APPLIED AND ENVIRONMENTAL MICROBIOLOGY, Apr. 1993, p. 1155-1161 Vol. 59, No.

4
0099-2240/93/041155-07$02.00/0
Copyright X 1993, American Society for Microbiology

Degradation of Degradable Starch-Polyethylene Plastics in a

Compost Environmentt
KENNETH E. JOHNSON, ANTHONY L. POMETTO III,* AND ZIVKO L. NIKOLOV
Department of Food Science and Human Nutrition and Center for Crops Utilization
Research, Iowa State University, Ames, Iowa 50011
Received 29 September 1992/Accepted 6 January 1993

The degradation performance of 11 types of commercially produced degradable starch-polyethylene plastic

compost bags was evaluated in municipal yard waste compost sites at Iowa State University (Ames) and in
Carroll, Dubuque, and Grinnell, Iowa. Masterbatches for plastic production were provided by Archer Daniels
Midland Co. (Decatur, Ill.), St. Lawrence Starch Co. Ltd. (Mississauga, Ontario, Canada), and Fully
Compounded Plastics (Decatur, Ill.). Bags differed in starch content (5 to 9%/o) and prooxidant additives
(transition metals and a type of unsaturated vegetable oil). Chemical and photodegradation properties of each
material were evaluated. Materials from St. Lawrence Starch Co. Ltd. and Fully Compounded Plastics
photodegraded faster than did materials from Archer Daniels Midland Co., whereas all materials containing
transition metals demonstrated rapid thermal oxidative degradation in 70°C-oven (dry) and high-temperature,
high-humidity (steam chamber) treatments. Each compost site was seeded with test strips (200 to 800 of each
type) taped together, which were recovered periodically over an 8- to 12-month period. At each sampling date,
the compost row temperature was measured (65 to 95°C), the location of the recovered test strip was recorded
(interior or exterior), and at least four strips were recovered for evaluation. Degradation was followed by
measuring the change in polyethylene molecular weight distribution via high-temperature gel permeation
chromatography. Our initial 8-month study indicated that materials recovered from the interior of the compost
row demonstrated very little degradation, whereas materials recovered from the exterior degraded well. In the
second-year study, however, degradation was observed in several plastic materials recovered from the interior
of the compost row by month 5 at the Carroll site and almost every material by month 12 at the Grinnell site.
The plastic bags collected from each community followed a similar degradation pattern. To our knowledge, this
is the first scientific study demonstrating significant polyethylene degradation by these materials in a compost
environment.

Plastics developed during the last 5 decades are charac-
teristically inert and resistant to microbial attack. Different
degradable plastics, such as polylactides, poly(3-hydroxy-
butyrate-3-hydroxy valerate), ethylene-carbon monoxide
polymers, vinyl ketone copolymers (Guillet process), and
starch-filled polyethylene (Griffin process) (15), have been
developed. These plastics differ in degradation rate, appli-
cation, and price. In one development, plastics' inertness
and resistance to microbial attack was reduced by incorpo-
rating starch and later prooxidants (transition metals and oil)
(9). Three types of degradation of polyethylene in these
degradable starch-polyethylene polymers can occur by dif-
ferent molecular mechanisms: chemical degradation, photo-
degradation and biological degradation. Chemical degrada-
tion occurs when the prooxidants catalyze the formation of
free radicals in polyethylene, which react with molecular
oxygen to attack the polyethylene matrix (1). Heat and
oxygen accelerate this chain scission of the polyethylene.
Photodegradation also occurs within the polyethylene matrix
whereby UV light catalyzes the autoxidation and generation
of free radicals (5). Biological degradation of these polyeth-
ylene films has been reported in pure-culture studies with
Streptomyces species after chemical degradation was initi-
ated (12) and with their corresponding extracellular enzymes
*
Corresponding author.
t Journal paper J-15087 of the Iowa Agriculture and Home
Economics Experiment Station, Ames, Iowa (project no. 2889 and
0178).
1155
(13). Recently enacted state-promulgated laws regarding
yard waste disposal have stimulated the use of degradable
bags as a vehicle for transporting yard waste to a compost
site. Therefore, a comprehensive evaluation of different
degradable plastic bags is necessary to ensure that these
materials will degrade along with yard waste.
In this study, we characterized the chemical degradation,
photodegradation, and biological degradation of 11 commer-
cially produced degradable starch-polyethylene bags. The
data illustrate different rates for chemical degradation and
photodegradation within a 20-day or an 8-week period,
respectively. Major reductions in weight-average molecular
weight of polyethylene were observed for materials from
Archer Daniels Midland Co. (ADM) (Decatur, Ill.) (26 to
54%; Grinnell site) and St. Lawrence Starch Co. Ltd. (SLS)
(Mississauga, Ontario, Canada) (20 to 28%; Carroll site)
recovered from the interior of a compost row at 12 months.
MATERIALS AND METHODS
Degradable plastics. (i) Film production. Eleven different
degradable starch-polyethylene bags were produced by Pe-
toskey Plastics, Inc. (Petoskey, Mich.). Five types were
made according to the specifications of ADM, five types
were made according to SLS specifications, and one type
was made according to Fully Compounded Plastics (FCP)
specifications (Decatur, Ill.) (Table 1). The bags were dis-
tributed to each municipal compost site for community yard
waste collection. Each type of degradable bag was obtained
from each compost site and stored at 4°C.
1156 JOHNSON ET AL. APPL. ENVIRON. MICROBIOL.

TABLE 1. Transition metal composition and starch concentration direction, placed into a steam chamber with continuous
present in each degradable starch-polyethylene plastic steam flow, and harvested after 2, 4, 6, 8, 10, 12, 16, and 20
Level (ppm) of: days. The plastic strips were placed on a vinyl-coated test
Plastic type % Starch tube rack and regularly moved within the chamber to pro-
Copper Iron Manganese vide even exposure. The harvested samples were washed in
ADM 70% ethanol and dried overnight at 45°C. Film mechanical
ADM-3 3 13 140 6 properties and polyethylene molecular weight distributions
ADM-4 2 64 135 6 were determined.
ADM-6 2 14 91 6 (iii) UV light treatment. A long (365-nm)-wave UV lamp
ADM-7 2 230 74 6 was used to evaluate the photosensitivity of each film.
ADM-11 1 300 113 6 Plastic strips (2.54 by 15.24 cm) were cut in machine
direction and placed into a UV box (17.78 by 40.64 cm) at a
EcoStar Inc. distance of 17.78 cm from the lamp for 8 weeks (12). The
SLS-2 51 203 1 9 plastic strips were turned twice a week to ensure even
SLS-5 43 153 1 5
SLS-8 4 19 3 9 exposure to the light. Samples were removed after 1, 2, 3, 4,
SLS-8p 63 3 210 9 and 8 weeks. Film mechanical properties and polyethylene
SLS-10 63 4 214 6 molecular weight distributions were determined.
Seeding of plastic strips at compost sites. (i) Test strip
FCP 2 184 100 6 preparations. Each plastic film was cut in machine direction
(4.5 by 40 cm), color coded with colored tape on one end,
and taped together with strapping tape in a specific order. In
the first-year study, plastic films ADM-3, ADM-4, ADM-6,
(ii) Determination of transition metal content. The transi- SLS-2, SLS-5, and SLS-8 were used. In the second-year
tion metal content for each type of bag was determined by study, all the materials in Table 1 were used except ADM-6.
atomic absorption (11) (Table 1). Samples of each plastic Therefore, in the second-year study, the materials used from
were combusted in an open flame and then in a tube furnace the first-year study had been stored at 4°C for 1 year before
to ensure complete combustion. The ash content of each seeding.
plastic was determined, and a known amount of ash (25 mg) (ii) Seeding the compost rows. Compost rows were main-
was solubilized with 10 ml of American Society for Testing tained at Iowa State University (ISU) (Ames) and in Carroll,
and Materials type II deionized water plus 10 ml of trace- Dubuque, and Grinnell, Iowa. Lawn and garden materials
metal-grade 70% HNO3 in a 125-ml Erlenmeyer flask. The were collected in starch-polyethylene bags from residences.
solution was refluxed gently to boil off the water. Approxi- Upon collection, the material was ground in a tub grinder
mately 40 ml of water was added, and the sample solution and spread into rows, periodically turned by landfill person-
was filtered (Whatman no. 41 filter) and brought to 100 ml in nel. During the grinding process, 800 test strips were ran-
a volumetric flask with water. All treatments were replicated domly added to the shredded material being discharged by
three times, and one reagent blank (no ash) was prepared the grinder. Rows were typically 1.8 to 2.5 m high, 3 to 4.5
along with each set of ashed samples. Before use, all m wide, and 6 to 9 m long. The ISU compost pile in Ames
glassware was rinsed with 70% HNO3 to remove any con- was an exception to this practice and was neither ground nor
taminants. Concentrations of iron, copper, and manganese turned and had a much lower level of biological activity. In
in each sample solution were analyzed with a Smith-Hieftje the first-year study, rows of unground bags were also eval-
12 atomic absorption spectrophotometer (Thermo Jarrel Ash uated at each compost site.
Corp., Franklin, Mass.). (iii) Stapled strips for outdoor light exposure. The same
(iii) Determination of starch content of each plastic. The strips prepared for the second year of seeding were stapled
starch content of each plastic was determined according to to a fence at the ISU compost site in mid-August. Strips
the phenol-sulfuric acid procedure of Fratzke et al. (6) (Table were stapled on both sides of the fence, 1 m above ground.
1). A 60-mg plastic sample was dissolved in 4 ml of Decalin Strips were removed at 1, 5, and 12 months for polyethylene
and heated to 150°C for 40 min. After brief cooling, 5 ml of molecular weight distribution analysis.
1 M HCl was added to solubilize, hydrolyze, and extract the (iv) Evaluation of compost activity and recovery of test
starch at 100°C for 30 min. After heating, the Decalin was strips. At each sampling, the internal temperature of each
removed with a Pasteur pipette, 1 to 2 ml of the aqueous compost row was determined. Test strips on the outer layer
phase was transferred to another tube, and the phenol- of the row (external) were recovered first. A front-end loader
sulfuric acid analysis was performed. The sample aliquot was employed to turn the pile to retrieve internal test strips.
was added to distilled water (total volume, 1 ml) plus 1 ml of Compost rows were turned on sampling days, except at the
6% phenol and 5 ml of concentrated H2SO4. After 30 to 60 Dubuque site, where a compost fluffer tended to destroy our
min, the A490 values of phenol-sulfuric acid samples relative test strips.
to that of distilled water were read. A standard curve was Film evaluations for degradation. (i) Mechanical properties.
prepared with native corn starch. The percentage of elongation was determined at room tem-
Accelerated laboratory degradation assays. (i) Oven treat- perature with an Instron model 4502 Universal Tester (In-
ment. Plastic strips (2.54 by 15.24 cm) were cut in machine stron Corporation, Canton, Mass.), which was operated at
direction (parallel to axis of blown film), placed in a forced- 500 mm/min with a 5-cm initial grip distance. All samples
air oven (70°C), and removed after 2, 4, 6, 8, 10, 12, 16, and were equilibrated to 50% relative humidity for at least 40 h
20 days for evaluation of degradation (12). Film mechanical before analysis (3). Mechanical properties of the plastic
properties and polyethylene molecular weight distributions recovered from the compost sites were not measured be-
were determined. cause nicks or mechanical distortions present in samples
(ii) High-temperature, high-humidity (HT-HH) treatment. skewed the mechanical property analysis.
Plastic strips (2.54 by 15.24 cm) were cut in machine (ii) Polyethylene molecular weight distribution. A Waters
VOL. 59, 1993 DEGRADATION OF STARCH-POLYETHYLENE PLASTICS 1157

so weight-average molecular weights (MOs) and number-aver-

Vr^a
w, .
o ADM-a
ADM-4
0 ADM-3
A ADM-4 age molecular weights (M0s) of the polyethylene samples.
2000
ADM-6
a ADM-7
z 60)o
0
* ADM-6
a ADM-?
-
The Af, range for accurate analysis is from 2,700 to 610,000,
CZ
0 0~~~~~
ADM-11- P 3o ADM-11 based on polystyrene standards.
0
2 15000

& .0 0 L1 z
0

z 300

1510
4
Statistical analysis. Analysis of variance was used to
determine the significant differences between films recov-
ered from the compost sites and their corresponding zero-
time controls by using an SAS program (14). Data from the
HT-GPC were evaluated, and values for which P was <0.05
0 4 a 12 is 20 were considered significantly different.
0 4 8 12 16 20

0 8IS-2
25000 30 &~~~~12-8
80-5 RESULTS AND DISCUSSION
a
z Oven treatment. The rate of oxidative degradation in the
20000DO, 81S-1
I* p
0 70°C oven differed among plastics (Fig. 1). Reduction in
150(0 0o
elongation of each film paralleled reduction in molecular
C,I weight. The most rapid degradation was observed for
10000

0.
2060
0 4 a 12 15 20
4 a 12
TIME (DAYS) TIME (DAYS)
FIG. 1. Weight-average molecular weight and percent elongation
change of degradable plastics in 70°C-oven treatment for 20 days.
Each value is the mean of two replicates.
model 150-C (Waters/Millipore Co., Milford, Mass.) high-
temperature gel permeation high-pressure liquid chromato-
graph (HT-GPC) was used to determine changes in the
molecular weight distribution of polyethylene. Three Waters
pStyragel HT linear GPC columns (7.8 by 300 mm) were
used in series. The procedure of Lee et al. (12) was used for
sample preparation and for chromatographic evaluation (mo-
bile phase, 1,2,4-trichlorobenzene; flow rate, 1 ml/min; in-
jection volume, 200 iLI). With each run, a set of polystyrene
molecular weight standards (molecular weights of 4,016,
53,500, and 610,000) was included. Maxima 820 computer
software (Waters/Millipore Co.) was used to determine
ADM-7, ADM-11, SLS-8p, SLS-10, and FCP films, whose
initial MW was reduced to 50,000 after 4 days. The ADM-3
and ADM-4 samples needed 8 days, SLS-2 and SLS-5
15
needed 10 days, and ADM-6 needed 16 days to reach an MW
of 50,000. The slowest degradation was measured for SLS-8
films. The degradation profile for each plastic type was not
always linear but exhibited plateaus, as illustrated by
ADM-3, ADM-4, ADM-6, SLS-2, SLS-5, and SLS-8. The
undulating pattern for ADM-6 reported by Lee et al. (12) was
observed. The rise in MW for ADM-6 is probably due to
cross-linking of polyethylene (5). Prooxidant transition metal
combinations FR-Mn and Mn-Cu (the underlined metal being
dominant) demonstrated the greatest effect on thermal deg-
radation in the 70°C-oven study (Table 2). The plastic films
containing either transition metal combination required 3 to
5 days to reach an MW of less than 50,000. The other
transition metal combinations, as well as Mn alone, were
less effective in accelerating the degradation. The overall
ranking of the different transition metal combinations based
on the enhancement of chemical degradation is E-Mn =
Mn-Cu > Mn-Fe = R-Cu > Mn. The SLS-8 film contained
no additional transition metals, and its degradation was the

TABLE 2. Comparison of degradation performance under different conditions as related to prooxidant transition
metal composition of the respective materials
% Reduction in M, after
Transition Transition L 12 mo at:
metals' metal ratio Film type Oven HT-HH UV light Carroll Grinnell

Es-Cu 4.5 SLS-2 10 5 3 24" 0

3.5 SLS-5 10 >20 3.75 23 20d
En-Mn 3.1 ADM-7 3 11 8 28' 37'
2.7 ADM-11 3 11 6.5 2 54e
1.8 FCP 3 17 2.75 42' 15d
Mn NAf ADM-3 9 >20 7.5 4 39'
NAf ADM-6 17 >20 >8 NDg NDg
Mn-Cu 3.3 SLS-8p 3 4 2.75 25 lld
3.8 SLS-10 5 5 2.5 20 7
Mn-Fe 2.1 ADM-4 9 20 6.5 28d 26'
None NAf SLS-8 >20 19 >8 0 od
a Transition metals detected in each film, with the dominant metal underlined.
b The time at which each film's
polyethylene Mw was <50,000.
c The time at which each film's polyethylene Mw was <75,000.
d Significant reduction
(P 0.05) in Mn only was detected.
<
Significant degradation was detected for the polyethylene in the second-year study for and Mn (P
calculated by dividing the 12-month value by the corresponding initial value.
Afw < 0.05). The percent reduction in MW and M" was
f NA, not applicable.
g ND, not done.
1158 JOHNSON ET AL.
C)
* u
\ 0
0 u
I L
hJ
TIME (DAYS) TIME (DAYS)
FIG. 2. Weight-average molecular weight and percent elongation
change of degradable plastics in HT-HH treatment for 20 days. Each
value is the mean of two replicates.
slowest, demonstrating the requirement for transition metal
addition.
HT-HH treatment. The rate of oxidative degradation oc-
curring in the steam chamber differed significantly from that
in the 70°C oven (Fig. 2). The loss of elongation, as measured
with the Instron, occurred in a span of 2 to 4 days. The
elongation measurements were variable and did not corre-
spond to the degradation data obtained from the HT-GPC.
For example, an MW of 150,000 for FCP (8-day sample) and
one of 125,000 for ADM-11 (8-day sample) had correspond-
ing percent elongations of 389 and 30%, respectively. Once
the MW went below 125,000, the plastic film became brittle
and fractured under minimal load. Therefore, only HT-GPC
was used to measure the amount of degradation occurring
below this Mw.
Some HT-HH-treated films displayed longer degradation
lags or very little degradation (Fig. 2) compared with 70°C-
oven-treated films (Fig. 1). The HT-HH conditions more
closely simulated a compost environment with high temper-
atures, high humidity, and low oxygen tensions, but they
lacked biological activity. Furthermore, ADM-7 and
ADM-11 in the HT-HH and 70°C-oven treatments yellowed
more than did the other films; this finding indicates the
possible absence of antioxidants in the film (10). Very little
degradation was observed for ADM-3, ADM-6, and SLS-5,
which contained transition metals Mn, Mn-Fe, and E-Cu,
respectively. But the SLS-8 film, which contains no transi-
tion metal additions, illustrated an undulating degradation
pattern and was significantly degraded by day 20. ADM-4,
ADM-7, ADM-11, and FCP samples demonstrated a slight
undulating pattern for degradation with a slight plateau
before reaching an M, of c75,000. The prooxidant transition
metal combinations that produced the greatest effect on
thermal degradation in this HT-HH study were Mn-Cu,
E-Mn (ADM films), and E-Cu (SLS-2 film) (Table 2).
UV light treatment. The UV treatment spanned 8 weeks
(Fig. 3). The SLS materials were more sensitive to UV light
than were the ADM materials, except for SLS-8. The FCP
material had a lower initial degradation rate before week 2
and was identical to the SLS materials afterwards. The ADM
APPL. ENVIRON. MICROBIOL.
O ADM-3
0 ADM-3
ADM-4
.A ADM-4
A
z so6, ADM-8-
*~~~0ADM-6 0 * ADM-7
ADM-7 ADM-.
o 1
0 ADM-11
0C
z
LIx
15
0 2 4 6 8
0
C,Ir v SLS-2
A SLS-5
z 60)o S SLS-3
0 a SLS-8p
z 45so o
FCP
SLS-10
z 3C6,
CL 156,-
4 6
TIME (WEEKS) 2 4 6
TIME (WEEKS)
FIG. 3. Weight-average molecular weight and percent elongation
change of degradable plastics exposed to UV light (365 nm) for 8
weeks. Each value is the mean of two replicates.
materials exhibited an undulating pattern in Mw up to week
4 and then a steady decrease to week 8. This pattern may be
due to cross-linking of the polyethylene fragments and was
previously observed for ADM-6 by Lee et al. (12). The
prooxidant transition metal combinations that generated the
greatest response of plastics to photodegradation were
Mn-Cu and E-Cu (Table 2). As the a-Mn ratio increased,
the rate of photodegradation decreased. The presence of Mn
alone did not accelerate the degradation of ADM samples.
Field compost study. Consumer verbal reports of bag
performance were excellent. No bag lost any of its mechan-
ical properties during collection and transportation to the
compost site. Bags piled and not initially ground did not
degrade unless exposed to sunlight. The portion of a bag
exposed underwent substantial photodegradation and be-
came brittle after 5 months, whereas the underside from the
same bag demonstrated no change. Furthermore, the biolog-
ical activity in the rows containing unground bags was
marginal and produced a foul odor indicating anaerobic
conditions. All ground-compost rows of both studies exhib-
ited excellent biological activity with internal temperatures
of 65 to 95°C for at least 12 months.
The seeded strips after 8 months at the municipal compost
sites in the first study showed minimal degradation (Fig. 4).
Sample collection beyond 8 months at each site was ob-
structed by the inability to locate samples in the compost
rows (numbers of test strips were quadrupled in the second
study). Samples recovered from the interior displayed no
measurable degradation for any plastic materials. The
ADM-3, ADM-4, and ADM-6 exterior samples exhibited
significant polyethylene degradation at the Grinnell site after
8 months, whereas the SLS materials did not (exposure time
to sunlight for each film is unknown). The SLS films, which
responded better to the laboratory UV light treatment, did
not demonstrate the same trend at the compost sites after
exposure to compost conditions.
The second-year study involved five additional plastic
materials, and the number of test strips added to each row
was increased to facilitate sample recovery. The samples
VOL. 59, 1993 DEGRADATION OF STARCH-POLYETHYLENE PLASTICS
30
300000
150000-
Lo 1D 0000
50000
1LJ 50000
100000
250000-
0-
FIG. 4. Weight-average molecular weight change of degradable
plastics from first-year municipal compost study. Each value is the
mean of four replicates. Symbols indicate months of degradation as
follows: 0, 0; 0, 2; 4; [II, 6;
E, 0, 8.
were seeded immediately after the grinding of collected
compost bags. During the fifth month of composting, degra-
dation began to occur in six types of plastic at the Carroll site
but not at the Grinnell and ISU compost sites (Fig. 5). Two
types of plastic (SLS-8 and SLS-8p) had significant reduc-
tions (P < 0.05) of Mw and MS, and four types of plastic
(SLS-2, SLS-10, ADM-3, and ADM-4) had a significant
reduction only of Mn at the Carroll site after 5 months of
composting. The ADM-7 and ADM-11 samples were notice-
ably brittle after 9 months. During the collection of seeded
strips, ADM-7 and ADM-11 samples were missing from half
of the recovered test strips; therefore, the analyzed samples
represent those not broken off. As a result, our data are
probably biased and give more weight to the more slowly
degrading samples. The other plastic materials were rarely
separated from the test strips, and there was no evidence of
degradation for these samples after 9 months. At 12 months,
ADM-3, ADM-4, ADM-7, ADM-11, and FCP had significant
degradation (P < 0.05) of both MW and M,. The SLS
materials had significant reduction of Mn solely. Reductions
in M, are considered the best indicators for degradation
performance of these materials in a compost site. At the
Grinnell site, the ADM films demonstrated an average loss in
MW of 39%, with their actual values ranging between 26 and
54%. At the Carroll site, SLS films demonstrated an average
loss of 23% in Mw, with values ranging from 20 to 28%. Some
differences were observed for the same film at the Carroll
1159
2000
3200000 -
200000-
X b v X 0 X
300000
rUr
FIG. 5. Weight-average molecular weight change of degradable
plastics from second-year municipal compost study. Each value is
the mean of four replicates. Symbols indicate months of degradation
as follows: 0, 0; 0, 2; U, 5;m, 9; 0, 12.
and Grinnell compost sites (ADM-3, ADM-11, and SLS-10).
These data suggest that the transition metal combination of
Fe-Mn, present in ADM-7 and ADM-11, was the best to use
for the municipal compost site (Table 2). The second-year
study rarely demonstrated a significant reduction in MW
before 9 months of composting, which explains why no
degradation was observed during the 8-month period in the
first-year study.
Polyethylene degradation and not starch degradation was
the main focus of this study. Previous researchers have
confirmed starch biodegradation in these degradable starch-
polyethylene plastics (4, 7, 8, 17). Sung and Nikolov (17)
reported a 10% enzymatic hydrolysis of the total starch in
untreated ADM-6 films, and they observed a corresponding
increase of starch hydrolysis only in heat-treated films
(70°C-oven treatment). Therefore, properly processed de-
gradable starch-polyethylene films will have 90% of the
starch granules covered with polyethylene, which restricts
the access of hydrolytic enzyme to starch until the polyeth-
ylene is degraded.
Degradation patterns observed in the laboratory studies
did not necessarily correspond to the field compost patterns.
Even though composting temperatures were between 65 and
95°C for 12 months, a very low degradation rate was ob-
served compared with the 20-day 70°C-oven and HT-HH
treatments. Although the HT-HH test was performed at a
higher temperature (100°C) than was the 70°C-oven treat-
1160 JOHNSON ET AL. APPL. ENVIRON. MICROBIOL.

formation could therefore be responsible for reducing the

B ~~~~~A
ADM-4 oxygen tension on the film surface sufficiently to slow
250000 *ADM-7 chemical and biological degradation in the compost environ-
200000
ment.
Conclusion. The 70°C-oven and HT-HH film treatments
:2 150000- were appropriate methods by which to evaluate the oxida-
0
tive degradation of starch-polyethylene plastics. The
0
< 100000o HT-HH treatment, in addition, illustrated the effect of re-
duced oxygen tension and humidity on the oxidative degra-
50000 dation of starch-polyethylene plastics. The oxygen tension
on the surface of the film appears to be the rate-limiting
o 3 6 9 12
component for degradation in the compost environment.
Because the levels of starch in the various films were similar,
300000 the prooxidant additive (transition metal) was critical in
o SLS-2
promoting the oxidative degradation of polyethylene. The
250000 SI-5
i* SLS-8
S Fe-Mn additive displayed the best catalytic activity in the
ry
field and laboratory studies. This study is the first published
1
1~~~~~
~USLS-8p
200000 work, to our knowledge, that confirms degradation of these
0
10 v FCP starch-polyethylene plastics in a natural environment.
150000
0
<100000 ACKNOWLEDGMENTS
50000
This research was supported by the Iowa Corn Promotion Board,
the Iowa State University Center for Crops Utilization Research,
0
the U.S. Department of Agriculture, the Iowa General Assembly,
0 3 6 9 12 the Iowa Department of Natural Resources, and the Iowa Agricul-
TIME (MONTHS) ture and Home Economics Experiment Station.
We thank Al Fratzke for maintaining the HT-GPC and for the
FIG. 6. Weight-average molecular weight change of degradable atomic absorption transition metal analysis and Meera Kim for her
plastics from outdoor stapled exposure study. Each value is the help in statistical analysis. We also thank Jim Ulveling of Carroll,
mean of two replicates. Tom Bylund of Dubuque, and Glenn Baker of Grinnell, Iowa, for
their assistance in the construction and management of compost
rows in their respective cities.
ment, the oxidative degradation in the steam chamber was
slower than that in the 70°C oven. This observation suggests REFERENCES
that the lower oxygen tension at the film surface retarded the 1. Albertsson, A. C., S. V. Andersson, and S. Karisson. 1987. The
chemical oxidative degradation of the polyethylene. Oxygen mechanism of biodegradation of polyethylene. Polym. Degrad.
concentration is directly proportional to the production of Stability 18:73-87.
degradation products (aliphatic hydrocarbons and oxygen- 2. Albertsson, A. C., C. Barenstedt, and S. Karlsson. 1992. Suscep-
ated organic compounds) from polyethylene in the temper- tibility of enhanced environmentally degradable polyethylene to
ature range of 75 to 2000C (16). Johnson et al. (11) demon- thermal and photooxidation. Polym. Degrad. Stability 37:163-
strated that films heated (650C) in an aqueous environment in 171.
the absence of oxygen do not degrade. Furthermore, photo- 3. ASTM D882. 1983. Standard test methods for tensile properties
degradation in the field was opposite from what was indi- of thin plastic sheeting. In 1983 Annual book of ASTM stan-
dards, American Society for Testing and Materials, Villanova,
cated in the laboratory UV light study. When films were Pa.
stapled to a fence at the ISU compost site, however, the SLS 4. Barak, P., Y. Coquet, T. R. Halbach, and J. A. E. Molina. 1991.
and FCP materials photodegraded significantly faster than Organic chemicals in the environment. J. Environ. Qual. 20:
did ADM materials (Fig. 6), as observed in the laboratory 173-179.
UV study. A rapid decrease in M, was seen for ADM-11 and 5. David, C., M. Trojan, and A. Daro. 1992. Photodegradation of
for all SLS materials at month 1 and was followed by a polyethylene: comparison of various photoinitiators in natural
slower decrease. FCP, ADM-3, ADM-4, and ADM-7 exhib- weathering conditions. Polym. Degrad. Stability 37:233-245.
ited a steady decrease up to month 5. No SLS-type film was 6. Fratzke, A. R., W. Sung, R. L. Evangelista, and Z. L. Nikolov.
present at 12 months, whereas all ADM materials were still 1991. Chemical method for the determination of starch in
intact. The main difference was that these stapled films polyethylene. Anal. Lett. 24:847-856.
7. Gilmore, D. F., S. Antoun, R. W. Lenz, S. Goodwin, R. Austin,
possessed no biofilm or organic matter. These data suggest and R. C. Fuller. 1992. The fate of 'biodegradable' plastics in
that the presence of a microbial biofilm and/or dirt on the film municipal leaf compost. J. Ind. Microbiol. 10:199-206.
surface in the compost row inhibits chemical degradation 8. Goheen, S. M., and R. P. Wool. 1991. Degradation of polyeth-
and photodegradation. Microbial growth on the film surface ylene-starch blends in soil. J. Appl. Polym. Sci. 42:2691-2701.
has been observed via electron microscopy of biologically 9. Griffin, G. J. L. 1973. Biodegradable fillers in thermoplastics.
treated films, showing extensive grooves and pits (7), and of Am. Chem. Soc. Div. Org. Coat. Plast. Chem. 33:88-92.
thermally treated films (2). Gilmore et al. (7) isolated 193 10. Gugumus, F. 1990. Antioxidants, p. 1-104. In R. Gachter and H.
bacterial species and 28 fungal species from the surfaces of Muller (ed.), Plastic additives handbook, 3rd ed. Hanser Pub-
lishers, Munich.
starch-polyethylene films exposed to a leaf compost row. 11. Johnson, K. E., A. L. Pometto, L. Somasundaram, and J. Coats.
Furthermore, extensive fungal biofilm formation on ADM-6 Microtox" assay to determine the toxicity of degradation
film in a pure-culture study by Lee et al. (12) has demon- products from degradable plastics. J. Environ. Polym. Degrad.,
strated inhibition of chemical oxidative degradation. Biofilm in press.
VOL. 59, 1993 DEGRADATION OF STARCH-POLYETHYLENE PLASTICS
12. Lee, B., A. L. Pometto HI, A. Fratzke, and T. B. Bailey, Jr. 1991.
Biodegradation of degradable plastic polyethylene by Phanero-
chaete and Streptomyces species. Appl. Environ. Microbiol.
57:678-685.
13. Pometto, A. L., Ill, B. Lee, and K. E. Johnson. 1992. Production
of an extracellular polyethylene-degrading enzyme(s) by Strep-
tomyces species. Appl. Environ. Microbiol. 58:731-733.
14. SAS Institute Inc. 1985. SAS user's guide: statistics, version 5
ed. SAS Institute Inc., Cary, N.C.
1161
15. Scott, G. 1990. Photo-biodegradable plastics: their role in the
protection of the environment. Polym. Degrad. Stability 29:135-
154.
16. Spore, R. L., and R. M. Bethea. 1972. Technique for oxidative
degradation of polyethylene. Ind. Eng. Chem. Prod. Res. Dev.
11:36-45.
17. Sung, W., and Z. Nikolov. 1992. Accelerated degradation stud-
ies of starch-filled polyethylene films. Ind. Eng. Chem. Res.
31:2332-2339.