International Biodeterioration & Biodegradation (1996) 85-92

Copyright 0 1996 Elsevier Science Limited

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Assessment of Biodegradability of Plastics under

Simulated Cornposting Conditions in a Laboratory
Test System

Andreas Starnecker’ & Michael Menner

Fraunhofer-Institute for Food Process Engineering and Packaging, Steinerstr. 15, 81369 Munich, Germany

An automated laboratory-scale test system was developed for measuring the

aerobic biodegradability of degradable plastics under simulated composting
conditions. Biodegradation was monitored by measuring microbial carbon
dioxide formation and oxygen consumption. Completeness of biodegradation
was assessed in an aquatic test by conducting a carbon mass balance. The
percentage of plastic carbon degraded to carbon dioxide, biomass and water-
soluble byproducts were determined. The rate of biodegradation under simulated
composting conditions was measured in a fixed-bed system with mature compost.
A time-dependent temperature profile was applied to simulate the natural self-
heating of a composting process. The aquatic test was conducted at a constant
temperature of 30°C as well as with a temperature profile. The rate of
biodegradation was significantly higher in the aqueous environment. Equal
degrees of mineralization were reached in the aquatic and the fixed-bed system
only if the same temperature profile was applied. Conducting the aquatic test at a
constant temperature of 30°C less microbial carbon dioxide formation was
observed. However, a carbon mass balance revealed that taking into
consideration the portion of the plastic’s carbon incorporated into biomass, a
similar degree of biodegradation was reached. Consequently, the measurement of
microbial carbon dioxide production is not sufficient to assess the extent of
biodegradation of plastics. In the heterogeneous matrix ‘compost’, it is not
feasible to assess the completeness of biodegradation due to limited possibilities
to analyze degradation intermediates and biomass growth. Therefor& a new
fixed-bed system with an inert, carbon-free packing material was developed. The
inert material was inoculated with an aqueous eluate from compost. First results
showed biodegradation rates similar to a compost environment. Copyright 0
1996 Elsevier Science Limited.

INTRODUCTION In Germany, admission criteria for input

materials of an industrial composting process are
Composting represents an increasingly important specified in the German federal states guidelines
route of disposal for the organic fraction of for compost (LAGA M 10, 1995). Only input
municipal solid waste. In the future also, materials materials which are completely biodegradable are
that are not of native-organic origin are planned as accepted for cornposting. Non native-organic
input materials for composting facilities. One materials have to pass a suitability test. Figure 1
important group of those man-made materials are shows the current test procedure for the assessment
biodegradable plastics. Unlike most of the of compostability as proposed by the working
commodity plastics, these polymers can be committee ‘Biodegradable Plastics’ FNK 103.3 of
degraded and utilized as a source of .carbon and the German Institute for Normification (DIN)
energy by a variety of microorganisms, if they get (Schroeter et al., 1994).
into an environment favourable for microbial First, there is a basic chemical product analysis
activity (e.g. compost, soil, waste water). to identify pollutants (e.g. heavy metals, poly-
‘Paper presented at the fourth meeting of the Biodegradable chlorinated aromatics) or non-biodegradable
Plastics Group, International Biodeterioration Research components of the plastic. Second, two laboratory-
Group, Winchester, UK, May 3-5, 1995. scale tests for the assessment of complete aerobic

85
86 A. Starnecker, M. Menner

Laboratory-scale

Pilot plant-scale
+Lzzq
field-proven model experiment

*
Field testing

Fig. 1. Test procedure for the assessment of compostability (draft proposal DIN FNK 103.3).

biodegradability are proposed: an aquatic biodegradation (Gilbert & Watson, 1977). Biomass
screening test and a solid-state compost simulation itself eventually will be degraded to carbon dioxide.
test. Existing biodegradability lab-tests for plastics However, over the usual time scale of a biode-
(e.g. ASTM 5209-92, ASTM 5338-92) are currently gradation test, complete mineralization to carbon
being modified to experimentally prove complete- dioxide generally will not be observed. Therefore,
ness of biodegradation. The next two steps of the the DIN proposes to conduct a carbon mass
test procedure examine the suitability of the plastic balance to assess ultimate biodegradation
material for cornposting. This is assessed under
controlled conditions in C plastic - Cc02 + Cbiomass + Csoluble
pilot plant-scale
cornposting units and under practical conditions in + Cresidual polymeric material
technical cornposting plants (Streff et al., 1994).
The carbon content of the plastic can, in princi-
Finally, utilization properties and ecotoxicology of
ple, either be degraded to carbon dioxide (C&J,
the compost obtained by adding a certain
biomass (Cbiomass) or water-soluble intermediates
percentage of the plastic as input material are
(C soluble). The percentage of residual, non-biode-
investigated.
graded material can be calculated from the differ-
Ultimate biodegradation ence to the initial plastic carbon (Cplastic). The
carbon content of the plastic can either be derived
Microbial degradation of plastics is initiated by the from its chemical structure or from experimental
secretion of enzymes, which cause a chain cleavage (elemental) analysis. Ultimate biodegradation is
of the polymer into oligomers or monomers, reached if 100% of the plastic’s carbon is degraded
respectively. These water-soluble enzymatic to carbon dioxide and biomass. Currently, a
cleavage products are absorbed into the microbial carbon mass balance can only be conducted in an
cell where they are metabolized. End-products of aquatic system where the plastic is the sole source
the aerobic metabolism are basically carbon of carbon. In compost - a heterogeneous matrix
dioxide and water. A portion of the plastic’s with various carbon sources - the build-up of new
carbon is utilized for the build-up of new biomass. biomass and the formation of degradation inter-
According to the definition of the DIN, a plastic mediates cannot be determined with sufficient
is called biodegradable if all of its organic accuracy. As a consequence, complete biodegrada-
components undergo a total biodegradation to tion in compost only can be guaranteed if 100%
naturally occurring metabolic end-products mineralization of the plastic’s carbon to carbon
(Pantke, 1994). This process is called ultimate dioxide is measured (CcoZ = Cpiastic).
 Assessment of biodegradability of plastics 81

Automated laboratory test system preparation of biodegradable polymer blends due

to its compatibility with other polymers. PCL was
At the Fraunhofer-Institute for Food Process applied as a powder which was separated into
Engineering and Packaging (FhILV) an automated different particle size fractions by sieving to
laboratory test system was developed to measure investigate the influence of particle size on the
the aerobic biodegradability of plastics (Fig. 2). biodegradation rate. As a second test material, a
Biodegradation tests are conducted in an aquatic plastic bag made from a blend of corn starch and
system as well as in a solid-state compost synthetic polymers was investigated. This bag is
environment. The biodegradation process is used for the collection of bio-waste from
continuously monitored by measuring the households and is supposed to be composted
microbial carbon dioxide formation and oxygen together with the bio-waste.
consumption. Currently, the test system consists of Mature compost from an industrial composting
16 bioreactors with a capacity of 1.5 1 each for the plant was used for the fixed-bed system. The
aquatic test and 51 each for the fixed-bed test, compost had a volatile solids content of 50% (w/w)
respectively. The bioreactors are temperature- of dry solids, a C/N-ratio of 12 and a pH of 7.6.
controlled to simulate the natural self-heating of a The percentage of carbon and nitrogen in the
composting process. The aeration rate of each compost was measured with a total organic carbon
reactor is automatically controlled based on the analyzer (Model Coulomat 702, Stroehlein Instr.,
measured oxygen concentration to avoid anaerobic Germany) and a total nitrogen analyzer (Model
conditions in the bioreactors. In standard aquatic Macro N, Foss-Heraeus, Germany). The moisture
biodegradation tests aeration is performed with air content of the compost was adjusted to 50% (w/w).
free of CO2 (e.g. ASTM 5209-92). However, the For the aquatic test, a mineral salt solution was
absence of carbon dioxide in the test medium in used that provided all essential nutrients for
some cases may delay the onset of biodegradation microbial growth, but no source of carbon (Table
(Pitter & Chudoba, 1990; Gilbert & Watson, 1977). 1). The medium was inoculated with an aqueous
Therefore, aeration of the bioreactors is performed eluate from the above mentioned mature compost.
with air of ambient C02-concentration. The inoculum represented a broad mixed microbial
flora specific for compost. For the aquatic test and
the fixed-bed test, a time-dependent temperature
MATERIAL AND METHODS profile according to ASTM 5338-92 was applied
simulating the natural self-heating of a composting
Poly-e-caprolacton (PCL) (Tone@ P-767, Union process (Table 2). Additionally, the aquatic test
Carbide) was chosen as a test polymer. PCL is a was conducted at a constant temperature of 30°C.
synthetic aliphatic homopolyester with a molecular In the aquatic system a carbon mass balance was
weight of Mn = 43 OOODa and a melting performed. Biomass growth was assessed by
temperature of 60°C. PCL is used frequently in the measuring the intracellular biomass protein

Biodegradable plastic
(powder, film)

Mineral salts solution

Mixed microbial population

(eluate from compost)

Biodegradable plastic

Fig. 2. Automated laboratory test system for measuring biodegradability of plastics.

88 A. Starnecker, M. Menner

according to a modified method of Lowry mass was assumed (Schlegel, 1992). Water-soluble
(Sperandio & Puechner, 1993). An average protein intermediates were determined by measuring the
and carbon content of 50% (w/w) of the cell dry concentration of dissolved organic carbon (DOC)
with a total organic carbon analyzer (Model TOC-
Table 1. Composition of the Mineral Salt Solution 500, Shimadzu Corp., Japan) after filtration
through a 0.2 pm membrane filter.
Component Concentration [g 1-‘I
NazHP04 * 2 HZ0 6.97
KH2P04 3.75 RESULTS AND DISCUSSION
(m)2so4 4.0
MgS04 * 7 H20 0.2 Carbon balance
CaC12 * 2 H20 0.13
FeCls * 6 HZ0 0.002 7 Figure 3 shows the time course of microbial C02-
Trace elements solution 0.001
(Drews, 1968) formation and carbon mineralization during
biodegradation of PCL in the aquatic system. A
microbial adaption (lag-) phase of approximately
Table 2. Time-dependent Temperature Profile for the Fixed- one day was observed followed by an exponential
bed Test and the Aquatic Test
phase of microbial CO*-formation. The CO*-
Time [days] Temperature [“Cl evolution rate reached a maximum after two days
O-l 35 of incubation. After eleven days, 80% of the
l-5 58 polymer carbon was degraded to carbon dioxide.
5-28 After a duration of 2, 3, 4 and 9 days, a carbon
2845
mass balance was performed. Figure 4 reveals that

100

/ -- 90
;:I’;:;

- I,2 --
d
2 I--
6
t 0.9 --
E
&
e 0,6 --

8 0,4 --

0,2 -- ~,~ ~.

01
0 1 2 3 4 5 6 7 8 9 10 11

Time I d

Fig. 3. Microbial COz-formation rate and carbon mineralization in the aquatic test Polymer: PCL powder, 18&200pm, test
concentration; 1.Og l-l, temperature: 30°C.

c 76 W C-residual polymer
.o
(calculated)
2 60
'C q C-soluble
g66 0 C-biomass
m c-co2
546
e
J 30

2 days 3 days 4 days 9 days

Fig. 4. Carbon distribution during microbial degradation of PCL in the aquatic system.
 Assessment of biodegradability of plastics 89

a significant portion of the plastic’s carbon was (increasing surface area) of the polyester powder.
incorporated into biomass. After 3 days biomass However, the degree of mineralization after 20
carbon reached a maximum of 38% of the initial days was similar for all particle size fractions.
polymer carbon. Summing up the percentage of Consequently, a comparison of the degradation
carbon dioxide and biomass carbon a biodegrada- rate of different biodegradable plastics is only valid
tion degree of approximately 80% is reached if the test specimens have similar geometry
already after 3 days. After 9 days 78% of the (powder, film) and surface area.
plastic was mineralized to carbon dioxide, 13%
was incorporated into biomass and 9% was Comparison of compost simulation test and aquatic
measured as water-soluble metabolites. From the test
carbon balance it is apparent that after 9 days no
more residual polymeric carbon was left. Figures 6-8 show the results of a biodegradation
test for a starch-based plastic bag in compost in
Influence of particle size on biodegradation rate comparison with the aquatic test. Figure 6 is a plot
of the microbial carbon dioxide production in the
Figure 5 shows the rate of biodegradation for compost system as a function of time. The addition
different particle-size fractions of PCL powder in of the test material caused a significant increase in
the aquatic test. The biodegradation rate increased the microbial respiration rate, compared to the
significantly with decreasing particle size blank compost assay without test material. The

0 2 4 6 8 10 12 14 16 18 20

Time I d

Fig. 5. Biodegradation of different particle size fractions of PCL powder in the aquatic system.

20 25

Time I d

Fig. 6. Time course of C02-formation in the compost simulation test (test material; starch-based plastic bag, film thickness: 50 pm)
(results are mean values from triple assays).
90 A. Starnecker, M. Menner

0 1

0 5 10 15 20 25 30 35 40 45

The I d

Fig. 7. Carbon mineralization in the compost system with temperature profile in comparison to the aquatic system with tempera
ture profile and constant temperature of 30°C (Test material: starch-based plastic bag, film thickness: 50 pm).

constant temperature temperature profile

( T = 30°C) ( T = 36-66~60-3SC )

Fig. 8. Influence of temperature on the carbon balance in the aquatic system after a test duration of 45 days.

80

10

0
0 5 10 15 20 25 30 35 40 45

Time I d

Fig. 9. Biodegradation in compost in comparison with a carbon-free fixed-bed (Test material: starch-based plastic bag, 50 pm).
 Assessment of biodegradability of plastics 91

influence of the temperature profile on the gated whether a part of the plastic’s carbon may be
microbial respiration rate can be seen clearly. incorporated into biologically-stable humic
COZ-production due to microbial degradation of substances. Consequently, 100% mineralization
the test material was determined from the could not be measured even for completely biode-
difference in CO*-formation to the blank compost gradable materials. On the other hand, it is
assay. Figure 7 shows the time course of carbon reported that background C02-evolution of
mineralization in compost in comparison to the compost or soil may be enhanced by the addition
aquatic system. After 45 days, 68% of the plastic’s of a biodegradable material (Sharabi & Bartha,
carbon was degraded to carbon dioxide in the 1993). Carbon dioxide formation may be measured
compost environment. An equal degree of miner- that does not result from microbial degradation of
alization was reached in the aquatic test if the same the test material. Therefore, at our institute a new
temperature profile was applied. However, the lab-test was developed, which replaces the hetero-
biodegradation rate was significantly higher in the geneous matrix ‘compost’ by a biologically inert,
aquatic system. A carbon mineralization of nearly carbon-free material. Screening tests with different,
70% was measured already after 15 days, whereas porous materials indicated that environmental
it took more than double of the time in the conditions similar to compost could be created
compost system to reach the same degree of with those materials (e.g. water activity, porosity,
mineralization. Conducting the aquatic test at a storage of nutrients). Figure 9 shows the time
constant temperature of 30°C a reduced rate of course of microbial degradation of a starch-based
biodegradation was observed compared to the plastic bag in a tixed-bed with inert packing
aquatic system with time-dependent temperature material in comparison to compost. The inert
profile. Only 62% of the plastic’s carbon was packing material was inoculated with an aqueous
mineralized after 45 days instead of 70% when eluate from compost. Figure 9 demonstrates that
applying the temperature profile (Fig. 7). similar biodegradation rates could be observed
A carbon balance revealed that the ratio of compared to the compost system. Since the plastic
microbial carbon dioxide formation to biomass is the sole source of carbon in the fixed-bed, it will
growth was dependent on temperature (Fig. 8). be possible to conduct a carbon mass balance for
After 45 days less than half of the biomass was the assessment of ultimate biodegradation.
detected in the aquatic system with temperature
profile compared to the assay with constant
REFERENCES
temperature. However, the degree of biodegrada-
tion - combining carbon dioxide and biomass American Society for Testing and Materials (ASTM) (1992).
estimations - amounted to a similar value of 80 or Standard Test Method for Determining the Aerobic
77%, respectively. Biodegradation of Plastic Materials in the Presence of
Municipal Sewage Sludge. ASTM D5209-92, Philadelphia,
According to Fig. 8, approximately 20% of the USA.
plastic’s carbon was still not degraded after 45 American Society for Testing and Materials (ASTM) (1992).
days. Further investigations are under way to find Standard Test Method for Determining the Aerobic
Biodegradation of Plastic Materials under Controlled
out whether this portion of the plastic will be composting Conditions. ASTM D5338-92, Philadelphia,
biodegraded at extended test duration. USA.
The results of this experiment confirm that an Drews, G. (1968). Mikrobiologisches Praktikum fur Naturwis-
senschaftler. Springer, Berlin.
assessment of plastic biodegradation only based on
Gilbert, P. A. & Watson, G. K. (1977). Biodegradability
the measurement of microbial carbon dioxide testing and its relevance to environmental acceptability.
formation is not sufficient. In order to assess the Tenside Detergents, 14, 171-177.
completeness of biodegradation the portion of the Llnderarbeitsgemeinschaft Abfall (LAGA) Guideline M 10
(1995). Qualitdtskriterien und Anwendungsempfehlungen fur
plastic’s carbon which is incorporated into new Kompost (‘Quality criteria and recommendations for the
biomass has to be determined. use of compost’).
Pantke, M. (1994). Biologisch abbaubare Kunststoffe -
Begriffsbestimmung und Normung von Prtifverfahren.
Fixed-bed test with inert packing material Kunststoffe, 84, 1090.
Pitter, P. & Chudoba, J. (1990). Biodegradability of Organic
As already mentioned, ultimate biodegradation in Substances in the Aquatic Environment. CRC Press, Boca
compost can only be measured if 100% miner- Raton, FL.
Schlegel, H. G. (1992). Allgemeine Mikrobiologie. Georg
alization of the plastic’s carbon to carbon dioxide Thieme, Stuttgart.
occurs. So far, however, it has not been investi- Schroeter, J., DeWilde, B., Gottschall, R., Koch, R. &
92 A. Starnecker, M. Menner

Starnecker, A. (1994). Assessment of compostability of Gesamtproteine als Biomasse-Parameter in wll3rigen

polymeric materials. Draft proposal DIN FNK 103.3. Kulturen und auf Tragermaterialien aus Bio-Reaktoren.
Sharabi, N. E. & Bartha, R. (1993). Testing of some Wasser, Abwasser., 134,482-485.
assumptions about biodegradability in soil as measured by Streff, L., Gottschall, R., Bidlingmaier, W. & Vogtmann, H.
carbon dioxide evolution. Appl. Environ. Microbial., 59, (1994). Biodegradable plastics in cornposting. Conference
1201-1205. papers, Rocky Mountain Conf. of Composting, Denver (in
Sperandio, A. & Ptichner, P. (1993). Bestimmung der press).