhD
in Polymer Science and Technology at the Polymer Science Centre,
University of Manchester Institute of Science and Technology
(UMIST), UK. His current research interest includes biopolymers,
polymer blends and polymer composites.

Bereitgestellt von | De Gruyter / TCS

Angemeldet
Heruntergeladen am | 10.02.15 18:11
View publication stats