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Medicion de La Biodegradabiloidad PDF
Medicion de La Biodegradabiloidad PDF
12
Biodegradability of
Polymers: Regulations and
Methods for Testing
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 366
6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
methods used ± which had originated from anaerobic degradation), together with a new
the field of plastics biocorrosion ± proved biomass. The extracellular enzymes are too
unsuitable to characterize biodegradable large to penetrate deeply into the polymer
materials. At the time, the failure of these material, and so act only on the polymer
polyethylenes led to a generally negative surface; consequently, the biodegradation of
image of biodegradable plastics; however, plastics is usually a surface erosion process.
the subsequent development of suitable Although the enzyme-catalyzed chain
testing methods and evaluation criteria for length reduction of polymers is in many
biodegradable plastics has resulted in the cases the primary process of biodegradation,
definition of standards by various national nonbiotic chemical and physical processes
and international standardization bodies can also act on the polymer, either in parallel
during the past 10 years. Indeed, this or as a first stage solely on the polymer.
process is ongoing, as the number of These nonbiotic effects include chemical
different environments in which plastics hydrolysis, thermal polymer degradation,
may be degraded has made necessary the and oxidation or scission of the polymer
establishment of a complex and extensive chains by irradiation (photodegradation).
battery of test methods and evaluation For some materials, these effects are used
criteria for these materials. directly to induce the biodegradation process
[e.g., poly(lactic acid); pro-oxidant modified
polyethylene], but they must also to be taken
2 into account when biodegradation is caused
General Mechanism of Biodegradation, and predominantly by extracellular enzymes.
Definitions Because of the coexistence of biotic and
nonbiotic processes, the entire mechanism
The term ™biodegradable plastics∫ normally of polymer degradation could ± in many
refers to an attack by microorganisms on cases ± also be referred to as environmental
nonwater-soluble polymer-based materials degradation.
(plastics). This implies that the biodegrada- Environmental factors not only influence
tion of plastics is usually a heterogeneous the polymer to be degraded, they also have a
process. Because of a lack of water-solubility crucial influence on the microbial popula-
and the size of the polymer molecules, tion and on the activity of the different
microorganisms are unable to transport microorganisms themselves. Parameters
the polymeric material directly into the cells such as humidity, temperature, pH, salini-
where most biochemical processes take ty, the presence or absence of oxygen and the
place; rather, they must first excrete extra- supply of different nutrients have important
cellular enzymes which depolymerize the effects on the microbial degradation of
polymers outside the cells (Figure 1). As a polymers, and so these conditions must be
consequence, if the molar mass of the considered when the biodegradability of
polymers can be sufficiently reduced to plastics is tested.
generate water-soluble intermediates, these Another complicating factor in plastics
can be transported into the microorganisms biodegradation is the complexity of the
and fed into the appropriate metabolic plastic materials with regard to their possi-
pathway(s). As a result, the end-products of ble structures and compositions. In many
these metabolic processes include water, cases plastics do not consist simply of only
carbon dioxide and methane (in the case of one chemical homogeneous component, but
368 12 Biodegradability of Polymers: Regulations and Methods for Testing
contain different polymers (blends) or low- All of the above-described factors must be
molecular weight additives (e.g., plasticiz- considered when measuring the biodegra-
ers). Moreover, within one polymer itself dation of plastics and interpreting the
different structural elements can be present results, and this makes the testing of
(copolymers), and these may either be plastics biodegradability a highly interdisci-
distributed statistically along the polymer plinary process.
chains (random copolymers) or distributed The standardized evaluation of bio-
alternately (alternating copolyesters); they degradable plastics should always be based
may also be used to build longer blocks of on definitions, and what biodegradation
each structure (block-copolymers). Another with regard to plastics actually means.
structural characteristic of a polymer is the Several different definitions have been
possible branching of chains or the forma- published by national and international
tion of networks (cross-linked polymers). standardization bodies and organizations
These different structures of a polymer, (Table 1).
despite having the same overall composi- Whilst in the ISO definition of bio-
tion, can directly influence accessibility of degradable plastics only a chemical change
the material to the enzyme-catalyzed poly- of the material (e.g., oxidation) by micro-
mer chain cleavage, and also have a crucial organisms is requested, the CEN and DIN,
impact on higher-ordered structures of the in contrast, demand in their definitions the
polymers (crystals, crystallinity, glass tran- conversion of plastics into microbial meta-
sition) which have been shown predomi- bolic products. Other definitions such as
nantly to control the degradation behavior of inherent biodegradability or ultimate biode-
many polymers (Marten, 2000). Addition- gradability are adapted from the area of
ally, the crystallinity and crystal morphology degradation of low molecular- weight chem-
is dependent upon the processing condi- icals, but these can also be applied to
tions, and can change with time. polymers. Generally, the definitions do not
2 General Mechanism of Biodegradation, and Definitions 369
However, despite these apparently inho- ces, in some cases microorganisms can
mogeneous definitions, the different stand- partially attack the plastics and cause un-
ards and evaluation schemes are surpris- desired changes in the material properties,
ingly congruent. e.g. in the color or in mechanical properties
such as flexibility or mechanical strength
(Pantke, 1977; Seal and Eggins, 1981)
3 (Table 3).
Testing Methods Although this wide range of degradation
tests already existed, it was necessary to
Test methods to determine biological action develop special test methods when dealing
on man-made materials have been available with biodegradable plastics. The standards
for many years, and for different classes of listed in Table 3 do not consider the special
materials. Nowadays, the evaluation of the aspects (see above) of plastics materials, and
degradability of chemicals in the environ- for biocorrosion phenomena the question is
ment (and especially in waste water) as one not whether the plastic is degraded or not,
important aspect of the ecological impact of a but rather whether changes in the material
compound has become very important when properties may be caused by minor chemical
attempting to bring a new chemical product changes in the polymers (e.g., extraction of
to the marketplace. For this reason, a large plasticizer, oxidation, etc.).
number of standardized tests have been The test methods which have been devel-
developed for different environments, and oped especially for biodegradable plastics
with the use of different analytical methods during the past decade (It‰vaara and Vik-
(Pagga, 1997). An overview of existing man, 1996) are predominantly based on
international standards in this area is principles used for the evaluation of low
provided in Table 2. molecular-weight substances, but have been
Also for the evaluation of the influence of modified with respect to the particular envi-
microorganisms on polymer, test methods ronments in which biodegradable plastics
have been established long before bio- might be degraded. The methods also consid-
degradable plastics were first developed. er the fact that plastics often have a complex
Although conventional plastics are relative- composition and are degraded mainly by a
ly resistant against environmental influen- heterogeneous surface mechanism.
ASTM G21-96 Standard practice for determining resistance of synthetic polymer materials to fungi
ASTM G29-96 Standard practice for determining algal resistance of plastic films
ISO 846 ± 1997 Plastics: Determination of behaviour under the action of fungi and bacteria. Evaluation
by visual examination or measurement of changes in mass or physical properties
3 Testing Methods 371
Tab. 3 (cont.)
ISO/FDIS 14592 ± 1 Water quality ± Evaluation of the aerobic biodegradability of organic compounds at
low concentrations ± Part 1: Shake-flask batch test with surface water or surface
water/sediment suspension
ISO/DIS 14592 ± 2 Water quality ± Evaluation of the aerobic biodegradability of organic compounds at
low concentrations ± Part 2: Continuous flow river model with attached biomass
ISO 14593 ± 1999 Water quality ± Evaluation of ultimate aerobic biodegradability of organic
compounds in aqueous medium ± Method by analysis of inorganic carbon in sealed
vessels (CO2 headspace test)
ISO/TR 15462 ± 1997 Water quality ± Selection of tests for biodegradability
ISO 16221 B 2001 Water quality ± Guidance for determination of biodegradability in the marine
environment
EN ISO 7827 ± 1995 Water quality ± Evaluation in an aqueous medium of the ™ultimate∫ aerobic
biodegradability of organic compounds ± Method by analysis of dissolved organic
carbon (DOC )
EN ISO 9439 ± 2000 Water quality ± Evaluation of ultimate aerobic biodegradability of organic
compounds in aqueous medium ± Carbon dioxide evolution test
EN ISO 9408 ± 1999 Water quality ± Evaluation of ultimate aerobic biodegradability of organic
compounds in aqueous medium by determination of oxygen demand in a closed
respirometer
EN ISO 9887 ± 1994 Water quality ± Evaluation of the aerobic biodegradability of organic compounds in
an aqueous medium ± Semi-continuous activated sluge method (SCAS)
EN ISO 9888 ± 1999 Water quality ± Evaluation of ultimate aerobic biodegradability of organic
compounds in aqueous medium ± Static test (Zahn-Wellens method)
EN ISO 10634 ± 1995 Water quality ± Guidance for the preparation and treatment of poorly water-soluble
organic compounds for the subsequent evaluation of their biodegradability in an
aqueous medium
EN ISO 10707 ± 1997 Water quality ± Evaluation in an aqueous medium of the ™ultimate∫ aerobic
biodegradability of organic compounds ± Method by analysis of biochemical oxygen
demand (closed bottle test)
EN ISO 11733 ± 1998 Water quality ± Evaluation of the elimination and biodegradability of organic
compounds in an aqueous medium ± Activated sludge simulation test
EN ISO 11734 ± 1998 Water quality ± Evaluation of the ™ultimate∫; anaerobic biodegradability of organic
compounds in digested sludge ± Method by measurement of the biogas production
Inhibition tests
ISO 8192 B 1986 Water quality ± Test for inhibition of oxygen consumption by activated sludge
ISO 9509 B 1989 Water quality ± Method for assessing the inhibition of nitrification of activated
sludge microorganisms by chemicals and waste waters
ISO 10712 B 1995 Water quality ± Pseudomonas putida growth inhibition test (Pseudomonas cell
multiplication inhibition test)
ISO 11348 Part 1, 2, 3 Water quality ± Determination of the inhibitory effect of water samples and the light
± 1998 emission of Vibrio fischeri (Luminescent bacteria test)
EN ISO 8192 ± 1995 Water quality ± Test for inhibition of oxygen consumption by activated sludge
EN ISO 9509 ± 1995 Water quality ± Method for assessing the inhibition of nitrification of activated
sludge microorganisms by chemicals and waste water
EN ISO 10712 ± 1996 Water quality ± Pseudomonas putida growth inhibition test (Pseudomonas cell
multiplication inhibition test)
EN ISO 11348 Teil 1, Water quality ± Determination of the inhibitory effect of water samples on the light
2, 3 ± 1998 emission of Vibrio fischeri (Luminescent bacteria test)
3 Testing Methods 373
Fig. 3 Comparison of the enzymatic degradation of the polyester poly(tetramethylene adipate) with a lipase
from Pseudomonas sp. for a polymer film and polymer nanoparticles at pH 7 and 408C. Degradation expressed
as percentage of cleaved ester bonds (maximum ester cleavage of ~ 40% results from the dissolution of low
molecular-weight esters which are not accessible to attack by the lipase). (From Welzel et al., 2002.)