Article

Cite This: Environ. Sci. Technol. 2018, 52, 10441−10452 pubs.acs.org/est

Biodegradable Plastic Blends Create New Possibilities for End-of-Life

Management of Plastics but They Are Not a Panacea for Plastic
Pollution
Tanja Narancic,† Steven Verstichel,‡ Srinivasa Reddy Chaganti,§ Laura Morales-Gamez,∥
Shane T. Kenny,∥ Bruno De Wilde,‡ Ramesh Babu Padamati,*,§,∥ and Kevin E. O’Connor*,†,⊥
†
UCD Earth Institute and School of Biomolecular and Biomedical Science, University College Dublin, Belfield, Dublin 4, Ireland
‡
OWS nv, Dok Noord 5, 9000 Gent, Belgium
Downloaded via CTR OF POLYMER AND CARBON MATERIALS on January 7, 2019 at 11:39:26 (UTC).

§
AMBER Centre, CRANN Institute, School of Physics, Trinity College Dublin, Dublin 2, Ireland
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

∥
Bioplastech Limited, Nova UCD, Belfield Innovation Park, University College Dublin, Belfield, Dublin 4, Ireland
⊥
BEACON - Bioeconomy Research Centre, University College Dublin, Belfield, Dublin 4, Ireland
*
S Supporting Information

ABSTRACT: Plastic waste pollution is a global environ-

mental problem which could be addressed by biodegradable
plastics. The latter are blended together to achieve
commercially functional properties, but the environmental
fate of these blends is unknown. We have tested neat
polymers, polylactic acid (PLA), polyhydroxybutyrate, poly-
hydroxyoctanoate, poly(butylene succinate), thermoplastic
starch, polycaprolactone (PCL), and blends thereof for
biodegradation across seven managed and unmanaged
environments. PLA is one of the world’s best-selling biodegradable plastics, but it is not home compostable. We show here
that PLA when blended with PCL becomes home compostable. We also demonstrate that the majority of the tested bioplastics
and their blends degrade by thermophilic anaerobic digestion with high biogas output, but degradation times are 3−6 times
longer than the retention times in commercial plants. While some polymers and their blends showed good biodegradation in
soil and water, the majority of polymers and their blends tested in this study failed to achieve ISO and ASTM biodegradation
standards, and some failed to show any biodegradation. Thus, biodegradable plastic blends need careful postconsumer
management, and further design to allow more rapid biodegradation in multiple environments is needed as their release into the
environment can cause plastic pollution.

■ INTRODUCTION
Biodegradable polymers are promoted as an environmental
solution to plastic pollution. However, their degradation in
managed and unmanaged environments is not well under-
stood. Thus, humankind does not understand the end-of-life
management possibilities nor the environmental impact of
these polymers if they are released into the environment. The
fact that biodegradable polymers are blended together to
achieve functionality introduces further uncertainty for
biodegradable plastic waste management and environmental
impact. The aim of this study is to understand the
biodegradation of individual polymers and their blends in
managed and unmanaged environments.
Polymers are ideal materials used in thousands of industrial
and consumer products. A major application area for polymers
is plastics. However, the recalcitrant nature of oil-based plastic
coupled with a single-use throw away culture and release into
the environment results in negative environmental consequen-
ces; e.g., 4.6−12.6 million tonnes of plastic waste generated in
2010 by 192 costal countries have ended up in the ocean.1
While extreme weather events can result in plastic from seaside
properties entering into the marine environment, single-use
plastics are the major single contributor to plastic waste in
terrestrial and marine environments.2 For example, single use
plastic items make up 50% of marine and beach litter in
Europe.3 Plastic debris kills hundreds of thousands of sea
turtles, seals, whales, and seabirds due to ingestion or
entanglement.2,4,5
Some countries are singled out as major contributors to
plastic pollution, while others have a landfill ban in place.6,7
Nearly 30% of plastic waste is still landfilled in Europe, and the
current EU plan is to reduce landfilling of plastic to no more
than 10% by 2030.7 In the USA, 53% of total municipal solid
waste (MSW) is landfilled, with plastic waste representing 13%
of MSW.8 The recycling rate of nondegradable plastics remains
Received: June 1, 2018
Revised: July 27, 2018
Accepted: July 27, 2018
Published: August 29, 2018

© 2018 American Chemical Society 10441 DOI: 10.1021/acs.est.8b02963

Environ. Sci. Technol. 2018, 52, 10441−10452
Environmental Science & Technology Article

Table 1. Biodegradable Polymers Used in This Study, Their Characteristics and Application
polymer origin characteristics application ref
polylactic acid (PLA) biobased crystalline, brittle packaging 13, 14
polyhydroxybutyrate (PHB) biobased crystalline, brittle packaging 15
polyhydroxyoctanoate (PHO) biobased elastomeric medical 15, 20
poly(butylene succinate) (PBS) biobased, petrochemical crystalline packaging 16
thermoplastic starch (TPS) biobased brittle packaging 19
polycaprolactone (PCL) petrochemical elastomeric medical 18, 21

stubbornly low globally.9 While recycling technologies are
available, the high price and relatively low quality of the
recycled plastics limits market applications. Biodegradable
plastics are especially interesting for nondurable applications
such as packaging and agricultural films where biodegradability
offers new end-of-life management options not open to
nondegradable plastics, e.g., composting and anaerobic
degradation. Biodegradability is an advantage when inadvertent
environmental release occurs to aquatic and terrestrial
environments. Human behavior is a critical factor in preventing
this uncontrolled release. However, biodegradable plastics that
degrade across a wide range of managed and unmanaged
environmental conditions offer greater economic and environ-
mental rewards compared to those that are limited to
biodegradation in a narrower set of environments. While
biodegradability is an attractive postconsumer characteristic,
these plastics must demonstrate performance in the market
prior to disposal. Nonetheless, many biodegradable plastics
often lack characteristics such as flexibility, strength, and
toughness. Thus, they do not perform as well as their
established nondegradable counterparts, and they must be
blended together to combine characteristics and offer
functionality for applications such as packaging. We have
blended polymers to achieve characteristics suitable for
packaging as the latter represents one of the largest uses of
plastic material and carries the highest risk for environmental
pollution.
The polymers and blends used in this study (Table 1) were
selected based on their application as packaging material10 and
mechanical properties such as tensile strength 11 and
elongation.12 Polylactic acid (PLA) is one of the major
bioplastics on the market used mainly as packaging material.13
PLA was previously blended with other materials to improve
its material modulus.14 Polyhydroxybutyrate (PHB) and
polyhydroxyoctanoate (PHO) belong to the family of bacterial
polyesters, with the same backbone but different side-chain
lengths.15 Because of this structural difference, PHB is highly
crystalline and brittle, while PHO is a rubber-like material of
low crystallinity. With the emergence of biobased succinic acid
and 1,4-butanediol, poly(butylene succinate) (PBS) can now
be a biobased plastic16 with a melting temperature similar to
those of polyethylene and polypropylene.17 While polycapro-
lactone (PCL) is of petrochemical origin, it is biodegradable
and exhibits good elongation and good compatibility with
many types of polymers.18 Thermoplastic starch (TPS) is
completely biobased and biodegradable but is fragile compared
to petrochemical-based polymers such as polyethylene.19
The diversity of biodegradable materials and environments
makes it difficult to make simple and generic assessments of
their end-of-life fate. We have therefore investigated the fate of
a range of selected biodegradable plastics and their blends
simulating controlled vs uncontrolled environments to gain a
greater understanding of their potential environmental fate and
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possible future end-of-life management options. We identified
a surprising synergy but also antagonism between polymers in
plastic blends that affects both their biodegradability and
biodegradation rates which opens up new end-of-life manage-
ment options but also raises concerns about the release of
some of these biodegradable plastics in uncontrolled environ-
ments, e.g., soil, oceans, and rivers.
■ MATERIALS AND METHODS
Biodegradable polymers polylactic acid (PLA), polyhydrox-
ybutyrate (PHB), polyhydroxyoctanoate (PHO), poly-
(butylene succinate) (PBS), thermoplastic starch (TPS),
polycaprolactone (PCL), and their blends were tested for
biodegradation in managed (industrial composting, anaerobic
digestion, home composting) and unmanaged (marine, fresh
water, aquatic anaerobic digestion, soil) environments. The
polymers were blended at ratios that gave plastic characteristics
suitable for packaging applications. The mechanical properties
and morphology of the neat polymers and blends were
investigated.
Biodegradable Plastics Compounding. Neat polymers
and their plastic blends (Table 2) were processed using a
Table 2. Matrix of Polymers Used in This Study
polymer trade name supplier
PLA Biopolymer-4043D Nature Works, USA
PHB ENMATY1000 TiTAN
PHO Bioplastech R Bioplastech
PCL CAPA 6500 Perstorp
PBS PBE 003 NaturePlast
TPS Bioplast TPS BIOTEC
Brabender melt processor. Melt mixing of the polymers was
carried out for 10 min at a rotor speed of 50 rpm. Before
blending, all polymers pellets were dried in vacuum at 80 °C
overnight and 60 °C for PCL, PHA, and TPS. The melt-
processed samples were compression molded to 20 × 20 × 0.2
cm rectangular specimens at 180 °C with an applied pressure
of 200 MPa using a Servitech Polystat 200 T compression
press.
Mechanical Testing. Biodegradable plastic sheets were
punched with a cutter to dumbbell-shaped samples with
dimensions of 25 mm × 4 mm × 1 mm and were used for
stress−strain measurements. Tensile measurements were
carried out using a Zwick twin column tensile tester with a
100 N load cell and calibrated with a 2 kg standard. The tensile
tests were carried out at room temperature and a cross head
speed of 25 mm/min. Young’s modulus, ultimate tensile
strength, breaking strength, elongation at break and toughness
values were calculated by integrating the stress−strain data
obtained from the samples.
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Scanning Electron Microscopy (SEM). The surface
morphology of polymers and blends was examined using
SEM. The samples were fixed on the SEM stubs using carbon
tape and sputtered with gold/palladium (80/20 ratio) for 15 s.
The cross-section images of the composites were obtained by a
high-resolution field emission Zeiss Ultra Plus-SEM (Carl
Zesis AG, Oberkochen, Germany) with an accelerating voltage
of 5 kV under high vacuum. The internal morphology of the
biodegradable plastics was studied using the fractured surface
of the systems.
Differential Scanning Calorimetry (DSC). The glass
transition temperature (Tg) and melting temperature (Tm) of
polymers and biodegradable plastics were analyzed using a
PerkinElmer Pyris Diamond calorimeter calibrated to indium
standards. The samples were sealed in aluminum pans and
heated from −90 to +200 °C at a rate of 10 °C min−1. The
samples were run through a first cycle of heating and cooling to
remove the thermal history.
Biodegradation Tests. All tests were done according to
available international standards, where a minimum incubation
time was applied. In some cases, we prolonged the incubation
until we observed a plateau, and these cases are described for
each biodegradation test.
During the aerobic biodegradation of organic materials,
oxygen is consumed and carbon is converted to gaseous,
mineral carbon as carbon dioxide, CO2. Part of the organic
material is assimilated for cell growth. Under anaerobic
conditions, the organic carbon of the material is converted
into biogas CO2 and CH4. Biodegradation is calculated as the
percentage of organic carbon content of the tested sample
which has been converted to gaseous, mineral C in the form of
CO2 (aerobic conditions) or CO2 and CH4 (anaerobic
conditions).
The organic carbon content of cellulose as the reference
material used in these tests and bioplastics was determined by
subtracting the total inorganic carbon content from the total
carbon content using a Primacs SNC-100 analyzer. The carbon
content (g) at the start of incubation is designated as Ci. A
cumulative CO2 production (g) was then measured for each
reactor in all aerobic tests and this value was divided by the
molar mass of CO2 (44 g/mol) and multiplied by the molar
mass of carbon (12 g/mol) to obtain the amount of gaseous
carbon produced (Cg; g).
For the tests performed under anaerobic conditions, 1 mol
of solid carbon of the test item is converted into 1 mol of
gaseous CO2 or CH4 (C + 2 H2→ CH4 and C + O2→ CO2).
One mole of gaseous carbon occupies 22.414 Nl (Nl is a liter
at 0 °C and 1013.25 hPa), and this is converted to g of C using
the molar mass of carbon (12 g/mol).
The biodegradation (%) is calculated by dividing the
cumulative average net gaseous carbon production of the test
compound by the original cumulative average amount of solid
carbon of the test compound and multiplying by 100:
%biodegradation
[mean C test(g ) − mean Ccontrol(g )] × 100
= chromatograph (PerkinElmer Clarus 500) and TotalChem
Ci
In all biodegradation tests, control reactors without test item
are taken along to be able to measure the net CO2 or biogas
production derived from the degradation of the test material.
Cellulose was used as a reference material to evaluate the
validity of the test. The validity criteria, which were 90%
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relative biodegradation of the reference material cellulose, were
always reached. Standard deviation among three independent
replicates was calculated. A short description for each test is
given below.
Controlled Industrial Composting Conditions (ISO
14855). The controlled composting biodegradation test is an
optimized simulation of an intensive aerobic composting
process where the biodegradability of a test item under dry,
aerobic conditions is determined. The test is performed
according to ISO 14855-1 (2012). The maximum test period is
180 days.
The inoculum is derived from the organic fraction of
municipal solid waste, which is stabilized and matured in a
composting bin at the laboratory under controlled aeration for
more than 20 weeks. Before use, the mature compost is sieved
through a 5 mm sieve and the fine fraction is used as the
inoculum, rich in bacteria and fungi. Total solids content of the
compost inoculum is 50−55%, while volatile solids concen-
tration is >30% of dry solids. Typically, 80 g of test material is
added to 1200 g of inoculum. The reactors are incubated at 58
± 2 °C. The flow rate of pressurized dry air is controlled by a
gas flow controller and directed into the composting vessel at
the bottom through a porous plate. CO2 produced during the
test as well as O2 are analyzed continuously as part of the gas
leaving each individual reactor using a gas chromatograph
(PerkinElmer Clarus 500), while the flow rate is measured with
a Brooks 5860S mass flow meter. When the microbial activity
is reduced the test is converted to static conditions in which
the oxygen in the headspace is consumed by the micro-
organisms. The evolved CO2 is absorbed in a beaker using
KOH and determined by titration with a Metrohm 888
Titrando.
Controlled Composting Conditions at Ambient
Temperature (ISO 14855 at 28 °C). The test procedure is
the same as defined in ISO 14855 and described in the
paragraph above, but the test temperature is decreased to 28
°C ± 2 °C to simulate home composting conditions.
Maximum test duration is 1 year.
High-Solids Anaerobic Biodegradation Test: Anaero-
bic Digestion (AD; ISO 15985). The biodegradability of
samples in a solid-state anaerobic digestion system or in a
sanitary landfill is determined through high-rate dry anaerobic
batch fermentation. This method simulates and accelerates the
biodegradation process that takes place in a landfill because it
is a stationary (no mixing) and dry fermentation under optimal
conditions. The incubation temperature is 52 ± 2 °C, and the
duration of the test is at least 15 days. Test item (15 g) is
added to a large amount of highly active inoculum (1000 g)
derived from a digester that has been operated during several
months on the organic fraction of household waste and has
been stabilized during a short postfermentation of several days
to reduce biogas production rate to a level below 1.5 Nl
biogas/kg/day. The generated biogas is collected in an
inverted graduated cylinder in water. The water in contact
with the gas has pH < 2 during the whole period of the test to
avoid CO2 loss through absorption in the water. A gas
software are used for the determination of the concentration of
CH4 and CO2 in the biogas.
Soil Biodegradation Test (ISO 17556). The biodegra-
dation in soil is evaluated according to ISO 17556 (2012)
using standard soil. Maximum testing period is 2 years. The
standard soil consists of a mixture of 70% industrial quartz
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Environmental Science & Technology
Figure 1. Mechanical properties of biobased and biodegradable plastics (purple circles) and fossil-based biodegradable polycaprolactone (green
square) and their blends (blue triangles). By blending these biodegradable polymers (purple circles) with each other they are moving into new
design space (blue triangle) and thus opening up new opportunities for applications such as plastics.
sand, 10% kaolinite clay, 16% natural soil, and 4% mature
compost. The soil was collected from a sandy field in Lokeren
and 2 types of forest in Moerbeke (all located in Belgium). The
mixture consists of 1/3 field soil and 2/3 forest soils. The soil
is sieved over a 2 mm sieve to remove stones and other inert
materials, roots, and other plant debris and thoroughly mixed.
The mature compost is derived from the organic fraction of
municipal solid waste. The waste is stabilized and aerated in a
composting bin at the laboratory under controlled conditions
for at least 20 weeks. Before use, the compost is sieved through
a 5 mm sieve. Finally, salts are added to the standard soil by
means of nutrients solution (per l: KH2PO4 9.6 g, MgSO4 4.8
g, NaNO3 19.2 g, urea 9.6 g and NH4Cl 19.2 g/L) to obtain
the final inoculum. At start-up, 2.0 g of reference or test item is
mixed with 500 g of soil inoculum, while the control reactors
contain only 500 g soil inoculum. The reactors are closed
airtight and placed in the dark at 25 °C ± 2 °C. The evolved
CO2 is absorbed in a beaker with KOH and determined by
titration with a Metrohm 888 Titrando.
Marine Biodegradation (ASTM D6691). Testing is
performed according to ASTM D6691 (2009) and determines
the biodegradation of a test item under laboratory conditions
by incubation in seawater. The test material is brought into
natural seawater enriched with inorganic nutrients (0.05 g/L of
NH4Cl and 0.1 g/L of KH2PO4) and containing an indigenous
population of micro-organisms. The natural seawater was
collected from open sea via a 1 km pipeline from SEA LIFE,
Blankenberge, Belgium. At start-up, each reactor is filled with
250 mL of enriched seawater. The reference and test item
(approximately 25 mg) are added directly to the reactors. The
reactors are incubated at a constant temperature (30 °C ± 1
°C) in the dark for a period of minimum 28 days. The evolved
CO2 is absorbed in KOH and determined by titration with a
Metrohm 888 Titrando.
Biodegradation in Aerobic, Aquatic Conditions
(Fresh Water; ISO 14851). The test is performed according
to ISO 14851 (2005). The test material is brought into a
chemically defined (mineral) liquid medium, essentially free of
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other organic carbon sources, and spiked with micro-
organisms. The source of microorganisms is a mixture of
activated sludge, obtained from different aerobic wastewater
treatment plants (Destelbergen, Gent and Lokeren, all located
in Belgium), that treat wastewater from domestic and/or
industrial origin. At start-up, each reactor is filled with 245 mL
mineral medium and 5 mL of sludge inoculum. The reference
and test item (approximately 25 mg) are added directly to the
reactors. The reactors are incubated at a constant temperature
(21 °C ± 1 °C) in the dark for a period of minimum 28 days.
The evolved CO2 is absorbed in KOH and determined by
titration with a Metrohm 888 Titrando.
Aqueous Anaerobic Biodegradation Test (ISO
14853). The test is performed according to ISO 14853
(2005). A 90 g portion of anaerobic sludge (corresponding to
about 10% of the sludge concentration in a real digester),
suspended in an oxygen-free medium, is placed in a suitable
vessel leaving headspace into which any gases produced may
be evolved. The anaerobic sludge is derived from the
wastewater treatment plant Ossemeersen, Gent, Belgium.
Prior to sealing, 25 mg of test compound is added. The
vessels are incubated at a constant temperature of 35 °C ± 2
°C. The headspace pressure resulting from the production of
gas is measured with a pressure transducer (UMS, INFIELD7c
with T1 Stitch-Tensiometer), and the DIC (dissolved
inorganic carbon, this is the inorganic carbon (mainly CO2)
that is dissolved in the liquid phase) content of the digesting
liquid is determined by addition of hydrochloric acid to the
reactors and measuring the subsequent pressure increase. The
biodegradation is calculated from the sum of the measured
biogas in the headspace and DIC in the liquid medium. The
total test duration is 56 days.
■ RESULTS
Mechanical Properties of Biobased and Biodegrad-
able Plastics. To address shortcomings in performance of
individual plastics (i.e., PLA is hard but brittle and PHO is
flexible but soft), blends were created where characteristics of
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Table 3. Compatibility of the Blends Used in This Study Was Determined by Differential Scanning Chromatography (DSC)
blend compatibility comment
PLA−PCL(80/20) compatible mechanical properties of the blend are better than neat polymer; single Tg peak observed
PLA−PBS(80/20) inconclusive mechanical properties of the blend are better than neat polymer; multiple melting peaks observed
PLA−PHB(80/20) compatible mechanical properties of the blend are better than neat polymers
PLA−PHO(85/15) inconclusive mechanical properties of the blend are better than neat polymers; multiple Tg peaks observed in DSC
PHB−PCL(60/40) incompatible mechanical properties of the blend inferior than neat polymers
PHB−PBS(50/50) compatible mechanical properties of the blend are better than neat polymer
PHB−PHO(85/15) incompatible mechanical properties of the blend inferior than neat polymers
PCL−TPS(70/30) incompatible mechanical properties of the blend inferior than neat polymers
PBS−TPS(60/40) compatible mechanical properties of the blend are better than neat polymer

Figure 2. Biodegradation of individual polymers and their plastic blends in multiple managed environments: home composting (ISO 14855, 28
°C); anaerobic digestion (ISO 15985, 52 °C); industrial composting (ISO 14855, 58 °C). Biodegradation is expressed as a percentage of
biodegradation of cellulose (green dotted line). The cutoff point for a material to be considered biodegradable under tested conditions is presented
with a red dashed line (90% of the reference material). *PHB, PHB−PCL(60/40), and PCL−TPS (70/30) were not tested in this study for home
composting as PHB is certified for home composting,28 and PCL and TPS are both home compostable.

individual polymers were combined with additive and
synergistic effects to give properties suitable for packaging
applications. The ratio of polymers in the blends was chosen
based on the scientific literature and our experience with these
materials.22−25
The blending of these polymers moved the created blends
into a plastic designer space previously unoccupied by
biodegradable polymers (Figure 1). By adding PCL or PHO
to PLA at a relatively low loading (<20% w/w), the newly
created materials became more flexible (Figure 1). While some
polymers were compatible, others were characterized by
multiple Tg peaks but still showed improved mechanical
10445
properties (Figure 1, Table 3, Figure S1). This is in keeping
with previous literature reports where immiscible blends of
polymers still showed improved properties.24 While PCL in
general shows good miscibility with other polymers,26 DSC
analysis showed that PCL and PHB are incompatible, resulting
in a blend with poorer mechanical properties compared to neat
polymers (Table 3). Despite some polymer blends showing
decreased mechanical properties, they were brought forward to
allow a broad examination of their end-of-life fate in simulated
managed and unmanaged environments.
Biodegradation of Bioplastic in Managed Environ-
ments. Surprisingly, the PLA−PCL(80/20) plastic blend
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Figure 3. Anaerobic digestion under high solid thermophilic conditions (ISO 15985). BMP is shown in blue and CO2 production in pink. The
standard deviation among biological triplicates was <5%.
degraded under home composting conditions (Figure 2). PLA
alone is not home compostable, as PLA biodegradation is
normally triggered by temperature above 50 °C,27 a temper-
ature not reached in home composting. The PLA−PCL blend
with 80% PLA reaches the biodegradation level of the
reference material (cellulose) in 259 days (Figure S2).
We also show that PLA when blended with another home-
compostable polymer PHB in an 80:20 ratio failed to reach the
standard for home composting (Figure 2). Blending of low
levels (<20% by weight) of nonhome compostable polymer
such as PHO to home-compostable PHB28 or PCL slows the
biodegradation of the blend but still allows the polymer blend
to achieve the home-compostable standard (Figure S2 and
Figure 2). The blending of two nonhome compostable
polymers (e.g., PLA−PBS and PLA−PHO) did not give rise
to plastic blends that achieved the standard for home
compostability (Figure 2).
While anaerobic digestion (AD) has been widely reported
for a range of organic wastes,29,30 it is an option scarcely
looked at when considering biodegradable polymer end-of-life
management and has never been investigated for polymer
blends.31 We have therefore tested a range of biodegradable
polymers and their plastic blends under a high-solids anaerobic
conditions biodegradation test, a possible scenario under
which postconsumer biodegradable plastics would be managed
(Figure 2B and 3). With the exception of PBS-TPS(60/40)
and individual polymers PBS and PHO all plastic blends are
biodegradable under anaerobic thermophilic conditions
(Figure 2B and Figure S3). AD, also known as biogasification,
is a biotechnological approach to renewable biomass-derived
energy production.
It is important to note that while the clear majority of
biodegradable plastics degrade by AD their degradation time is
three to six times longer than the retention time in industrial
anaerobic digestion plants (Figure 2B).
Between 48% and 63% of the biogas output was methane,
with the remainder as CO2, as a result of AD of various
biodegradable plastics (Figure 3). Biodegradable plastics with
higher total carbon content produced more methane (Figure
S4). The PHB−PCL (60/40) blend has the highest
biochemical methane potential (BMP) of 561 NL/kg, followed
by PCL−TPS (70/30) with 546 NL/kg (Figure 3). In both
cases, plastic blends had higher BMP than individual polymers,
suggesting the metabolism of the blend favors methane
production and demonstrating synergistic effect of blending
these polymers. PCL−TPS (70/30) and PHB−PCL (60/40)
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blends produced 37% and 18% more methane than expected
from the performance of individual polymers during AD
(Figure 3, Table S1). Anaerobic digestion of PCL−TPS (70/
30) yielded the expected amount of CO2, while the CO2
fraction was 15% lower in the case of PHB−PCL (60/40)
blend (Table S1).
Another example of synergism comes from blending PBS,
which is nondegradable in AD, with PHB. The blend yielded
1.4-fold more biogas than expected from individual polymers,
and both methane and CO2 fractions were 37% and 38%
higher than expected (Table S1). The polymer blend PHB−
PHO (85/15) generated the expected biogas output based on
the composition of the individual polymers (Table S1).
Under industrial composting conditions all tested plastics
reach the biodegradation standard, at least 90% of the
reference material biodegradation in 180 days (ISO 14855;
Figure 4A−C). The tested materials could be clustered into
three groups based on their degradation rate. The materials
PCL, PHB−PCL (60/40), PHB, and PCL-TPS (70/30)
showed fast degradation rates and reached complete
degradation in 40 days (Figure 4A). PHB−PHO (85/15),
PBS-TPS (60/40), and PHB−PBS (50/50) exhibited an
interesting evolution of degradation starting with a fast
degradation rate and reaching up to 52% degradation in the
first 5 days, followed by a decreased rate of degradation
(Figure 4B). The remainder of individual polymers and plastic
blends consisting of PLA and PHO and PBS showed a third
type of behavior with a lag phase in the first 20 days of the
biodegradation test before the onset of a higher rate of
biodegradation (Figure 4C).
The home compostable PLA−PCL plastic showed complete
degradation in 60 days under industrial composting conditions,
while PLA alone reached 90% biodegradation after 70 days
(Figure 4C). While all blends in the current study containing
PLA meet the standard to be considered biodegradable under
industrial composting conditions, the slowest degradation rate
was observed for the PLA−PHO (85/15) blend, which
reached biodegradation threshold after 120 days (Figure
4C). Indeed, 89.3% of PHO alone degraded after 65 days,
which suggests an antagonistic effect of these two polymers on
biodegradation under industrial composting conditions.
Biodegradation of Biodegradable Plastics in Unman-
aged Environments. PHB and TPS degraded completely in
all tested aquatic conditions: marine pelagic (30 °C), fresh
water aerobic (21 °C), and aquatic mesophilic anaerobic (35
°C) (Figure 5A−C). Only 6% of PHO degraded in anaerobic
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Figure 4. Relative biodegradation of biodegradable plastics in
industrial composting. Cellulose was used as a reference material
(ISO 14855, 58 °C). The test is considered valid if after 45 days the
biodegradation percentage of the reference item is more than 70% and
if the standard deviation of the biodegradation percentage of the
reference item is less than 20% at the end of the test. (A) Fast
degrading materials. TPS degrades completely in 22 days, while
cellulose reaches complete degradation in 40 days. (B) Materials
showing bimodal degradation;. (c) Slowly degrading materials. The
green dotted line represents degradation level of cellulose, which is
completely degraded during this test. The red dashed line represents
the cut off value of 90% relative biodegradation for the biodegradation
test. The standard deviation (SD) among biological triplicates was
<5%, except for PLA−PHB (80/20) with SD 10%.
aquatic conditions and up to 51% in fresh water in the testing
time frame of 56 days (Figure 5B and C). PHB−PHO (85/15)
blend showed a slower degradation rate in the first 10 days
compared to PHB alone, but the blend reached the same level
of biodegradation as PHB in marine conditions after 56 days
(Figure S5). While PCL showed excellent biodegradation in
terrestrial environments (Figures 2−4) and good biodegrada-
tion in a marine environment, it reached 50% or less
biodegradation in fresh water and aquatic anaerobic digestion
in 56 days (Figure 5A−C). Blending PCL with PHB had no
effect on biodegradation performance in a marine environment
test. However, the biodegradation under fresh water and
anaerobic aquatic conditions suggests that PCL blended with
PHB is antagonistic for biodegradation under the tested
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conditions (Figure 5A−C). Blending PCL to TPS is
antagonistic for biodegradation in marine and fresh water
environment (Figure 5A,B). Only 2.1% of PCL degraded in
anaerobic aquatic digestion test (Figure 5C). Since PCL makes
70% of the PCL−TPS blend this material degraded poorly in
anaerobic aquatic digestion test.
Less than 15% biodegradation was observed for PLA−PHB
(85/15), while no biodegradation of PLA alone or other PLA
based plastics was observed in aqueous environments (Figure
5A−C). Thus, PLA and its blends do not differ significantly
from nondegradable plastics for biodegradation in aqueous
environments in the 56 days of testing.
The blends PHB−PHO (85/15), PHB−PCL (60/40),
PCL−TPS (70/30), and PCL−PHO (85/15) were the only
blends to achieve the biodegradable bench mark in the soil test
environment (90% relative biodegradation in up to 2 years;
Figure 5D). PHB, TPS, and PCL were the only individual
polymers biodegradable under the soil test conditions, showing
complete biodegradation after 136 days (Figure 5D). Neither
PLA nor its blends showed significant biodegradability in soil
after 141 days (Figure 5D).
■ DISCUSSION
All methods applied in this study are designed to simulate
specific environmental conditions, i.e., industrial and home
composting, degradation in soil, anaerobic digestion, and
degradation in aquatic environments (fresh water, marine,
aquatic anaerobic digestion). The tests’ methods are designed
to yield the percentage conversion of the carbon in the test
material to evolved carbon dioxide as well as the rate of
conversion, and to allow assessments in a reasonable time
frame. For example, the proposed duration of the soil
biodegradation test is up to two years at 25 °C. We recognize
that the temperatures used in international tests applied in this
study are higher than temperatures in the unmanaged
environments that tests mimic. Given that the majority of
neat biopolymers and blends do not meet test standards one
can expect even slower degradation in soil, oceans and rivers
with lower temperatures and this needs to be carefully
considered when shaping plastic waste policies and plastic
product design.
The end-of-life management of biodegradable plastics has
focused predominantly on composting,32−34 but other options
are now emerging, e.g., anaerobic digestion (AD). AD is
targeting biodegradable waste, e.g., organic fraction of
municipal solid waste (MSW).35 One can envisage AD as
part of an integrated waste management strategy for the
organic fraction of MSW which would include biodegradable
plastics used for food packaging. AD can contribute to
renewable energy targets as it can generate biogas which can
be combusted to produce electricity. It is projected that 80% of
total U.S. electricity demand could be supplied by renewable
electricity technologies in 205036 and EU countries have
agreed on a renewable energy target of at least 27% of final
energy consumption in the EU by 2030 as part of the EU’s
energy and climate goals for 2030.37
We demonstrate here that biodegradable plastics have high
biochemical methane potential (BMP) of 265−600 NL/kg,
while food waste has a BMP of 200−529 NL/kg, indicating
that these plastics should positively contribute to the methane
production in AD of mixed wastes containing food waste. As
the biodegradable plastics in the current study contain only
carbon, oxygen and hydrogen, their mixing with food and
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Environmental Science & Technology
Figure 5. Biodegradation of individual polymers and plastic blends in unmanaged environments: (A) marine pelagic (ASTM D6691, 30 °C); (B)
fresh water aerobic biodegradation (ISO 14851, 21 °C); (C) aquatic anaerobic digestion (ISO 11734, 35 °C); (D) soil (ISO 17556).
Biodegradation is expressed as a percentage of biodegradation of cellulose (green dotted line). The cutoff point for a material to be considered
biodegradable under tested conditions is presented with a red dashed line.
municipal waste rich in nitrogen could contribute to optimal
C/N ratio, required for efficient methane production.38
It is imperative that biodegradable plastics are managed and
directed to the appropriate organic stream in MSW collection
as the uncontrolled release of biodegradable plastics in landfill
will contribute to greenhouse gas (GHG) emissions.
Consumers and waste collectors need to understand the
value of biodegradable plastics to society as they provide
opportunities to return carbon to soil as compost and to create
clean energy. Furthermore, food-contaminated biodegradable
plastic can be composted, making management easier than
current non-degradable plastics which must be source
separated. The infrastructure required to effectively manage
biodegradable plastics needs to be understood and developed.
One should not look at biodegradable plastics as an undesired
contaminant in waste, rather that waste collection systems
need to adapt to the evolving composition of waste.
While industrial composting has been extensively studied
and implemented, there is a growing interest in home
composting. Since PLA is widely used as a packaging
material,39 biodegradability at ambient temperature in home
compost demonstrated here by blending PLA with PCL would
be a highly beneficial attribute, as it can avoid collection and
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transport of packaging material to an industrial composting
facility thus contributing to mitigation of GHG emission.40
When PLA is blended with PCL in ratio 80:20, PCL spherical
droplets are formed and distributed uniformly in the
continuous PLA matrix (Figure 6). This decreases the stiffness
of PLA, forming a more flexible blend (Figure 1 and Table S2).
The material stiffness of the PLA−PCL blend is 2.7-fold lower
than for PLA and 3.8-fold higher than PCL alone (Figure 1
and Table S2). While other ratios of the two polymers also
alter their properties the 80:20 ratio results in a polymer with
interesting performance characteristics for applications such as
packaging.41 However, blending nonhome compostable PLA
with a different home compostable polymer, PHB does not
give rise to a home compostable blend. In the PLA−PHB (80/
20) blend, we do not observe the formation of regions or
droplets of different polymers (Figure 6). This indicates that
specific spherical structures formed when PLA is blended with
PCL are important for home compostability of the blend.
In the past decade, the awareness of plastic pollution in
oceans and rivers has brought into sharp focus a major
opportunity for biodegradable plastics to replace nondegrad-
able plastics in products that are likely to end up in a water
environment. This substitution could lead to plastic degrada-
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Environ. Sci. Technol. 2018, 52, 10441−10452
Environmental Science & Technology
Figure 6. Scanning electron microscopy (SEM) micrograph of fracture surface of neat biodegradable polymers PLA, PCL, and PHB and home-
compostable plastic blend PLA−PCL (80/20) and noncompostable PLA−PHB (80/20).
tion rather than recalcitrance and reversing the current trend of
increasing plastic in the oceans and the death of wildlife due to
plastic ingestion.2,4,5 However, we show that PHB and TPS are
the only tested neat polymers that biodegrade in all tested
aquatic environments, in addition to PHB and PCL blends that
degrade in some aquatic environments (Figure 5).
We show that individual polymers and their plastic blends
exhibit excellent biodegradation under industrial composting
and even synergy to improve biodegradation in home
composting. However, polymer blends exhibit poor biode-
gradation and even antagonism in other environments such as
aquatic and soil which could lead to long residence times in
nature. Analysis of the profile of microorganism communities
present in inocula could clarify the different performance of
tested materials in different environments. For example,
despite the fact that PLA−PCL (80/20) blend is biodegrad-
able under home composting conditions, very little biode-
gradation was observed in soil (Figures 2A and 5D). These two
testing environments differ modestly in temperature (soil 25
°C vs compost 28 °C), pH (soil: pH 8.6 vs compost pH: 7.9),
and electrical conductivity (soil salt content 920 μS/cm vs
compost salt content 2260 μS/cm). Compost and soil also
differ in microbial population, with soil having a much lower
abundance of microorganisms which could dramatically affect
the biodegradability of the blend.42,43 In addition, PHB- and
PCL-degrading microorganisms are widely distributed in
different environments,44−46 therefore it is not so surprising
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to see these polymers performing well in different biode-
gradation tests. While spiking of the inocula for soil tests with
known degraders could be applied to enhance biodegradation,
our experience is that the addition of the nonindigenous
cultures to inocula causes competition with microorganisms
present in the consortium and lowers biodegradation capacity.
A possible explanation for the synergy observed in the case
of AD of PHB−PCL (60/40) and PCL−TPS (70/30) (Figure
3) is that the addition of amorphous PCL lowers the
crystallinity of the blends and therefore higher degradation,
and thus, higher methane and biogas production are observed
compared to neat polymers. The same blends exhibit
antagonism during biodegradation tests in aquatic environ-
ments (Figure 5A−C). A likely reason for this is the very poor
degradability of PCL in water environments (Figure 5A−C)
affecting the biodegradation rate in these cases. However,
further work is required to elucidate the mechanism and
kinetics of biodegradation and provide an explanation for this
synergistic and antagonistic behavior of blends.
Furthermore, the residence times estimated from the
biodegradation rates of polymers and their plastic blends in
unmanaged environments under the tested conditions vary
dramatically, from 1 month to 18 months for TPS-based
plastics in aquatic and soil, respectively, to 33 years and more
for PLA and its blends in soil environment and no
biodegradation in aquatic environments (Table S3).
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Environmental Science & Technology
Figure 7. Biodegradation capacity of tested bioplastics in managed and managed environments tested according to international biodegradation
standards.
TPS and PHB were the only bioplastics tested in this study
to satisfy the criteria for biodegradation proposed by
international standards across all seven tested environments,
while PBS and PHO reached standards criteria only in
industrial composting (Figure 7). It is worth noting that while
PBS used in this study (PBE 003, Table 2) shows poor
biodegradation across tested environments, BioPBS FD92PM
is certified for home composting.47 The performance of other
bioplastics varied across tested environments (Figure 7).
If society is to replace nondegradable with biodegradable
plastics we need to ensure that we understand the
biodegradability of these plastics and in particular their blends
as the latter are the most likely form that biodegradable plastics
will take in the marketplace. This knowledge can inform the
design and application areas of these materials so that they
have a positive impact on end-of-life management options and
low impact on the environment if inadvertently released; e.g.,
biodegradable plastics that degrade in a wide variety of
unmanaged environments could be prioritized for applications
where they have a higher chance of ending up in the
environment (for example, packaging used in coastal areas and
plastics used in marine applications).
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.est.8b02963.
Figures S1−S5 and Tables S1−S3 (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
*Tel: +353 1 716 2198. Fax: +353 1 716 1183. E-mail: kevin.
oconnor@ucd.ie.
*Tel: +35318962602. Fax: +353 1 896 2151. E-mail: babup@
tcd.ie.
ORCID
Tanja Narancic: 0000-0003-3269-2200
Kevin E. O’Connor: 0000-0001-7202-0076
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Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
T.N. acknowledges support under EU Horizon 2020 research
and innovation programme 633962 for the project P4SB. S.V.
and L.M.-G. acknowledge support by the EU 7th framework
programme for research, technological development, and
demonstration under Grant Agreement No. 311815 (SYNPOL
Project). R.B.P. and S.R.C. were funded by Science
Foundation Ireland (SFI) Grant No. SFI/12/RC/2278.
■
ABBREVIATIONS
PLA polylactic acid
PCL polycaprolactone
PBS poly(butylene succinate)
PHO polyhydroxyoctanoate
PHB polyhydroxybutyrate
TPS thermoplastic starch
AD anaerobic digestion
SD standard deviation
MSW municipal solid waste
GHG greenhouse gas
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Environ. Sci. Technol. 2018, 52, 10441−10452