Environmental Technology & Innovation 22 (2021) 101393

Contents lists available at ScienceDirect

Environmental Technology & Innovation

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

Can bioplastics be treated in conventional anaerobic digesters

for food waste treatment?
∗ ∗
Federico Battista , Nicola Frison , David Bolzonella
Department of Biotechnology, University of Verona, Strada Le Grazie 15, 37134 Verona, Italy

article info a b s t r a c t

Article history: The ‘‘European Strategy for plastics’’ approved by the European Union aims at drastically
Received 3 November 2020 reducing the use of plastic materials derived from fossil resources, especially single
Received in revised form 25 January 2021 use plastic (SUP). As a consequence, the adoption of biodegradable plastics is forced
Accepted 25 January 2021
by different national regulations, especially in France and Italy which banned the
Available online 8 February 2021
usage of single use plastics. Being classified as biodegradable and compostable, the
Keywords: major part of these materials is often collected with the Organic Fraction of Municipal
Anaerobic digestion Solid Wastes (OFMSW), basically due by food waste, and sent to biological treatment
Bioplastics plants, namely composting and anaerobic digestion for bioenergy recovery or their
Biogas combination. This study tested the specific methane production and the relative kinetics
Bio-Methane Potential tests of the most common single use biodegradable items (carrier bag, cutlery and plates),
available on the market. It was demonstrated that sugar cane cellulosic pulp materials
have good methane production of 390 LCH4 /kgTVS and a kinetic which is consistent
with the anaerobic digestion’s residence time typically applied for OFMSW. On the
contrary, starch-based bioplastic and PLA materials remained almost undegraded after
250 days and showed low specific methane production yields in the range 100–200
LCH4 /kgTVS . The adoption of acidic and basic pretreatments improved the anaerobic
digestion performances of starch-based bioplastic and PLA samples. Materials made of
poly-hydroxy-alkanoates (PHA) showed higher methane production rates, up to 402
LCH4 /kgTVS in short residence times (around 10 days), which make them adequate to
be treated together with food waste in anaerobic digestion plants.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction

Fossil plastics are a fundamental constituent of modern life and in some cases, like food primary packaging and
disposable medical items, seem to be essential so far. Unfortunately, collection and disposal of these materials are posing
a global threat as they accumulate in the oceans and slowly degrade into microplastics (Rochman and Hoellein, 2020).
Plastic wastes accumulation in the form of large floating islands in the seas and oceans is one of the most evident
consequences of the ‘‘linear economy’’ approach. According to this model, the raw materials are processed for the synthesis
of different products, which are thrown away after their usage, without being recycled (Battista et al., 2020). With the
plastic discover at the beginning of the last century, several innovative items have been synthetized from fossil resources.
The heterogeneity of plastics properties favoured their adoption in several fields, allowing for the rapid global diffusion
of this material. In 2016, 335 million tonnes of plastic were produced globally (European Commission, 2018a).

∗ Corresponding authors.
E-mail addresses: federico.battista@univr.it (F. Battista), nicola.frison@univr.it (N. Frison).

https://doi.org/10.1016/j.eti.2021.101393
2352-1864/© 2021 Elsevier B.V. All rights reserved.
F. Battista, N. Frison and D. Bolzonella Environmental Technology & Innovation 22 (2021) 101393

The main disadvantage of plastic material is that, if not properly collected, managed and disposed of, it accumulates
in the environment as an undegradable material. Consequently, plastics accumulated in great amounts, also as result of
the lack of an adequate waste management. It has been estimated that in the European Union, 70% of the collected
plastic waste ends in landfills or is incinerated (European Commission, 2018b). This mismanagement is emphasized
considering that 80%–85% of marine litter is plastic, with single-use plastic items representing 50% and fishing-related
items representing 27% of the total. Single-use plastic products include a diverse range of commonly used products that are
discarded after a single use (shoppers, balloons, food packaging. . . ). Single-use plastic products pose a severe risk to marine
ecosystems, to biodiversity and to human health and damage activities such as tourism, fisheries and shipping (DIRECTIVE
(EU) 2019/904, 2020). In the USA the situation is similar: 53% of total municipal solid waste (MSW) is landfilled, with
plastic waste representing 13% of MSW. The potential recycling of plastic waste remains largely unexploited, with very
low global rates which cover only 6% of the total demand for plastics (European Commission, 2018b).
Proper waste management remains essential for the prevention of ecosystems littering. EU existing legislation, and
policy instruments provide some regulatory responses to address plastic wastes. In particular, plastic is subject to overall
Union waste management measures and targets, such as the recycling target for plastic packaging waste laid down in
European Parliament and Council Directive 94/62/EC and the objective in the European Strategy for Plastics to ensure
that by 2030 all plastic packaging placed on the Union market is re-useable or easily recycled. At this scope, some
specific laws have been approved: the EU Directive 2015/720, aims to the reduction of the use of lightweight plastic
carrier bags (Calabrò and Grosso, 2018). Moreover, some EU Countries, e.g., Italy and France, have banned the use of non-
biodegradable and disposable plastic carrier bags and of single use items (Calabrò and Grosso, 2018). These measures
could create barriers to trade and distort competition in the Union (DIRECTIVE (EU) 2019/904, 2020). Consequently,
sustainable alternatives for single use plastics are starting to become common and the use of ‘biodegradable plastics’ is
increasing among European citizens. With the term ‘‘biodegradable plastics’’, it is indicated a plastic capable of undergoing
physical, biological decomposition in controlled aerobic or anaerobic conditions, with the releasing of carbon dioxide
(CO2 ) or methane (CH4 ), respectively, biomass and water. Instead, a plastic is defined ‘‘compostable’’ when it is biologically
decomposed during a composting process at a similar rate to other compostable materials and without leaving toxic
compounds (Sarasa et al., 2009). In all the cases, biodegradable and compostable plastics must respect the European
standards for packaging, recoverable through composting and anaerobic digestion (Narancic and O’Connor, 2019).
The most common bio-based plastics derives from polylactic acid (PLA), corn starch and sugar cane pulp. In particular,
PLA is produced through a combination of the fermentation of bio-based sugars, precursors of the lactic acid, and chemical
polymerization to convert the lactic acid to PLA. This material is highly crystalline, which gives it desirable properties
for different applications, in particular packaging applications (Narancic and O’Connor, 2019). Other biopolymers and
related bioplastic are obtained from starches, cellulose and vegetable oils. These have properties and characteristics
of use very similar to those of traditional plastics, but at the same time, it is biodegradable and compostable. These
renewable sources allow the production of several common single-use items, such as cotton bud sticks, cutlery (forks,
knives, spoons, chopsticks), plates, straws, beverage stirrers and food packing materials, such as carrier bags. However, the
high crystallinity degree, the hydrophobicity, the presence of functional groups, and the use of additives and plasticizers
in the fabrication process affect the biodegradability of polymers (Emadian et al., 2017).
Several testing methods are available (Ruggero et al., 2019) for the definition of biodegradability and compostability
and many standards (such as, but not limited to, EN 13432, ISO 14853, 2016; ISO 13975, 2019, ASTM D5511–18, 2020;
ASTM D5526–18, 2020) already exist for the definition of composting, AD and natural biodegradation. In particular, the
standards exploring the anaerobic degradations of the bioplastics are the ASTM D5511–18 (2020) and ASTM D5526–18
(2020), which are specific for high solids contents (superior to 30% w/w) and static (not mixed) conditions (ASTM D5511–
18, 2020; ASTM D5526–18, 2020). On the contrary, standards UNI ENI ISO 14853:2016 and ISO 13975:2019 (ISO 14853,
2016; ISO 13975, 2019) are more specific for wet or semi wet conditions (TS content lower than 15% w/w) but they require
a degradation of bioplastics within 90 days. At the best of authors’ knowledge, it is not present a standard reproducing
the conditions of anaerobic digesters of the Organic Fraction Of Municipal Solid Wastes (OFMSW), which degradation is
normally completed with 20–25 days.
The aim of this research work is to evaluate the degradability of the most common bio-based plastic items (cutlery,
plates and bags) in the anaerobic digestion conditions normally adopted for the treatment of OFMSW. According the
last European Bioplastics report, the adoption of bioplastics has increased to 2.11 Mt/year in 2019 and is expected to
increase to 2.4 Mt/year in 2024 (Polman et al., 2021). Being classified as biodegradable and being the landfill disposal
a practise to avoid, these items are often recollected with the OFMSW, and, consequently, sent to anaerobic digesters
for biogas production. The three most common examples of biodegradable single-use plastics (plates from sugars cane
pulp, starch-based bags and cutlery and PLA items), have been tested, with and without pretreatments, to evaluate their
compatibility with the conventional residence time of anaerobic digestion of OFMSW.

2. Materials and methods

2.1. Selection of the biodegradable single use materials

Three common items classified as single use biodegradable plastics were selected considering their availability in
the supermarkets and diffusion in the canteen and fast food restaurants. In particular, the three items selected for the
Bio-Methane Potential (BMP) tests were (Fig. 1):
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F. Battista, N. Frison and D. Bolzonella Environmental Technology & Innovation 22 (2021) 101393

Fig. 1. The biodegradable materials, alternative to fossil plastics items, tested in BMP tests.

Table 1
TS and TVS content of the biodegradable materials and of the digestate
adopted for the tests.
TS (% w/w) TVS (% TS)
Digestate (inoculum) 5.86 ± 0.05 59.87 ± 0.35
SCCP 94.53 ± 0.06 99.87 ± 0.13
MC 98.03 ± 1.65 98.57 ± 0.26
MB 96.32 ± 1.46 99.85 ± 0.09
PLA 97.32 ± 0.87 99.53 ± 0.10
PHA1 97.93 ± 0.95 99.80 ± 0.13
PHA2 98.47 ± 0.90 99.92 ± 0.10

(a) Sugar Cane Cellulosic-fibres Plates, SCCP (Fig. 1A);

(b) Starch bioplastics Cutlery, MC (Fig. 1B);
(c) Starch bioplastics carrier bag, MB, classified as UNI EN 13342. This code identifies the compostable bioplastics,
which are considered consistent also for the anaerobic digestion (Fig. 1C).

Other biopolymers were also tested. Some samples were cut from PLA items, in order to test the anaerobic degradation
of this material. In fact this material is starting to be largely diffused in the synthesis of different biodegradable products.
Polyhydroxyalkanoates (PHA) samples were also tested in form of commercial granules. PHA are one of the more
innovative biomaterials investigated in the last years and have the potential to become one of the most promising
candidates for the production of single use items.
Table 1 reports the Total Solids (TS) and the Total Volatile Solids (TVS) content of the above cited materials.

2.2. Set up and evaluation parameters of the BMP tests

The tests were built up to be consistent with the common operational parameters adopted in the majority of full-scale
anaerobic digestion plants treating OFMSW. As a consequence, mesophilic temperature, neutral pH and a TS concentration
lower than 10% w/w (wet condition) were considered. All the tested materials were reduced to a size of 2 mm for the
different BMP tests. The methane yield was evaluated through BMP which were carried out following the methodology
suggested by Angelidaki et al. (2009). Trials were carried out in 0.5 L reactors, with 200 mL working volume, sealed with
chloro-butyl caps. Each trial was performed in triplicate. The duration of the tests was determined following the protocol
by Holliger et al. (2016), which established that BMP tests have to be stopped when the daily biogas production is lower
than 1% of the cumulative one for three consecutive days.
Inoculum (Table 1) was incubated at the test temperature (37 ◦ C) for one week to reach the endogenous methane
production. The Inoculum: Substrates (I/S) ratio adopted for all the tests was 2:1 in terms of TVS, as suggested by Holliger
et al. (2016). Control tests (blank) were also conducted to determine the endogenous methane production. Moreover,
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F. Battista, N. Frison and D. Bolzonella Environmental Technology & Innovation 22 (2021) 101393

Fig. 2. The cumulative specific methane production (LCH4 /kgTSV ).

microcrystalline cellulose BMP tests were used as positive internal control (verification of inoculum activity). In particular,
if the specific methane production from cellulose is within the range of 325–415 LLCH4/ kgTVS , the results from BMP tests
can be considered reliable. All batch digesters were manually stirred once a day. The volume of biogas generated during
the batch trials was measured every day by water displacement method, while the methane content was determined
using a portable biogas analyser (Geotech Biogas 5000 by GeoTech, United Kingdom).
SCCP, MC, MB and PLA were tested under the following conditions: (i) no pretreatment; (ii) acidic pretreatment and (iii)
basic pretreatment. Acidic and basic pretreatments consisted in the soaking of SCCP, MC and MB in an aqueous solution
at pH 2 and 12, respectively, for 48 h. The acidic and basic aqueous solutions were realized adding HCl (1N) and NaOH
(1N), respectively, in 200 ml of distilled water until the reaching the desired pH. Then, the solutions were magnetically
stirred at 100 rpm for two days. After pretreatment, substrates were washed with distilled water in order to remove the
acid and base content which could negatively affect the microorganisms’ metabolism. Tests on PHA granules were carried
out only without pretreatment.
The BMP tests were evaluated considering their performances in terms of specific methane production, expressed as
LCH4 /kgTVS , and considering the degradation kinetic. In particular, different parameters were defined: (i) the t50 (d), which
is the time requested to reach 50% of the total final methane production, (ii) the hydrolysis rate kd (d−1 ), which expresses
the velocity of the compounds degradation and can be calculated according the equation included in the research work
by Jensen et al. (2011), (iii) the factor of degradation (Fd , %), which expresses the amount of the organic matter converted
into methane for each substrate, compared to the theoretical one of 490 LCH4 /kgTVS (Jensen et al., 2011).

2.3. Analytical methods

The pH was measured by a benchtop pH meter (Mettler Toledo, United States). Each substrate was analysed in terms
of dry matter (TS) and volatile solids (TVS) content according to the Standard Methods (APHA, 2012).

3. Results and comments

3.1. Conventional BMP tests

Fig. 2 shows the cumulative specific methane production for the BMP trials for SCCP, MB, MC and PLA samples.
With the exception of SCCP, all the substrates showed a low methane production and the need for prolonged residence
time to achieve significative biogas formation. The specific methane productions were of 391, 312, 201 and 130 LCH4 /kgTVS ,
for SCCP, MC, MB and PLA, respectively. The tests had a t50 of 13, 16, 83 and 144 days for SCCP, PLA, MB and MC,
respectively.
BMP tests demonstrated that the methane production and the correspondent kinetic is highly affected by different
factors: the chemical nature of the substrates, their crystallinity degree, the typologies of their specific function groups
and their mechanical properties (Pathak et al., 2014). Emadian et al. (2017) explained that bioplastics degradation follows
three main steps: (i) biodeterioration, which is the alteration of the mechanical, chemical, and physical properties of the
substrates as consequence of the growth of the microorganisms on their surface; (ii) bio-fragmentation, the reduction of
the long polymeric chains into shorter fragments or monomers and (iii) assimilation, consisting in the carbon acquisition
from monomers conducted by the microorganisms, with the consequent conversion of the substrates into biogas, biomass
and water.
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F. Battista, N. Frison and D. Bolzonella Environmental Technology & Innovation 22 (2021) 101393

The worst performance for BMP tests was that of PLA samples. Even if PLA is often indicated as a material having a
biocompatible nature among the bioplastics, the methane production was characterized by a lag phase of about 10 days,
not comparable with the lag phase of the digesters treating of OFMSW, whose degradation starts in few hours. Then, the
kinetic of the methane production had an exponential growth (11–20 days), reaching the final value of 130 LCH4 /kgTVS at
day 25 from the beginning of the BMP test. As commented above, the specific methane production was low and the PLA
samples remained almost unaltered. This result can be explained considering the PLA chemical nature and its crystallinity
degree. PLA is a thermoplastic polyester, whose monomer is represented by lactic acid (Bátori et al., 2018). Even if lactic
acid derived from a biologic process (the conversion of sugars by fermentation), its polymerization into PLA involves a
chemical process which reduce its biological access after polymerization (Kawai, 2010). Moreover, PLA is characterized
by the high crystallinity degree which does not facilitate the diffusion of microorganisms enzymes in its matrix with
a consequent elongation of the lag phase, as it was evident also from the test of the present research work. The low
anaerobic degradation performance for PLA was also observed by previous research studies: Massardier-Nageotte et al.
(2006) found that PLA was not converted into biogas along the 28 days of a test. The situation was not better with longer
residence times: Shin et al. (1997) did not obtain biogas production in more than 100 days of experimentation. Another
research led to the same conclusion after 170 days of residence time (Kolstad et al., 2012). The recalcitrant nature of PLA
can be due also to the fact that it is often blended to polycaprolactone (PCL) in order to improve the impact resistance,
which contributes to a further reduction of the biodegradability of PLA (Narancic and O’Connor, 2019; Sangeetha et al.,
2018). Consequently, PLA based bioplastics seem not suitable for anaerobic digestion.
Also its aerobic degradation seems to be not easy: Narancic et al. (2018) estimated that PLA can completely degraded
in soil only after long time in soil, that means in around 3 decades.
Also samples of starch based bioplastic were characterized by low specific methane production values, with an average
of 201 LCH4 /kgTVS . Although the lag phase was of only 2 days, the kinetic was slow along all the time of the BMP test, as
demonstrated by the value of the t50 parameter which was 83 days. A previous work by Vasmara and Marchetti (2016),
who performed the anaerobic digestion of similar materials both at mesophilic (35 ◦ C) and thermophilic conditions (55 ◦ C),
observed a specific methane production of 113 LCH4 /kgTVS at 55 ◦ C, while it was of only 33 LCH4 /kgTVS at 35 ◦ C. In both the
conditions, the productivity was lower than the one achieved by the present work in mesophilic conditions. Another work
achieved a similar performance: about 200 L of biogas per kgTVS were observed after 30 days of anaerobic digestion with a
low methane content of about 30% (Davis and Song, 2006). More recently, Zhang et al. (2018) confirmed the low methane
productivity from starch based materials, finding a yield of 69 LCH4 /kgTVS. These results demonstrated the recalcitrant
nature of starch based bioplastics under anaerobic conditions: these materials need for long times to achieve significative
methane production as revealed by our BMP tests and results reported in recent literature. These materials are normally
the result of a blend composed by corn starch and biodegradable polyesters. It is fundamental to remark that starch alone
is not useable for the production of carrier or shopping bags because of the poor mechanical properties (e.g. brittleness)
and its hydrophilic nature. Consequently, the additions of plasticizer and polymeric additives are essential to obtain a final
product with adequate mechanical performances (Sforzini et al., 2016). It reported that starch content in carrier bags is
around 50% w/w (Davis and Song, 2006; Pathak et al., 2014; Vasmara and Marchetti, 2016). Sometimes, starch is blended
with polycaprolactone (PCL). Although PCL is known to be one of the more degradable materials, it was concluded that
its degradation is better under aerobic conditions rather than under anaerobic ones (Ruggero et al., 2019). Massardier-
Nageotte et al. (2006) observed that starch based bioplastic items containing PCL achieved a degradation degree of 45%
under aerobic conditions, and only around 25% under anaerobic digestion. Another polymer, usually blended with starch, is
poly-vinyl-alcohol (PVA), a synthetic vinyl polymer that is water soluble and biodegradable. PVA is known to be degradable
both in aerobic and anaerobic condition, even if the kinetic are very slow in this last case (Russo et al., 2009). The anaerobic
degradation of bioplastics made of starch and PVA blends seems to be controversial, depending on the amounts of resins,
chemical additives and PVA in the blend. In general, several authors concluded that starch based bioplastics are more
suitable for composting process than for anaerobic digestion (Massardier-Nageotte et al., 2006; Russo et al., 2009; Bátori
et al., 2018).
Another starch based product tested along this experimental campaign was MC: in this case a better methane specific
production of 312 LCH4 /kgTVS was observed. But, as it turns out evident from Fig. 2, MC trials were characterized by very
slow kinetics with a lag phase of almost 25 days and a very high t50 of 144 days. These results allow us to confirm the main
conclusions derived from the previous tests on MB: (i) anaerobic digestion is probably not the adequate technology for
these products as it requires long residence times and led to relative low methane production; (ii) kinetical degradation
of these materials is strongly affected by the chemical composition and the crystallinity degree.
The last very common product adopted as alternative to the single use fossil plastics is sugar cane cellulose. SCCP
tests achieved good methane productivity of 391 LCH4 /kgTVS and was characterized by good kinetical performances: a lag
phase of few days (2–5) and a t50 of 13 days. Moreover, at the end of the BMP tests, the SCCP fragments were completely
dissolved in digestate (visual observation). A previous research work tested anaerobic degradation of paper-based items
(Calabro’ et al., 2020): obtained results are consistent with the ones achieved by this work. Calabro’ et al. (2020) found a
methane production around 250–300 LCH4 /kgTVS within 15 days. The best final specific methane production achieved in
the present work can probably be due to the longer residence time applied. In such conditions, conversion of the most
recalcitrant compounds, such as hemicellulose and lignin, was, at least partially, possible (Larsen et al., 2017), even if the
kinetic was considerably slower (Fig. 2).
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F. Battista, N. Frison and D. Bolzonella Environmental Technology & Innovation 22 (2021) 101393

Table 2
Specific methane production for no pretreated, acid and basic pretreated tests.
Specific Methane No pretreatment Acidic pretreatment Basic pretreatment
production (LCH4 /kgTVS )
SCCP 391.14 ± 21.06 342.64 ± 23.76 339.90 ± 38.15
MB 200.91 ± 4.60 203.87 ± 3.19 158.05 ± 4.51
MC 312.50 ± 8.20 302.51 ± 6.64 252.87 ± 7.90
PLA 130.00 ± 6.70 125.29 ± 5.40 103.93 ± 2.51

The last tested material was PHA: since we did not find on the market any PHA based single use product to test, we
decided to test directly PHA commercial granules to determine their BMP. Polyhydroxyalkanoates are a family of com-
pletely biodegradable polyesters, which are bio-synthetized in form of internal carbon granules by different gram-positive
and/or gram-negative microorganisms but also by anaerobic photosynthetic bacteria and archaea (Rodriguez-Perez et al.,
2018; Battista et al., 2020).
Fig. 2 shows the BMP curve of PHA. The specific methane production achieved results similar to those observed for
SCCP, 402 LCH4 /kgTVS , but the kinetic was slightly quicker with a lag phase of 4 days and a t50 of about 11 days. Similar
performances were obtained by Benn et al. (2016) which tested different PHA typologies, finding a methane production
within the range of 330–490 LCH4 /kgTVS. The same authors, in a comparative work between PHA and PLA, demonstrated
the recalcitrant nature of PLA under anaerobic conditions with a maximum methane production of only 60 LCH4 /kgTVS.
Chan et al. (2020) calculated a mathematical linear correlation between PHA content and the specific methane production,
which can be expressed in the form of BMP (mLCH4 /gTVS ) = 240 + 15.3 × PHA (mmolC/gTVS ). The maximum BMP obtained
by the authors was 401 mL CH4/g TVS with the biomass with the highest PHA content (9.80 mmol C/g TVS).

3.2. Effects of acidic and basic pretreatments on tested bioplastics

Two typologies of chemical pretreatment, the acidic and the basic ones, were selected to verify the possible improve-
ment of the performances of the anaerobic digestion process on bioplastic materials. Another common pretreatment
reported in literature is the enzymatic one, which is more known to be efficient in presence of high concentration of
lignocellulosic materials (Battista and Bolzonella, 2018). Even if lignocellulosic compounds are present in OFMSW, because
of the presence of vegetal residues, their concentration is not predominant (Battista et al., 2020) and an enzymatic
pre-treatment was not selected for these BMP tests. In the scientific literature, one research work emerged for the
adoption of enzymatic pretreatment (Ahmad et al., 2017) but its scope was the improvement of the tensile strength
of a bio-composite including PVOH (polyvinyl alcohol) and enzymatic treated wheat straw, not the improvement of the
degradation performances of a bioplastic.
Table 2 summarizes the values of the specific methane production found for non pretreated, acidic and basic pretreated
BMP tests. It emerged that acidic pretreatment was completely irrelevant on anaerobic digestion, while basic pretreatment
inhibited the anaerobic process, with a reduction of the specific methane production of 12.5% for the SCCP tests and of
around 20% for MB, MC and PLA tests. As reported above basic and acidic pretreatments were not tested on PHA.
Basic and acidic pretreatments are usually adopted to decrease the crystallinity degree, the available superficial area
and the disaggregation of polymers long-chains (Battista et al., 2016). In particular, basic pretreatment is known to
favour the saponification reaction which results in the hydrolysis of the organic substrates (Uma Rani et al., 2012). These
pretreatments effects led to an increase in the specific methane production. It did not occur along this experimentation,
as commented above. At the best of our knowledge, few works investigated the effect of chemical pretreatments on
single use biodegradable materials have been conducted. A previous work by Yu et al. (2005) seems to confirm the
inefficacy of the acidic pretreatment with sulphuric acid on the methane production from PLA and PHA, where it was not
observed an increase in the organic matter solubilization. On the contrary, basic pretreatments achieved an increase of the
methane productivity and a reduction of the lag phase in the trial for PLA bioplastics (Benn and Zitomer, 2018). But it is
fundamental remarking that in the mentioned study the basic pretreatment was combined with a thermal pretreatment,
at a temperature range between 90 ◦ C and 120 ◦ C, while no methane improvement was observed for temperature under
55 ◦ C. In the specific case of the present research, basic pretreatment led a significative reduction of methane production
(from 12 to 20%) in the BMP tests. It can be explained by a probable accumulation of Na+ ions in the reaction medium,
derived from the NaOH pretreatment, which could be retained by the substrates although the distilled water washing’s
step after the pretreatment, have causing the microorganisms inhibition (Bolzonella et al., 2019).
As for starch based bioplastics, we did not find previous experiments reported in literature. However, we can assume
that, although it derives from a natural substrate, its degradability is negatively affected by the presence of chemical
additives and PVA and PCL additions, which are not only used to improve the mechanical properties, but also to increase
the stability of the polymers even in presence of acidic and basic compounds (Bolzonella et al., 2018).
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Fig. 3. Factor of biodegradability vs. hydrolysis rate of the tested single use bioplastics and of OFMSW for comparison.

3.3. Final considerations and suggestions for the anaerobic digestion of the single use biodegradable products

Different samples of the most common single use biodegradable items were tested to determine the BMP value during
anaerobic digestion trials. In particular, sugar cane cellulosic pulp, starch based and PLA made products were considered
in this study. Being classified as ‘‘compostable’’ and ‘‘biodegradable’’ these items are often collected together with OFMSW
and sent to the anaerobic digestion plants for the biogas production. Therefore, we considered both the hydrolysis rate
and degradation fraction for OFMSW and the different tested bioplastics (Ge et al., 2011).
Fig. 3 shows that the hydrolysis rate and rate of biodegradability values of sugar cane cellulosic pulp products, such as
SCCP, are consistent with the anaerobic digestion of OFMSW, having a specific methane production similar to the OFMSW
one, which is in the range of 315–450 LCH4 /kgTVS according to its composition (Bolzonella et al., 2018; Shamurad et al.,
2020), with a correspondent Fd value in the range 62–89.5%. The t50 of SCCP test was of 13 days, which is compatible
with the conventional OFMSW’s residence time of 15–30 days (Pathak et al., 2014; Bolzonella et al., 2019). Also, the kd
value of 0,13 d−1 for SCCP is consistent with those found for OFMSW: 0,09–0,145 d−1 .
On the contrary, the two starch based made products considered by this work, the carrier bag and the cutleries emerged
as not suitable for the anaerobic digestion for the low methane specific production and, mostly, for the very long residence
time required by starch based materials to degrade. These residence times are from 4 to 10-fold higher than the ones
needed for OFMSW. The observed values of kd were also very low (Fig. 3). It means that, when treating in codigestion
with OFMSW, starch based items remain in the digesters almost in an undegraded form, with the serious risk to clog
pipes or damage mechanical parts (mixers) in the reactors. The same conclusion was formulated by Cho et al. (2011) who
observed degradation rates for starch based bioplastic items in the range 40%–70%, similar to the ones obtained for MB
and MC. Similarly, Bátori et al. (2018) and Shrestha et al. (2020) reported the necessity of long retention time in reactors
for the anaerobic digestion of starch based products. As discussed, acidic and basic pretreatments did not improve the
BMP performances. Similar results were obtained for PLA made products, which, consequently, cannot be considered easy
to treat in anaerobic digesters.
As alternative, the following three different routes could be adopted for future investigation on the biodegradability
of single-use products:

(i) The adoption of thermal pretreatments in a temperature range between 60 and 120 ◦ C, which some authors have
declared to be efficient in the hydrolysis of starch based and PLA materials (Benn and Zitomer, 2018; Bolzonella
et al., 2019);
(ii) The adoption of aerobic processes, which seems to be able to reduce 50% of starch based and PLA products mass in
90–150 days when disposed in soil (Bandini et al., 2020). Considering the absence of inert, emerged by the TVS to
TS ratio (Table 1), the investigation of the performances and emissions of alternative processes for the degradation
of starch based and PLA materials, such as pyrolysis, gasification or incineration, is worth to be conducted;
(iii) Finally, according to obtained results, PHA made products could be an interest alternative when disposed of with
food waste. They showed good specific methane production and need for short residence times, which made them
consistent for the co-treatment with OFMSW. The PHA performances are very similar to those of OFMSW both
7
F. Battista, N. Frison and D. Bolzonella Environmental Technology & Innovation 22 (2021) 101393

in terms of Fd and in term of kd , as evident from Fig. 3. Some authors already demonstrated that their addition
with sewage sludge was able to improve the biogas production (Wang et al., 2015). It is however important to
remark that the influence of the addition of co-polymers and additives to PHA matrix has not been investigated
yet. Consequently, their effects on the anaerobic digestion process are still unknown.

4. Conclusions

The single-use plastics ban led to the diffusion of alternative biodegradable materials, as sugar cane cellulosic pulp,
starch-based and PLA made items. These materials are classified as compostable and/or biodegradable and could be
disposed of with OFMSW, reaching anaerobic digestion and composting plants. BMP trials demonstrated that these
materials are only partially degradable in anaerobic conditions and need for very long retention time to show acceptable
degradation rates.
Starch based and PLA bioplastic samples achieved low biogas production and required very long residence time as effect
of their high crystallinity degree, the presence of additives and other polymers, used to improve the mechanical properties
of the materials. On the contrary, materials made of sugar cane cellulosic pulp demonstrated to be as treatable as OFMSW
having a high methane production of about 390 LCH4 /kgTVS and requiring short residence times. Acidic and basic chemical
pretreatments at room temperature was completely inefficient in improving the degradation performances. Lastly, the
BMP tests carried out on samples of PHA granules demonstrated they are suitable for the anaerobic digestion process but
further investigations are needed to verify the influence of additives and co-polymers.
The combination of anaerobic digestion, composting and natural conditions on bioplastics items should be verified in
order to clarify the fate of these materials along the treatment chain.

CRediT authorship contribution statement

Federico Battista: Ideation of the process, Conduction of the tests, Writing of the manuscript. Nicola Frison:
Supervision of the project and of the manuscript. David Bolzonella: Supervision of the project and of the manuscript.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have
appeared to influence the work reported in this paper.

Acknowledgements

This study was supported by the (i) Join Project 2018 ‘‘Study of a biorefinery for the production of VFA, biogas, and
PHA from agro-residues’’ financed by the University of Verona and (ii) Reti Innovative Regionali (RIR) financed by Regione
Veneto, Italy.

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