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Keywords: Petroleum-based plastics have come under a lot of scrutiny in the past decade owing to the properties that made
Bioplastics them ubiquitous items; their durability and expendability. The exploitation of such features during the industrial
Greenwashing era has now culminated into the major environmental issue of plastic pollution. As a means of mitigating this
Disposal
issue, bioplastics are being considered as an environment-friendly alternative. However, not all materials under
Environmental benefits
Biodegradable
this category are the same and this has caused many misconceptions about the commodity and its after-life
processing, which has led to false advertising and consumer indifference. Proper disposal and sorting proced
ures required for many of these bioplastics are not well known, which affects their optimum degradation. This
review aims to: (i) outline the production and properties of the most prominent bioplastics along with their
impacts on the environment and the economy, (ii) discuss the differences between biodegradable and com
postable materials, (iii) explore the basic differences in the disposal of bioplastics compared to conventional
plastics, and (iv) enumerate the future directions that can help them become a ubiquitous commodity. Proper
knowledge of the various bioplastics and the implementation of proper disposal methodologies may alleviate
health as well as environmental impacts of plastics and reduce plastic pollution.
petroleum based plastics for the simple reason that they are economi
cally non-viable. As of 2017, a kilogram of poly(3-hydroxybutyrate) or P
1. Introduction (3HB), the most common type of PHA, was priced at US$ 5.5 while a
kilogram of PLA filaments cost around US$ 21 [8]. In contrast, con
Since the early 2000s, plastic pollution has been a topic on the table ventional plastics such as polypropylene (PP) and polyurethane (PU)
in every United Nations Climate Summit and various countries have cost approximately US$ 1.3 to US$ 1.7 per kilogram [9]. Many com
tried to include the alleviation of this major concern into their 5 year panies involved in the production of bioplastics such as Bio-On, Novon
plans [1,2]. Rapid industrial advancements, the fossil fuel crisis, and the and Cereplast had to shut down due to the debilitating losses they faced
abundance of loop holes in environmental laws misused by multina [10–12]. However, methodologies to reduce these costs are underway
tional companies have brought about the Great Garbage Patches in the with polymers such as Bio-PET priced at only US$ 3.13 per kilogram
Pacific and Atlantic Oceans which in turn has aggravated the issue of [13]. Innovative methods to reduce the cost of extraction involved in the
rapid climate change [3,4]. production of commercially available cellulose-based bioplastics such as
For this reason, bioplastics are being looked into by many countries carboxymethyl cellulose have also been explored along with redirecting
and corporations to replace these conventional plastics since many of food waste and industry waste into bioplastic production thereby
them are touted to be biodegradable and hence can be the solution to reducing the cost in terms of raw material [14,15]. Although PHA and
plastic pollution. Bioplastics were discovered nearly a century ago with other bioplastics like polylactic acid (PLA) and polycaprolactone (PCL)
Galalith and Polyhydroxyalkanoates (PHAs) being some of the oldest [5, are being promoted for their green prospects, current literature seems to
6]. At present, there are many bioplastics on the market including but be heavily divided on whether they may be able to reduce pollution or
not limited to polylactic acid (PLA), poly(butylene adipate-co-tereph add to it since most bioplastics need specific conditions for degradation.
thalate) (PBAT), Mirel and Bio-PET. Starch-based polymers such as Some papers even claim that the degradation products of bioplastics,
blends with polycaprolactone (PCL) and polybutylene succinate (PBS) though non-toxic, may inadvertently affect the acidity of the soil and
currently dominate the market [7]. Even though many varieties of microbial diversity [16,17]. Although bioplastics are biodegradable,
bioplastics exist, they have not been able to phase out conventional
* Corresponding author.
E-mail address: ksudesh@usm.my (K. Sudesh).
https://doi.org/10.1016/j.rser.2021.111237
Received 7 August 2020; Received in revised form 26 April 2021; Accepted 17 May 2021
Available online 25 May 2021
1364-0321/© 2021 Elsevier Ltd. All rights reserved.
A. Nandakumar et al. Renewable and Sustainable Energy Reviews 147 (2021) 111237
certain steps will need to be taken in their disposal to ensure safe and biodegradable, a report by the United Nations Environment Programme
rapid biodegradation. This review aims to clear misconceptions about stated that they only physically degrade, due to the addition of metal
the terms related to bioplastics as well as their properties, and give a compounds to conventional plastics, and are not broken down or taken
compact procedure on their disposal. up by microbes. Another newcomer is the enzyme-mediated degradable
bioplastic, which one should also be wary of for the same reasons as
2. The basics of bioplastics mentioned for oxo-biodegradable plastics [21].
Bioplastics have been and continue to be used as an umbrella term to 2.2. Types of bioplastics
encompass many types of materials, some that do not quite fit into the
consumer’s basic understanding or expectations for the product. Recent Examples of bioplastics, based on the broad definition, are catego
technological advancements have added to the inventory, which also rized as follows:
implies that there can be a bioplastic substitution for every need.
(i) Starch-Based Bioplastics -Polymers that contain native or modi
2.1. Definition fied starch moieties fall under the category of starch based
polymers. Blends of natural or synthetic plastics with starch as
Although there is no standardized definition for a bioplastic, ac well as polymers produced from the fermentation of starch can
cording to the most widely accepted meaning, a bioplastic is a polymer also be included in this group. This accounts for approximately
that is biobased or biodegradable or both [18]. This brings to light a very 50% of the global bioplastics market and constitutes many of the
important point that not all bioplastics are biodegradable, i.e., biobased thermoplastics in use today [7,22]. E.g., Bio-PET, Thermoplastic
does not imply biodegradable, and certain non-biobased plastics are Starch (TPS)
biodegradable, such as PBAT. Even some conventional plastics, such as (ii) Cellulose-Based Bioplastics - Derived from cellulose esters or
polyolefins of low molecular weight, can give rise to create products of other cellulose derivatives. Cellulose contains glucose molecules
low molecular weight that can be utilized by microbes through abiotic connected to each other by a β(1,4) linkage which explains why
processes like photodegradation and thermal degradation. Significant specific symbiotic microbes are required for its digestion by ru
biodegradation under a reasonable time period mandates that the minants [23]. E.g., cellulose acetate, methyl cellulose
average molecular weight should be under 5000 Da. A decrease in the (iii) Aliphatic Polyesters - Include materials that are more resistant to
number of carbonyl groups during degradation is a good indicator of hydrolytic degradation. E.g., PHA and PLA
microbial growth. The final products of the degradation of these smaller (iv) Protein-Based Bioplastics - Derived from sources like milk, wheat
polyolefins are water and carbon dioxide. Prodegradant additives may gluten and other sources of protein. Very similar to the process of
also be added to these polymers to accelerate their rate of degradation cheese-making. E.g., casein bioplastics
and usually include metal salts [19]. (v) Lignin-Based Bioplastics - Although lignin has long since been
Bioplastics of more recent origin such as Bio-PET are termed so only obtained as a byproduct of cellulose production, it is only with
because they are biobased, as the monomers are produced from corn, the recent advent of biorefinery projects that this polymer has
but the polymerization process is chemical and the polymer has the same gained importance [24]. E.g., PP-lignin polymer blends,
properties as conventional PET, which makes the resulting polymer non- PHA-lignin polymer blends, etc.
degradable. However, the International Union of Pure and Applied (vi) Chitin-Based Bioplastics - Chitin is a biopolymer made of N-
Chemistry (IUPAC) in 2015 defined bioplastics as “a biobased polymer acetyl-D-glucosamine units linked by β(1,4) bonds and is the
or a polymer issued from monomers derived from the biomass”, and for second most abundant biopolymer after cellulose. Although
this reason the IUPAC has stated that the term bioplastics can be very chitin is found in the cell walls of yeast and fungi and in the
misleading and suggests avoiding the term completely and using terms exoskeletons of arthropods, the primary source of its extraction is
like biobased polymers instead [20]. This is not to be confused with from the shells of crustaceans like crabs, prawns, shrimps, etc.
compostable plastics that decompose as a result of biological activities [25]. E.g., Chitosan based bioplastics, chitin blends with PP, etc.
over the period of their degradation. More on this has been discussed in
later sections. Some argue that plastics that are completely petrochemical in na
While on this topic, a good representative of misunderstood terms is ture, like PCL and PBAT, may also be considered as a bioplastic as they
oxo-biodegradable plastics. Although the name suggests that they are are completely biodegradable.
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2.3. Production structure. The addition of plasticizers such as glycerol or sorbitol may
also help in ensuring that thick films can be synthesized without
In terms of production, bioplastics may be broadly grouped into worrying about the brittleness however, increasing the amount of
three types: (i) polymers directly extracted from biomass, (ii) polymers plasticizers also reduced the tensile strength of the material. Such
produced from bio-derived intermediates, and (iii) polymers produced properties were seen to help extend the shelf life of food products such as
by microorganisms. cheese since these casein films acted as oxygen barriers [36]. The major
Polymers such as those derived from lignin, cellulose, starch, chitin issues with using casein as a biopolymer include the problems associated
and even milk fall under the category of bioplastics derived from with the acquisition of raw material, the complex manufacturing pro
biomass. Lignin, cellulose and starch based polymers are often used to cesses and poor resistance to moisture. Methods such as processing the
produce intermediates so as to make blends with other plastics. polymer with high pressure CO2 are currently underway in hopes of
Of the biomass resources in the world, the ones obtained from the increasing the hydrophobicity and decreasing the solubility of the
byproducts of the wood industry and agricultural fields seem to be the polymer [37].
largest. Furthermore, lignocellulose makes up 90% of this plant biomass Starch is considered a good filler for conventional plastics since it is
and nearly a half of the carbon present in this lignocellulosic material biodegradable and has adequate thermal stability so as to not interfere
contains cellulose [26]. Cellulose based polymers such as cellulose ac with the melt flow processing of the polymer. However since it is a
etate, cellulose nitrate and methyl cellulose can be synthesized from hydrophilic molecule, it causes a loss in mechanical properties and
processes such as acylation, acetylation and esterification with other produces low adhesion due to the hydrophobic nature of the conven
components such as carboxylic acids and their derivatives [27]. The tional plastics that causes poor formation of starch-polymer interfaces.
main factor to keep in mind during cellulose processing is its extraction The use of starch by itself is not viable since it neither shows resistance to
as it is crucial to keep the cellulose intact while the other polymers like humidity nor does it show sufficient properties for melt-process [7]. On
pectin, hemicelluloses and lignin are removed. This serves as the the other hand, TPS contains starch and a plasticizer however, unlike
rate-limiting step in biomass conversion to cellulose in terms of both starch blends, thermomechanical energy is applied to the polymer to
yield and cost [28]. The most common methods of cellulose extraction create hydrogen bonds between the starch and the plasticizer thereby
consist of the Kraft method, Caustic Soda processing and the Sulfite severing the hydrogen bonds between the hydroxyl groups of starch.
method. All three processes entail a mixture of wood chips with chem Insufficient amounts of plasticizers though impair the formation of a
icals ranging from sodium hydroxide to sodium sulfite so as to cleave the homogenous layer and can instead cause some starch granules to remain
bonds between hemicelluloses and lignin to cellulose. However, these intact. TPS in turn exhibits drawbacks in the form of poor water resis
processes, especially the Kraft process, have been considered contro tance and inferior mechanical properties. Remedies to mediate these
versial due to the environmental impacts, odorous substances and large issues though are limited by the cost incurred [10]. TPS can also be
amounts of liquid waste produced as a byproduct of these methods [29, blended with non-biodegradable synthetic plastics to increase the
30]. modulus of the polymer however, this is also seen to decrease the
The use of lignin in polymer applications, while attractive, had ductility. In cases of TPS blends with non-polar synthetic polymers,
proven to be quite difficult due to its macromolecular structure. Spec there arises the issue of immiscibility however, the addition of citric acid
troscopic analyses suggest that the structure of individual molecules was seen to counter this drawback [7]. In other cases such as Bio-PET,
within the sample itself may significantly vary [24]. The processes for the monomers are derived from renewable resources like corn or po
lignin extraction can vary based on if the extrude is to be used at an tato, but the polymerization follows the same pattern as
analytical or industrial level. Similar to cellulose extraction, lignin too petroleum-based conventional plastics.
can be extracted using the Kraft method. However during this process, Polymers produced by microorganisms include PHA and in some
the backbone of this polymer gets cleaved due to the harsh chemicals cases, even extracellular polymeric substances like alginate. The mi
and at times new functional groups may be introduced into the polymer croorganisms may be grown on carbon-rich sources such as glucose or
as well [31]. Organic solvents can also be used to solubilize degraded oil and the organisms accumulate this carbon as polymers, i.e., the
forms of lignins and are structurally most similar to native lignins as polymerization takes place in vivo.
compared to lignin produced by other industrial methods. The major From Table 1, it can be seen that PHA is the only bioplastic that is
drawback is that the amounts of lignin produced by these processes are biobased, biodegradable as well as biologically produced [38]. There
extremely low as compared to the amount of solvent required and the may be some dispute over the exclusion of PLA from such a grouping, as
disposal of these solvents also provide an environmental hazard [24,32]. various studies have shown that PLA is just as difficult to degrade as
Due to the laboriousness of its melt processing and poor thermal sta petroleum-based plastics if devoid of conducive conditions such as
bility, the use of lignin directly as a polymer does not seem viable. elevated temperature and moisture [17].
Instead lignin is blended with other polymers to provide resistance
against UV degradation and thermo-oxidation since the phenol groups in 2.4. Uses
lignin are able to scavenge free radicals [33].
Chitin based polymers may also be deemed a fairly plausible Bioplastics like PHA are biodegradable and can bypass the use of
replacement to conventional plastics since there is no deficit in chitin fossil fuels, since most of them are produced from biomass, which im
resources due to the rise in fishing and aquaculture systems. However, plies potential carbon neutrality. For these reasons, there has been an
extraction, yield and final product quality are some points of concern increase in the usage of these materials, in the form of blends or com
with respect to the polymers produced from it [25]. Chitin extraction, posites with synthetic polymers that are degradable or non-degradable.
whether chemical or biological, follow the same steps; demineralization This is not a new concept as parts of machines like the Ford Model T
and deproteinization. The chemical method uses dilute hydrochloric were once derived from corn and soybean oil [49]. At present, the most
acid for demineralization and deproteinization is done using sodium common use of bioplastics is in single use items like food packaging,
hydroxide and removal of lipids using organic solvents. The major utensils, film wrap, etc [50].
drawbacks of this method include the use of high volumes of hazardous Another benefit of the biodegradable nature of bioplastics is that the
solvents and the loss in mass post processing. On the other hand the end products can be reclaimed as raw materials, thereby eliminating the
biological method of extraction uses microbes such as lactic-acid bac need for virgin raw material and giving the product multiple end-of-life
teria, proteolytic bacteria and even mixed cultures of the same [34,35]. options. For example, a company proficient in producing casein plastics,
Casein polymer films are made by denaturing the proteins using heat Lactips, claims that their plastic is edible since it is made of milk protein
which forms disulfide linkages that may contribute to the film like [17]. Casein protein polymers are majorly synthesized to be used as
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A. Nandakumar et al. Renewable and Sustainable Energy Reviews 147 (2021) 111237
of chemicals like ethanol and methanol, and even for the synthesis of
synthetic petroleum. Although the incineration of plastics for heat
generation is already a frequently used option in many parts of Europe,
the shift to bioplastics provides the opportunity to obtain renewable
energy from the biogenic carbon. Such measures also ensure that the use
of landfills is minimized in the long run, hence allowing the reclamation
of land for other purposes [79]. Therefore, replacing a good portion of
fossil fuel-based plastics with biobased ones may help achieve EU
Climate Protection targets and even UN Sustainable Development Goals
[76].
3. Properties of bioplastics
3.1. Biodegradability
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Fig. 2. Prospective Substitutions by PHA. This figure shows how day to day products that use petroleum based plastics can be manufactured with variants of PHA
hence ensuring that the products are biodegradable and yet maintain the physical properties required for their application. Modified from“PHA bioplastics a ‘tunable’
solution for convenience food packaging” by Lingle, R. (2018, April 10) [75].
[87]. Studies have also shown that cellulose fibres used in the textile
Table 2
industry show different rates of biodegradability due to variations in
PHA degrading microorganisms. This table provides examples of the various
crystallinity, degree of polymerization and manufacturing processes. In
types of microorganisms that can degrade PHAs under various conditions; at the
these studies, it was shown that rayon was the most biodegradable while physiological pH of 7.4, in soil, marine and freshwater environments, as well as
acetate was the least biodegradable. Although cotton has a higher hy in the activated sludge system.
drophilicity than rayon, its high crystallinity made it less biodegradable
Conditions Microorganisms Reference
than rayon. And although acetate is the least crystalline, the replace
ment of hydrophilic acetyl molecules with hydrophobic acetate mole Aqueous Alcaligenes faecalis, Comamonas Mukai et al., 1993 [92]
solution [pH testosterone, Chromobcaterium
cules makes it more difficult to degrade [88].
7.4] viscosum Pseudomonas fluorescens,
Lignin provides strength and protection to the plant cell wall due to Pseudomonas pickettii
the presence of strong ether and carbon-carbon linkages and can also Soil Pseudomonas sp., Streptomyces Emadian et al., 2017
guard the plant against cellulolytic microbes [26]. However due to these bangladeshensis, Bacillus subtilis, [97]
Actinomadura sp.
properties, in addition to its insolubility, it is a difficult polymer to
Marine Gracilobacillus sp., Enterobacter, Volova et al., 2011;
enzymatically depolymerise. Save for a few basidiomycetes or white rot Planococcus, Micrococcus sp, Volova et al., 2013 [96,
fungi, other microbes, including brown rot fungi, can only modify the Cellulomonas, Corynebacteriu, 98]
polymer [89]. Freshwater Acidovorax sp., Pseudomonas sp., Morohoshi et al., 2018;
The degradation rate of most bioplastics appear to depend on the Thiomonas sp., Cupriavidus sp. Vigneswari et al., 2019
[99,100]
surface area of the polymer, as this seems to be the limiting factor in
Activated Micrococcus sp., Bacillus sp. Emadian et al., 2017
most cases of degradation.This can be attributed to the fact that rapid sludge [97]
degradation of these materials is caused by enzymes, the activities of
which are inherently constrained by surface area. Depending on the
equilibrium between the rate of hydrolytic chain scission of the polymer other polymers, such as seaweed based polymers that do not have a very
and the rate of water diffusion into it, uncatalysed hydrolytic degrada long shelf life in many conditions [93]. The degradation time for bio
tion can also occur at the surface or through the bulk of the material. polymers may depend on factors such as porosity and the physical state
This degradation is dependent on factors such as crystallinity, of the polymer, but it also heavily relies on the microbial density and
morphology, temperature and thickness of the material. Surface degra diversity of the environment, temperature, pH, salt concentrations, etc.,
dation is much faster, especially in the soil, and over time this degra and how frequently these variables fluctuate [94]. However studies that
dation causes an increase in surface area and roughness. This, in turn, have estimated the time for complete degradation of PHA to be around
provides a larger area for the attachment of microbes, which makes the 1.5–3.5 years have also suggested that the dearth of information on this
polymer more amenable to further degradation [90]. For example, in the topic makes it difficult to point out a single environmental or morpho
case of PHAs, they are usually degraded by the action of extracellular logical factor as the key determinant of the rate of biodegradation [95].
depolymerases such as PHA depolymerases, lipases, etc [91]. These An unusual advantage of PHA in terms of biodegradation comes forth in
enzymes are mostly present only in soil and sediment dwelling microbes an indirect way due to its ability to settle quickly on the ocean floor since
[92]. Hence although PHAs can be considered biodegradable due to its even with the addition of fillers and additives the density of PHA is
capacity to be broken down into oligomers or monomers by many mi usually greater than 1.1 [96]. Therefore, if we were to deposit PHA in an
croorganisms as listed in Table 2, it is also more durable as compared to ocean with the appropriate temperature for its degradation, the chances
of it floating into other oceans with colder temperatures is reduced,
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unlike in case of plastic bags that are always floating. commercial composting facilities, most compostable materials can
degrade despite the external conditions [109].Chitin on the other hand
3.2. Compostability can be easily degraded in many areas like the sea, soil and even the
human gut. This is due to the presence of chitinases in many microbes
A compostable material can be broken down into nutrient-rich which degrade this polymer through chitinoclastic or deacetylation
biomass in three months or less under composting conditions. To be mechanisms [56].The rate of degradation depends on factors like the
considered compostable, bioplastics must meet the ASTM D6400 stan thickness of the material, the composting conditions, and the chemical
dard for compostability. Compostable materials must not have any makeup of the material. Home composting is often quite variable due to
physical or visual remnants past the specified composting time and the the quality of soil, the moisture content, temperature and how often
products of this decomposition should not leave behind any toxic resi turning over occurs. Industrial or commercial composting, on the other
dues [101]. However, there are different types of composting systems hand, is more regulated as all materials are ground and turned over
such as: (i) home/garden composting, where the maximum temperature intermittently, and higher temperatures can be reached by heating
may reach 40◦ C; and (ii) industrial composting, which is a much more processes. Commercial composting can be a more energy expensive
mechanical and controlled process [102]. A bioplastic that meets the process but the composting period is significantly reduced and is often
ASTM standard but without specification as to which sort of composting preferred for compostable materials like compostable utensils, wherein
it would have to go through can cause some confusion. The European the thickness may not allow them to breakdown in home composting
standard (EN 13432), on the other hand, requires the bioplastic to be systems even after years [102]. Composting conditions are very
degraded by industrial composting. The characteristics tested under this important as in some cases the plastic may just thermally degrade if it
standard include disintegration, biodegradability, as well as the effect surpasses a threshold and it might not be possible to convert the plastic
and presence of residues [103]. into the required biomass leaving only remnants. In this way many
Table 3 expands on the major differences between biodegradable and bioplastic companies recommend industrial composting rather than
compostable materials along with logos that will help consumers home composting for their products since commercial composting
distinguish if the material is biodegradable or compostable. A study conditions can be well controlled [110,111].
done in Brazil revealed that with the introduction of compostable carrier Danimer Scientific claims that the PHAs they produce are compost
bags, the use of PE carrier bags reduced over time. The same was able in both industrial and home composting systems as they meet the
observed in the introduction of compostable garbage disposal bags and ASTM and European Standards, with third party certification from
tableware, since waste materials generated during large functions or Vinçotte for home composting [112].These claims have also been sup
events can now be disposed in one single compostable outlet [104,105]. ported by a study in 2018 by the University of Georgia that studied the
As in the case of biodegradable materials, a misconception seems to degradation and compostability of P(3HB-co-3HHx). Hence, although P
exist in the case of compostable materials as well. There are petroleum- (3HB) is easily thermally degraded, PHAs containing larger monomers
based resins that are compostable in both garden and industrial com are more heat stable thereby allowing them to be both durable as well as
posts, and there are some forms of cellulose that may biodegrade but easily composted even in domestic settings, unlike other compostable
may not be compostable. Although all biodegradable materials are not plastics like PLA that require the higher temperatures of industrial
compostable, all compostable materials are biodegradable. Major dif composting facilities [113].
ferences between the two have been listed in Table 3. Compostable
materials provide an added benefit of enriching the humus depending on 3.3. Eco-toxicity due to polymer breakdown
the byproducts released in the process [106–108].
Although some materials like PLA do require high temperatures in Conventional plastics, when left in the soil, can break down into
small microparticles and additives such as Bisphenol A may be released
into the soil. These particles and chemicals can then enter our food chain
Table 3
Biodegradable versus Compostable. This table summarizes the differences
via the water we drink and finally cause biomagnifications in humans
between biodegradable and compostable materials. From the table, it is evident who are at the top of their respective food chain. In fact, BPA is known to
that certifying a material as compostable requires the adherence to stringent be a hormone disruptor in vertebrates and can even cause changes in
guidelines hence making it a clearer term than biodegradable. It should also be gene expression [114,115]. Oxo-degradable plastics contain metals,
noted that all compostable materials are biodegradable but the reverse is not which were added to enable quick degradation of the compound, and
true. these metals can leach into the soil and change the nutrient composition
Biodegradable Compostable or may even affect the water table [116]. In the same way, if not
disposed of properly, the byproducts of some, but not all, bioplastics can
Standards EN17033 acts as the standard for Must meet the ASTM D6400
followed biodegradable mulch films while or EN 13432 standard cause debilitating damage to the surrounding ecosystems and the food
ISO17556 is used to determine web it holds. For example, the degradation of PLA in marine sediments
aerobic biodegradation of plastics was shown to affect the microbial diversity and increase the decompo
Duration >90% should be converted to CO2 Less than or equal to three sition of organic carbon as well as reduce the inorganic nitrogen release,
within two years months
Byproducts No requirement regarding the No physical remnants should
which can affect N and P recycling, and that could have a lasting impact
absence of remnants be found and no toxic on the diversity of flora and fauna growing in the area [117]. In some
byproducts should be degradation studies, although the amount of bacterial biomass in
produced PLA-degraded soils did not vary significantly, it was seen that the di
Interrelation All biodegradable materials are not All compostable materials
versity varied, which reduced the oxidative activities of ammonium and
compostable are biodegradable
Logo nitrite ions [118,119]. To date, the byproducts of PHA have not been
shown to have any toxic effects on the surrounding environment,
including soil, marine sea beds or even the human body. In fact, a study
has shown that the placement and degradation of PHA can increase the
microbial diversity in the surrounding soil over the period of degrada
tion, as it may serve as a carbon source to surrounding organisms [71,
120].
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4. Bioplastics disposal incineration to reclaim heat, as practiced in Sweden [128]. Even in these
cases, it is difficult to recycle agricultural plastic products as it is quite
Contrary to popular belief, not all bioplastics can be left out in the costly to remove the contaminants [129,130]. In such situations, the
open to decompose and often require controlled conditions for their plastic may be converted to oil through plastic pyrrolysis, which does
degradation and even separation from conventional plastic waste to not require water as the process occurs in vacuum or can even be used
achieve the optimal rate of degradation as commercialized. for road laying [131,132]. However, even with these alternatives,
landfilling and incineration still take place today and may start to show
4.1. Disposal strategies for conventional plastics detrimental effects in the future.
Before the population boom and land crises, dumping waste into 4.2. Disposal strategies for bioplastics
landfills was the most common way to dispose of plastics. Often there
was no segregation in this case; plastics and biological waste materials One of the biggest misconceptions regarding the disposal of bio
were thrown together. However, the presence of other compounds can plastics is that it can be dumped anywhere and degradation is assured.
cause some additives in the plastics, such as metal compounds in oxo- This is not true of most of the bioplastics including PLA. For polymers
degradable plastics or epoxy stabilizers, to break down into toxic sub made from seaweed, this holds true however such polymers have their
stances, which could leach into the soil and degrade the quality of the own drawbacks with regards to thermal stability [53,109,133].
land as well as surrounding water resources over time [121]. As the As mentioned before, not all bioplastics are degradable and in fact,
landfills fill up, the waste will eventually be incinerated, which may there is no issue in recycling these non-degradable bioplastics with
cause massive air pollution in many areas. The segregation of plastics conventional plastics since they are indistinguishable in terms of poly
from other materials is an important aspect of sustainable change, mer properties. The real problem lies in the disposal of degradable and
however at present, some municipalities still dump them together in the compostable plastics, which will not mix with conventional plastics
landfills thus rendering the segregation futile. during the degradation processes. For this reason, it is very important to
Although there are still issues of people dumping plastic wastes into note that degradable or compostable bioplastics should not be disposed
the ocean, with tourism and corporate irresponsibility being the largest with normal plastics [106]. Fig. 4a and b elucidate some of the pro
contributors, more care is now being taken by governments of various cesses, like mechanical or organic recycling, that post consumerism
countries to remedy the issue by holding clean up drives or campaigns, bioplastics may go through. Most bioplastics seen in the market undergo
such as the Swachh Bharat Abhiyan or Clean India Movement started in mechanical recycling since many of them possess physical and chemical
India in 2014 [122,123]. As of today, countries like Sweden and properties identical to conventional plastics. On the other hand, organic
Singapore use the plastic waste generated for the production of heat and recycling is more well suited to plastics that are compostable and which
electricity through controlled incineration and via multiple filters to can biodegrade under general industrial composting conditions [134,
prevent air pollution [124–126]. 135].
The biggest problem in both developed and developing countries Recycling of bioplastics, especially if for food-grade applications,
seems to be the widespread use of single use plastics. Recycling seems to requires a lot more processing to free the plastic of contaminants. Hence,
be the best end of life option for these plastics and this can be achieved some compostable plastics should instead be collected with biowaste
through proper doorstep segregation [127]. As shown in Fig. 3, there are and can be used to create enriched compost, which is more valuable
many options for recycling wherein primary to tertiary methods include [136].This is much easier said than done because the compostable
the use of recycled material to create a product that may be used again as plastics look no different from the non-degradable plastics unless they
a raw material, whereas quaternary recycling is essentially just have been demarcated by any symbols or logos that pertain to the nature
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A. Nandakumar et al. Renewable and Sustainable Energy Reviews 147 (2021) 111237
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A. Nandakumar et al. Renewable and Sustainable Energy Reviews 147 (2021) 111237
Fig. 5. Disposal of PLA. This figure depicts the general flow of events asso
ciated with PLA along with the various end of life options for waste PLA. Since
PLA is only biodegradable under specific conditions not offered by home Fig. 6. Disposal of PHA. This figure depicts the life of PHA from production to
composting, it has to first go through an industrial composting facility before it disposal to recycling. If PHA is collected with other polymers like PLA it can be
can be mixed with the soil. Another option is for the products to go through sent for industrial composting and the waste can be used as a substrate for PHA
Filabot recycling, wherein PLA products (usually failed prints) are extruded into production. In case PHA is collected alone with food waste, the waste can be
filaments which can then be used for 3D printing. used as agricultural mulch or can be put through sewage treatment since PHA
degrading microbes are present in soil as well as in sludge.
integrated into industrial composters as well as home composting sys
tems. Danimer Scientifics’ PHA meets the European and ASTM stan consumer’s eyes.
dards as well as the Vinçotte standard for home composting [112]. PHAs
may also be degraded in aerobic lagoon water treatment systems since 5.1. Greenwashing practices
PHA is more degradable in water than in soil, and these systems contain
a good number of microbes [98,99]. This also means that separation of An important term to be included in a discussion on bioplastics
PHA and biowastes need not be as stringent as in the case of other would be ‘greenwashing’, which is defined as “the act of misleading
bioplastics, which could reduce the need for separate bins and com consumers regarding the environmental practices of organizations
posting systems. (firm-level greenwashing) or the environmental benefits of a product or
Although not ideal, even if PHAs were to end up in landfills, their service (product/service-level greenwashing)” [151]. Coined by Jay
degradation would still occur in anaerobic conditions, albeit a lot slower Westerveld in 1986, this term was meant to imply putting on a pretense
[145,146]. PHAs can be disposed into anaerobic wastewater treatment of being more environmentally conscious than one actually is. Green
digesters since the activated sludge contains microbes that are capable washing is often seen in the form of false advertising wherein important
of degrading the polymer, and such systems were even shown to be details are often left out or false claims are made. Westerveld came up
improved due to the denitrification imposed by the polymer [147]. In with the term after seeing a note at a hotel that asked guests to reuse
this manner, the disposal of PHA can be integrated into already existing their towels to save the environment. It was evident that the hotel did
disposal systems thereby reducing set up costs. Such waste systems may not actually care about the environment as they were expanding into the
also generate carbon sources used to produce PHA [148,149]. Fig. 6 beach front at the time, hence endangering many coral reefs, and in
depicts the possible disposal mechanisms for PHA products. reality wanted to save on the laundry costs [4]. Often such practices are
Unfortunately, recycling of some PHAs like P(3HB) may not be a means of capitalising on the conscious consumer and their growing
feasible since it is not very stable at high temperatures, and may be need for environmentally sound items. Greenwashing practices bring
difficult to isolate if mixed with PET and other conventional plastics in about consumer skepticism towards such products but also inadver
recycling units [111]. Recently, research was conducted to investigate tently towards actual green products, which can hinder the development
the prospects of chemically recycling PHA products, since many prod of sustainable societies.
ucts such as crotonic acid can have a second life as herbicides, plasti
cizers,etc. The decomposition of these products to monomers do not
require very high temperatures, which could reduce costs of running 5.2. Drawbacks of bioplastics
such units although the pyrolytic reaction may take a longer time [150].
Although most bioplastics have been touted for their contribution to
5. Economical and environmental outlook sustainable living, we have been viewing most of them through green
tinted glasses. For example, companies like Pepsico have been lauded for
Bioplastics may seem like the obvious solution to our current prob moving onto 100% biobased PET, which is actually bio-based but not
lems, however, one must also take into consideration the cost of such an biodegradable. Other examples include oxo-degradable plastics [152],
implementation and the effects it would have on our economy and the as already discussed in an earlier section of this review.
working class population. The general hype around bioplastics has also The IUPAC has clarified that a biobased polymer with properties
caused many companies to resort to pulling wool over the conscious similar to a petroleum-based one is not more favorable in terms of their
environmental impact unless a life cycle assessment (LCA) comparison
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A. Nandakumar et al. Renewable and Sustainable Energy Reviews 147 (2021) 111237
deems it so [20]. An LCA or cradle-to-grave analysis checks the envi PVA can be produced using renewable sources like ethylene gas or
ronmental impacts of all the processes related to the product starting ethanol as raw materials, but these processes have proven to be
from the raw material to its disposal or degradation [153]. Such an commercially non-viable [158]. However, with the rising ubiquity of
analysis has not been covered by many companies that focus only on the bio-ethanol, production costs of PVA may decrease in the subsequent
carbon footprint of the bioplastic production. For example, the biomass years [165]. Starch can be added to PVA to make it economically
often used for PLA production is corn or maize and the land required to feasible and improve the biodegradability of the polymer [166].
produce that amount of raw material can create a food conflict, espe In the case of PHAs, methods to reduce environmental and economic
cially in countries like Brazil where there is extensive research on bio costs have been underway, such as: (i) genetically engineering strains for
plastic production from agricultural produce [154]. LCAs have shown efficient PHA production, (ii) using agricultural waste materials and
that indeed there is a huge problem of food versus bioplastic production wastewater as substrates, and (iii) recycling the solvents used for
but a report from the Institute for Bioplastics and Biocomposites in extraction [167,168].Wastewater from sewage treatment plants are also
Hanover stated that bioplastics currently only use 0.02% of agricultural being considered as a carbon substrate for PHA production. The acti
land [155,156]. The addition of non-biodegradable components into vated sludge present in such processes would have a very diverse mi
biopolymers to improve their mechanical properties simultaneously crobial community, and the mixed carbon sources could enhance the
reduces their biodegradable properties too [157]. production of PHA since some microbes may be able to use up the
A case study comparing Mater-Bi (a starch-based plastic) and PE substrates that could be limiting to the other. This is evident in the case
revealed that although production of Mater-Bi reduces the use of fossil where anaerobic methane production increased by 25% in plants that
resources, the production of its raw material (corn) requires extensive contain microbes able to accumulate PHA granules [169].
use of fertilizers and pesticides, which can cause detrimental after effects Several companies in the field of PHA production, such as BioMatera
like acidification of the soil and eutrophication. Furthermore, the LCA and BioOn, are attempting to use new techniques to reduce the cost, and
showed that recycling the PE products produced an overall reduced the prosperity of these companies, unlike their forefathers, can also be
environmental impact than recycling or composting the Mater-Bi plas linked to the increasing environmental awareness of the general masses
tics [157]. As for PVA, its major drawback lies in the fact that it is today [170]. Some novel methods for PHA extraction include Aqueous
produced from non-renewable resources like oil, and the fluctuating Two Phase Extraction (ATPE) and biological recovery methods such as
nature of the price of raw materials acts as a major setback in the growth the use of mealworms. These methods can minimize the amount of toxic
of its market [158]. Unlike most polymers, PVA also requires compo solvents required for purification processes and reduce the volume of
nents like poly(vinyl acetate) for polymerization due to the instability of water required to treat and dispose of them, hence alleviating some of
its own vinyl monomers. Additionally, if the polymer is created through the economical and environmental burden [171,172].
alcoholysis, large quantities of methanol are required and the disposal of In addition, PHAs can be tailor made for far more diverse applica
such toxic solvents can cause many environmental side effects [159]. tions by varying the monomer compositions and are also known to be
PVA and Mater-Bi cost about US$ 2.16/kg and US$ 2.3/kg, respectively, highly hydrophobic, and sink when placed in aqueous solutions [173].
and it is evident that neither of these can compete with the market price Since PHA production requires microorganisms, some toxic materials
of US$ 1.3 - US$ 1.7/kg of conventional plastics [160,161]. like halogens may be transformed during fermentation. Using cyano
Although PHA was predicted to be in high demand by 2020, as of bacteria to produce PHAs may also make the process independent of the
now, the market for this polymer is very poor as it is almost four times agriculture sector, since algal farms can be set atop buildings, on in
the cost of conventional plastics [9]. A large fraction of the cost goes to dustrial sites or even in the ocean [174]. These various advantages and
the carbon substrate as well as purification processes. Sterilization the novel methods for its extraction make PHA an environmentally
processes, poor microbial growth and poor carbon to PHA conversion sound choice to replace at least some conventional plastics.
are other factors that contribute to the high price [162]. Among the
extraction techniques, solvent extraction is the most established, but 6. Future perspectives
environmental impacts and the high cost of scaling up the process makes
it a hazardous option. Methods to use waste solvents for extraction are Although plastic pollution is a global issue, awareness of its severity
currently underway to lower environmental risk as well as the overall is still lacking among the general population, or neglected due to the fast
cost through recycling. While enzymatic digestion may seem like the paced life that is obsessed with convenience as seen in most cities. In
best choice in terms of minimal degradation as well as reduced envi Singapore, many supermarkets have commented that consumers are
ronmental footprint, the high cost of enzymes makes it unfavorable for quite indifferent to biodegradable shopping bags despite the many
large scale production [40]. W.R. Grace and Company was the first promotions [126]. This could be due to greenwashing practices, which
company to start P(3HB) production but had to close down due to low have caused consumers to revert back to using conventional plastics and
synthesis efficiency and problems with purification. Similarly, in 2006, a pay less attention to any sort of bioplastic campaigning. However, the
joint venture by the name of Telles aimed to achieve high PHA pro existence of different varieties of bioplastics and how to properly dispose
duction but collapsed in 2012 due to poor sales [163]. of them should be made common knowledge by now. Under the guise of
being sustainable, many companies have added to the problem by
5.3. Current methods of mediation switching to oxo-degradable plastics or neglecting to inform consumers
of the same disposal mechanisms that they may have been informed of
LCA is frequently carried out without considering the logistics by the bioplastic provider. States have been advised to implement the
behind processes such as collection and sorting of waste, hence over ‘naming and shaming’ strategy to get corporations to make voluntary
looking the advantages that bioplastics, in the form of disposable cutlery cuts and transitions to reduce their ecological footprint [175]. A study in
or compostable bags, can provide [157]. Moreover, companies and re Germany showed that though compostable biobased plastics appeal to a
searchers alike are now focusing on devising novel methods to reduce majority of the consumers, proper disposal as instructed on the pack
the costs involved in the production processes. Starch-based polymers aging is not followed through. Hence, it is important to make consumers
reinforced with corn and wheat husks as fillers have improved gas familiar with the types of biobased products and the steps to be taken in
barrier properties while at the same time decreasing energy inputs and their disposal to gain the full environmental benefit of these plastics
overall costs since the raw material used is an agricultural byproduct. [176]. To reduce the amount of effort by the consumers, it would be a
Cost effective techniques like surface coating and crosslinking have also good idea to use bioplastics that are easily compostable like PHAs and
been developed to reduce the moisture sensitivity of this polymer lignocellulosic polymers since these can be easily disposed along with
without having to drastically reduce the starch content in blends [164]. other organic waste. To expedite the commercialization and integration
11
A. Nandakumar et al. Renewable and Sustainable Energy Reviews 147 (2021) 111237
of these bioplastics into our daily lives, research on these polymers is authors have given approval to the final version of the manuscript.
currently focused on reducing the cost in terms of raw materials and Ardra Nandakumar: Conceptualisation, Writing- Original Draft. Jo-
fermentation processes. In case of PHAs, the major cost of production is Ann Chuah: Writing- Reviewing and Editing, Validation. Kumar
borne by the acquisition of raw materials and for this reason, PHA Sudesh: Supervision, Funding acquisition.
production is currently being integrated with other processes such as
wastewater treatment and PET degradation [149,177,178]. On the other
hand, in case of starch-based polymeric blends whose major disadvan Declaration of competing interest
tage lies in its poor gas barrier properties, studies have shown that
reinforcement with other natural substances such as corn or wheat hulls The authors declare that they have no known competing financial
can improve these properties of these blends. The components were also interests or personal relationships that could have appeared to influence
compatible with each other due to the hydrophilic nature of the mate the work reported in this paper.
rials involved. The cost of transportation of these polymers can also be
diminished by splitting the foaming system into two steps [164]. Pichia Acknowledgment
pastoris, a methylotrophic yeast, is under consideration as a potential
producer of protein-based polymers due to high product yields and ease This study was supported by the grant from the Ministry of Higher
in downstream processing due to secretory production and methods to Education Malaysia titled “Soil Analysis and Value-Addition to Oil Palm
further improve protein expression in this host and to decrease prote Trunk (OPT) and Sap Through Biotechnology” [203/PBIOLOGI/
olysis are being looked into [179]. From an environmental perspective, 67811001] as well as Science and Technology Research Partnership for
solvents used in the production can often be recycled and researchers Sustainable Development (SATREPS). We would like to thank Dr. S.
have also found a new method of converting waste PLA into a green Choudhury from Vigilenz® Medical Devices Sdn. Bhd. for providing the
solvent known as methyl lactate that can in turn be used for the pro image of a medical suture.
duction of nitrocellulose and is also low in toxicity [180]. Shift from
metal based catalysts to organic catalysts also provide a potential Appendix A. Supplementary data
method to reduce the ecological impact of bioplastic production [181].
Supplementary data to this article can be found online at https://doi.
7. Conclusion org/10.1016/j.rser.2021.111237.
12
A. Nandakumar et al. Renewable and Sustainable Energy Reviews 147 (2021) 111237
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