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Anaerobic digestion of aliphatic polyesters


Pavla mejkalov, Veronika Kunkov, Jan Merna and Son a Hermanov

ABSTRACT
Anaerobic processes for the treatment of plastic materials waste represent versatile and effective
approach in environmental protection and solid waste management. In this work, anaerobic
biodegradability of model aliphatic polyesters, poly(L-lactic acid) (PLA), and poly(-caprolactone)
(PCL), in the form of powder and melt-pressed lms with varying molar mass, was studied. Biogas
production was explored in batch laboratory trials at 55 1 C under a nitrogen atmosphere. The

Pavla mejkalov
Department of Water Technology and
Environmental Engineering,
University of Chemistry and Technology,
Technick 5, Praha 6 Dejvice 166 28,
Prague,
Czech Republic

inoculum used was thermophilic digested sludge (total solids concentration of 2.9%) from operating
digesters at the Central Waste Water Treatment Plant in Prague, Czech Republic. Methanogenic
biodegradation of PCLs typically yielded from 54 to 60% of the theoretical biogas yield. The
biodegradability of PLAs achieved from 56 to 84% of the theoretical value. High biogas yield (up to
677 mL/g TS) with high methane content (more than 60%), comparable with conventionally

Veronika Kunkov
Jan Merna
Son a Hermanov (corresponding author)
Department of Polymers,
University of Chemistry and Technology,
Technick 5,
Praha 6 Dejvice 166 28,
Prague,
Czech Republic
E-mail: sona.hermanova@vscht.cz

processed materials, conrmed the potential of polyester samples for anaerobic treatment in the
case of their exploitation in agriculture or as a packaging material in the food industry.
Key words

| anaerobic digestion, biodegradable polymers, methane, poly(L-lactic acid),


poly(-caprolactone), sludge

INTRODUCTION
The utilisation of polyester-based materials in packaging and
agricultural applications is justied by their susceptibility to
the hydrolytic scission and their biodegradation under various environmental conditions (Yavuz & Baba ; Kale
et al. ; Mensitieri et al. ; Gorrasi & Pantani ;
Karamanlioglu & Robson ). Among aliphatic polyesters,
poly(L-lactic) acid (PLA), and poly(-caprolactone) (PCL),
represent compostable and biodegradable thermoplastics,
which are decomposed to carbon dioxide and methane
along with water and mineral salts during their mineralisation in compost and sludge, respectively (Gartiser et al.
; Calil et al. ; Funabashi et al. ; Yagi et al.
).
Polymer particle size, molar mass, and thermal history
signicantly affect the degradation rate (Murthy et al.
). For both polyesters anaerobic biodegradation rate
was signicantly enhanced in the thermophilic conditions
(55 C) in comparison with the mesophilic ones (35 C)
(Itvaara et al. ). This accelerating effect of temperature
is ascribed to both increased mobility of chains regularly
arranged in crystalline phase and those being in disordered
glassy state (Marten et al. ; Ndazi & Karlsson ;
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doi: 10.2166/wst.2016.088

Kolstad et al. ) and different compositions of thermophilic microbial community. The biodegradability of PLA lms
under thermophilic anaerobic conditions ranges from 86 to
99% depending on the specimens size (Yagi et al. ).
Smaller sized specimens were disadvantaged due to oating
in the solution layer above highly active sludge sediment.
Consequently the larger sized specimens degraded faster.
The nal biodegradability of PCL in the form of the
powder decreased from 91 to 81% depending on particle
size under thermophilic sludge conditions. Particles with
smaller size degraded faster due to the higher accessible
specic surface (Yagi et al. ). Albertsson et al. reported
a decrease in number-average molar mass (Mn) by 80%,
accompanied with the crystallinity increase by 45% for
lm-blown PCL (0.04 mm thickness) degraded in anaerobic
sewage sludge for 29 days (Albertsson et al. ).
In this study, we investigated the degradation behaviour
of PLA and PCL in the powder form and the form of meltpressed lm (10 10 0.7 mm) under anaerobic sludge
conditions at 55 C in a 150 day timeframe. Water uptake
values, molar mass reduction, thermal properties and mineralisation (percentage of the theoretical biogas amount) were
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Anaerobic digestion of aliphatic polyesters

Water Science & Technology

used as the indicators of the abiotic and enzyme-catalysed


hydrolytic scission and biodegradation, respectively. Our
objective was also to evaluate aliphatic polyesters in various
forms as materials for anaerobic treatment.

METHODS
L-Lactic acid (85 wt % aqueous solution) and -caprolactone, -CL (97%), were purchased from Sigma Aldrich. CL was vacuum distilled from calcium hydride before use.
PLA was supplied by Nature Works LLC. The value of
specic optic rotation of 148.1 refers to that of PLA
with 98.5% of L-LA units (150 ) (Tonelli & Flory ).
The polyester samples, which were selected for anaerobic biodegradation study, were either obtained from
suppliers or synthesised in the laboratory. Ring-opening
polymerisation of -CL was performed in bulk using tin
2-ethylhexanoate as the initiator to prepare samples in
powder form with various molar masses. For the purpose
of PLA sample preparation with various molar masses,
L-lactic acid aqueous solution (250 mL, 85 wt % aqueous
solution) was dehydrated in a round-bottomed ask
(500 mL) at 150 C under gradual lowering atmospheric
pressure to reduced pressure (4.7 kPa) (Olewnik et al. ).
For the purpose of lm preparation, PCL in powder
form was melt pressed (64 C, 3 min, pressure 0.35 MPa)
and sectioned into square specimens (10 10 mm) with a
thickness of 0.7 mm. In the case of PLA lm, granules supplied by Nature Works LLC were melt pressed (186 C,
3 min, pressure 0.35 MPa) and sectioned into square specimens (10 10 mm) with a thickness of 0.7 mm.
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Biodegradation of polyester powders and lms under


anaerobic conditions
Batch test was carried out in 120 mL serum bottles at a
temperature of 55 1 C under the nitrogen atmosphere.
The inoculum used in this test was thermophilic digested
sludge from operating digesters at Central Waste Water
Treatment Plant (CWWTP) in Prague, Czech Republic.
The polymer in the form of lms and powders were placed
into the serum bottle with 80 mL of sludge. After certain
time interval (10, 29 and 49 days), the PLA and PCL lms
were taken out, carefully washed with distilled water to
remove solid sludge particles and dried until constant
mass loss. Samples in the powder form were incubated without periodical removal and material analysis.
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To determine the appropriate ratio of polymer specimen to sludge, the chemical oxygen demand (COD) of
the samples was estimated ISO 15705:. CODT was
2.23 g/g for PCL, 1.41 g/g for PLA, both in the lm form.
CODT of the model powder samples was in the range of
1.12.2 g/g.
The characteristic parameters of inoculum were as follows: TS, total solids (28.6 g/l); VS, volatile solids (14.7 g/L);
TSS, total suspended solids (26.7 g/L); and VSS, volatile suspended solids (13.5 g/L), concentrations were determined
according to Standard Methods (APHA-AWA-WPFC ).
According to starting mass of polyester melt-pressed specimens the initial organic loading of inoculum was
0.38 g COD/g and 0.15 g COD/g VSS for PCL and PLA,
respectively. For model powder materials the initial organic
loading of inoculum was in the range from 0.2 to 0.9 COD/g
VSS. These values belong to the optimum value range of
0.11.0 g COD/g VSS for the system in our study.
The biogas production was measured volumetrically at
regular time intervals using a gas-tight burette with NaCl
saturated solution as a stop liquid. The bottles were stirred
before each measurement. The gas composition was analyzed by a gas chromatograph (Fisons Instruments GC
8000Top) equipped with a thermal conductivity detector
HWD 800 and a Separon AE (200300 m) glass column
(2.5 m, 3 mm inside diameter). Argon was used as a carrier
gas at a pressure of 100 kPa. The test was stopped when
the biogas production was close to zero, i.e. after 150 days.
Biodegradability is expressed as an achieved percentage of
the theoretical biogas yield calculated according to Buswell
equation (Buswell & Mueller ).
Abiotic degradation and water uptake of polyester lms
For the purpose of water uptake test and abiotic degradation,
the samples in the lm form were incubated. The polymer
lms were placed into the serum bottle with 80 mL of phosphate buffer (pH 7.5) with sodium azide (0.03%) and kept
at 55 1 C for 29 days. Phosphate buffer with pH of 7.5
was selected as incubation medium as this pH value was
measured in serum bottles with digested sludge already
after 24 hour incubation of all polyester lms and persisted
up to 49 days. Such slight decrease could be ascribed to the
accumulation of degradation products ending with carboxylic
groups undergoing a deprotonation or simply metabolic
changes and transformations due to anaerobic digestion of
these products within the biomass cells.
Water uptake study was carried out independently of biodegradation test in digested sludge and phosphate buffer (pH
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7.5) for 10 days. Three separately incubated lms (80 mL of


sludge or buffer) were periodically removed, dried with ltering paper, weighed, and immersed again into the bottles.

RESULTS AND DISCUSSION

Polyester characterisation

Both polyester samples, PCL and PLA, underwent the


hydrolysis to release degradation products which were rapidly
converted to biogas in the rst few days of incubation. This
was documented by no evident lag phase and correlation
between the theoretical amount of produced gas and PCL
specimens mass loss during 29 days (Supplementary
Material, available with the online version of this paper).
Given that in anaerobic digestion the biological hydrolysis is
assumed as the rate-limiting step of biogas production, one
must consider that different susceptibility of polyester samples
to hydrolytic scission would inuence their anaerobic digestion prole. In accordance with this assumption lower rate
of biogas production was measured for PCL than for PLA
(Table 1). Maximal specic biogas production rates were comparable for both PCL (1.01 mL/(ggh)) and PLA (1.06 mL/
(ggh)) samples. Both polyester samples were comparable
with solid substrates frequently used in biogas plants for codigestion, such as straw (0.68 mL/(ggh) at mesophilic conditions, 0.95 mL/(ggh) at thermophilic conditions) and
maize silage (1.6 mL/(ggh)). These natural substrates were
evaluated independently of polymers under the same conditions (data not shown).
Biodegradability achieved 60 and 74% of expected value
calculated according to Buswell equation (with methane
content of 67 and 62%) for PCL and PLA lms, respectively
despite PCL materials are suggested as almost completely
degradable in thermophilic anaerobic digestion process in
the literature. Ponsart et al. showed that biodegradation of
tritiated PCL proceeded up to the ultimate stage over
ca. 72 days, giving tritiated water (8090%) and biomass

Sample mass loss (%) and water uptake gain (%) were calculated as follows:
(m0  md )
100,
m0
mw  m0
100,
water uptake %
m0

mass loss (%)

where m0 denotes the initial mass of the lm, md denotes the


mass of the dried degraded lm, and mw is the mass of wet
sample.
For the differential scanning calorimetry (DSC) experiments, DSC Q100 (TA Instruments) was used. Samples
were heated and cooled at a rate of 5 C/min under a nitrogen ow rate of 50 mL/min. The measurement was (i) 25
200 C, (ii) 20025 C, (iii) 25200 C and (iv) 20025 C
for PLA and (i) 0100 C, (ii) 1000 C, (iii) 0100 C and
(iv) 1000 C for PCL. Crystallinity of lms was evaluated
according to the following equation, where Hm is
measured melting enthalpy and H0m is melting enthalpy
for hypothetically 100% crystalline sample. H0m 93.1 J/g
for PLA and 139.5 J/g for PCL were used for crystallinity
calculation (Crescenzi et al. ). For PLA cold crystallisation (cc) was taken into account.
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Hm
Hm  Hcc
100, %
100
Hm 0
Hm 0

Average molar masses of polyester samples were determined using size exclusion chromatography (SEC) with
refractive index (RI) detection (Watrex P102 pump, Schambeck RI2000 detector). Separation was performed on one
polystyrene (PS) Mixed C column (8 300 mm, 5 m) in
CHCl3 as a mobile phase at ow rate 1 mL/min. Relative
calibration using narrow polystyrene (PS) standards (580
3,250,000 g/mol) was used to calculate apparent molar
masses. Data were evaluated using Clarity 5.0 data processing software.
Molar mass of oligomer poly(L-lactic acid) out of calibration of SEC was calculated according to respective
proton signals in nuclear magnetic resonance spectrum. 1H
NMR spectrum was measured on NMR Spectrometer
Bruker Avance DRX 500 at laboratory temperature in CDCl3.

Anaerobic digestion of polyester lms

Table 1

Biodegradability of polyester lms and lower-molar mass samples in powder


form

Mn ()

Biodegradabilitya

Biogas yieldb

[kg/mol]

[%]

[L/kg]

PCL(lm)

58.1 (2.3)

60

663

PCL (powder)

38.0 (2.0)

54

643

PCL (powder)

13.0 (2.8)

57

676

PLA (lm)

44.5 (2.0)

74

677

PLA (powder)

3.4 (1.7)

56

520

PLA (gel)

0.35

84

625

Biodegradability of the samples is expressed as an achieved percentage of the theoretical

biogas yield calculated according to Buswell equation (Buswell & Mueller 1952).
b

To sample mass (TS), under standard conditions (STP standard temperature 273.15 K

and pressure 105 Pa).

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(Ponsart et al. ). Albertsson et al. reported on the biodegradation corresponding to theoretical amount of produced
gas from the amount of PCL incubated in sewage sludge
(Albertsson et al. ).
It is worth mentioning that the biodegradability values
could be inuenced by the sludge concentration; concretely
undiluted sludge with TS concentration of 2.9% was used in
this study.
The biodegradability concept states that all polymer
carbon is converted into gaseous carbon (CO2, CH4) when
complete mineralisation (100% value calculated according to
Buswell equation) occurs. However, the inoculum introduces
into the digestion process a wide range of ballast substances.
During the decomposition of complex molecules it can be
expected that polymer degradation intermediates interact
with these substances or are sorbed in the sludge. Consequently they become unavailable for further degradation and
mineralisation within cells. Besides, some portion of degraded
polyester specimens was assumed to be incorporated into biomass under the incubation conditions of this study. That is why
complete mineralisation was not achieved.

Figure 1

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To simulate the digestion of the polyester lm in the


later phase of incubation when it is disintegrated, eroded,
and has shorter chains, lower-molar mass samples of both
polyester types in the powder form were subjected to
anaerobic incubation in sludge. In accordance with the
expectation, model samples are more susceptible to biodegradation. Their biodegradation has a faster onset and
progression, i.e. biogas production (Figures 1(a) and (b)),
due to both shorter chains and also higher-surface area.
These factors are supposed to also accelerate the abiotic
hydrolysis in comparison with the higher molar mass lms.
On the other hand, the total biodegradability of polymer
powder does not exceed the value reached for the lm form
of polyesters (Figures 1(c) and (d)) and similar situation was
found for the biogas yield (Table 1). This was probably
caused by oating of ne particles on the surface of the
liquid phase without their sufcient contact with the
sludge. For PLA sample in gel form this problem does not
occur as gel sediments readily. So due to good contact
with the sludge and low molar mass it reached the highest
biodegradability.

Time of 80% decomposition (dark bars) and maximal specic biogas production rate (light bars) for PCL samples (a) and PLA samples (b) differing in apparent molar mass under
thermophilic sludge conditions; specic biogas production related to sample mass (TS) in anaerobic biodegradation test of samples PCL (c) and PLA (d) under thermophilic
sludge conditions.

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Each type of aliphatic polyester lms is assumed to


undergo the hydrolytic scission of ester bonds exhibiting
particular behaviour due to different chemical structure
and related steric hindrance of ester linkages and also different morphology (crystalline versus amorphous). To bring
more insight into the course of anaerobic digestion process,
incubated lms were removed at certain time intervals, analysed and the results were compared with changes induced
by incubating in phosphate buffer.

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specimens thickness (0.7 mm) and the morphology of polymeric materials, the hydrolytic scission is supposed to begin
at the lm surface generating new hydroxyl and carboxylic
groups and then to progress into inner layers depending on
the competition between water diffusion and hydrolytic reaction. Hydrolytic degradation under conditions of this study is
assumed to be either OH ions-catalysed random chain scission (sludge and buffer) or extracellular enzymes catalysed
unzipping reaction (sludge), which can occur only at the lm
surface. Activities of extracellular hydrolases capable of
acting on ester bonds cleavage in digested sludge are shown
in Supplementary Material.
Water uptake values of both polyester lms were very low
in phosphate buffer, which reected slow water diffusion into
semicrystalline (PCL) and amorphous glassy (PLA) matrix.
Water uptake of PCL lms incubated in sludge was almost
the same as in the abiotic environment which means possible
occurrence of hydrolytic scission only at the sample surface.
Signicantly increasing water uptake values of biotically
incubated PLA lms reected pronounced hydrolytic scission starting at the surface and rapidly approaching inner
layers up to samples disintegration.

Water uptake of polyester lms


Water uptake measurement was performed to evaluate the
extent of increasing bulk hydrophilicity of polyester specimens during initial 10-day period of incubation in digested
sludge and phosphate buffer (Figure 2). Assuming the

Changes in molar mass of polyester lms

Figure 2

The extent of hydrolytic scission was evaluated according to


changes in average molar mass of dried samples taken from
digested sludge and the resulting characteristics were compared with those of samples immersed in phosphate
buffer. Overall results are summarised in Table 2.
For PCL lm, a surface erosion mechanism prevailed
during the whole 49-day incubation. Initially enzymecatalysed chain unzipping is suggested to occur as no

Water uptake prole of PLA lm (a) and PCL lm (b); sludge (solid square),
buffer (empty square).

Table 2

Molar masses and thermal properties of polyesters after the incubation in digested sludge (29, 49 days) and phosphate buffer (29 days)

Sample

Man [kg/mol]

T1st
[ C]
g

T1st
m [ C]

T1st
[ C]
c

1st [%]

T2nd
[ C]
m

2nd [%]

PCL 0

58.1

2.3

n.d.b

68

31

55

61

41

29-buffer

38.4

2.1

n.d.

70

35

55

60

41

29d-sludge

37.1

2.2

n.d.

73

34

56

60

43

49d-sludge

30.0

1.8

n.d.

74

34

61

60

45

PLA-0

44.5

2.0

65

169

n.d.

10

168

21

29d-buffer

5.9

2.6

n.d.

161

109

69

161

67

29d-sludge

1.5

1.5

n.d.

146

100

72

143

42

49d-sludge

0.82

1.8

n.a.c

n.a.

n.a.

n.a.

n.a.

n.a.

Conditions: sludge with initial pH 8.0, phosphate buffer with initial pH 7.5, temperature 55 C.
a

Molar masses determined by SEC according to the PS calibration.

b
c

n.d. not detectable under conditions of DSC analysis due to the high content of crystalline phase.
n.a. not analysed due to small amount of solid sample residues.

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reduction in molar mass (Figure 3) and mass loss up to 2.6%


for 10-day biotically incubated PCL lm was achieved in
comparison with no mass loss of abiotically incubated
one. During following incubation OH ions-catalysed
random chain scission took place which is supported by
the same extent of the reduction in molar mass of both abiotically and biotically incubated PCL lms.
PLA lms were found to be more susceptible to random
hydrolytic scission in alkaline conditions that PCL ones as
evidenced by a signicant drop in average molar mass
(Mn, Mw) during samples incubation in both sludge and
buffer (Figure 3). Monomodal character of elution curves
supported the homogenous way of proceeding degradation
in the lm. Pronounced decrease in molar mass of PLA
lms incubated in sludge is ascribed to extracellular
enzymes action on the sample surface making it more
hydrophilic and vulnerable to water diffusion into entire
specimen which in turn accelerated the random scission.

Thermal properties of polyester lms


Thermal properties of polyester lms before and after the
incubation were determined to understand the changes
induced by hydrolytic scission and physical aging
(Table 2). DSC analysis of PCL lm before the incubation
shows that it is a semicrystalline material with a relatively
high crystallinity of 55%. The crystallinity of abiotically
aged and biodegraded PCL samples remained almost
unchanged after 29 days of their incubation and only slightly
increased following incubation. The temperature of incubation media, 55 C, was close to melting point of PCL
(Tm 68 C) and so could act as the annealing temperature.
Consequently physical aging took place during samples
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incubation as documented by higher melting point


measured after the rst heating scan and the same thermal
characteristics obtained after the second heating scan of
starting and incubated sample. Slight increase in crystallinity of samples incubated for 49 days in sludge could be
the consequence of the degradation proceeding preferentially in amorphous domains.
According to DSC analysis PLA lm showed glass transition temperature of 65 C with the structural relaxation,
cold crystallisation and melting temperature of 169 C.
During the incubation both in sludge and buffer the
sample lost the transparency, became brittle and signicantly increased crystalline phase content. Such increase is
ascribed to the preferential degradation and release of the
amorphous part of the solution, which is evident for biotically incubated PLA lms, where the reduction of
amorphous content was accompanied by comparable mass
loss. The formation of new crystallites during the secondary
crystallisation means another possibility to explain this crystallinity increase. The scission-induced crystallisation (Han
& Pan ; Gleadall et al. ) is suggested to occur in
PLA lms immersed in buffer for 29 days as documented by
relevant drop in molar mass, low mass loss (2 wt%),
and comparable increased crystallinity calculated according
to the rst and the second heating scan.
In conclusion, the crystallinity of all incubated polyester lms was found to increase due to preferential
cleavage and release of amorphous regions, secondary
crystallisation of embedded degraded chains and physical
aging. Consequently, one may expect that the hydrolysis
process of the solid residual material becomes slower and
probably also less complete under the conditions of the
study.
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CONCLUSIONS

Figure 3

Time course of the decrease in number-average molar mass of incubated PCL


and PLA samples.

The anaerobic biodegradation test, used in this study,


enables good evaluation of the polymer materials biodegradation, which is very important for understanding plastic
waste behaviour under real environmental conditions.
Methanogenic biodegradation of PCLs typically yielded
from 54 to 60% of the theoretical biogas yield. The biodegradability of PLAs achieved from 56 to 84% of the
theoretical value. The biogas yield about 676677 mL/g TS
of original material with satisfactory methane content in
excess of 60% conrmed the potential of these materials
for anaerobic treatment in the case of their exploitation in
agriculture or as a packaging material in the food industry.

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Concerning the degradation mechanism, surface erosion pattern was conrmed for PCL melt-pressed lms;
whereas both surface erosion and bulk degradation
occurred in PLA lms. Despite general concept of random
abiotic hydrolysis, which is assumed to occur at the beginning stage of polymer samples incubation, we clearly
proved that also enzyme-catalysed unzipping took place.
Formed monomeric products were rapidly mineralised
yielding biogas (no lag phase). However, during following
incubation random hydrolytic scission begin to prevail and
the lms degradation, i.e. chains scission proceeded more
rapidly than biodegradation process itself.

ACKNOWLEDGEMENTS
The authors thank specic university research no. 20/2015
and MSM6046137308 for nancial support.

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First received 9 November 2015; accepted in revised form 29 January 2016. Available online 16 February 2016

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