International Biodeterioration & Biodegradation 52 (2003) 69 – 91www.elsevier.com/locate/ibiod Microbiological deterioration and degradation of synthetic polymeric materials: recent research advances Ji-Dong Gua; b;∗ a Laboratory of Environmental Toxicology, Department of Ecology & Biodiversity, The University of Hong Kong, Pokfulam Road, Hong Kong SAR, People’s Republic of China b The Swire Institute of Marine Science, The University of Hong Kong, Shek O, Cape d’Aguilar, Hong Kong SAR, People’s Republic of China Received 11 July 2002; received in revised form 9 September 2002; accepted 21 November 2002 Abstract Biodeterioration of polymeric materials a/ect a wide range of industries. Degradability of polymeric materials is a function of the structures of polymeric materials, the presence of degradative microbial population and the environmental conditions that encourage microbial growth. Our understanding of polymer degradation has been advanced in recent years, but the subject is still inadequately addressed. This is clearly indicated by the lack of information available on biodeterioration of polymeric materials, particularly the mechanisms involved and the microorganisms participated. In this review, polymers are treated according to their origin and biodegradability, and grouped as biopolymer, chemically modi6ed natural polymers and recalcitrant polymers. Selective examples are used to illustrate the mechanisms and microorganisms involved in degradation of speci6c polymeric materials, and detection methods used for degradation and deterioration tests are discussed. In addition, new detection techniques and preventive measures are also presented. ? 2003 Elsevier Ltd. All rights reserved. Keywords: Biodeterioration; Biodegradation; Biodeteriogens; Fiber-reinforced composites; Fungi; Polymers; Prevention 1. Introduction All surfaces under natural and arti6cial conditions except for extremely clean rooms are covered ubiquitously with microorganisms. This unique characteristic of bacterial association with surfaces was evident from the very beginning of bacterial existence and has remained part of normal living (Angles et al., 1993; Gu et al., 2000b,d; Marshall, 1976, 1992; W?achtersh?auser, 1988; Woese, 1987). The process in which a complex community of microorganisms is established on a surface is known as “microfouling” or formation of bio6lm. Bio6lms, consisting of both microorganisms and their extracellular polysaccharides, are highly diverse and variable in both space and time. They are common on all surfaces in both terrestrial and aquatic environments (Caldwell et al., 1997; Fletcher, 1996; Ford et al., 1991; Ford, 1993; Geesey and White, 1990; Gehrke et al., 1998; Neu, 1996). ∗ Corresponding author. Laboratory of Environmental Toxicology, Department of Ecology & Biodiversity, The University of Hong Kong, Pokfulam Road, Hong Kong SAR, People’s Republic of China. Tel.: +852-2299-0605; fax: +852-2517-6082. E-mail address:
[email protected] (J.-D. Gu). 0964-8305/03/$ - see front matter ? 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S0964-8305(02)00177-4 Materials including metals (Gu et al., 2000a), inorganic minerals (Gu et al., 1996d, 1998c, 2000c) and organic polymers (Gu et al., 2000b) are susceptible to the formation of microbial bio6lms under humid conditions, particularly those in tropical and subtropical climates (Gu et al., 2000d). Subsequent damage of materials is a result of natural processes catalyzed by microorganisms. Complete degradation of natural materials is an important part of the nutrients cycling in the ecosystem (Swift et al., 1979). Bio6lm formation is a prerequisite for substantial corrosion and/or deterioration of the underlying materials to take place (Arino et al., 1997; Gu and Mitchell, 2001; Gu et al., 2000a–d; Hou, 1999; Saiz-Jimenez, 1995, 1997; Walch, 1992). 2. Biolms and fouling on materials Bio6lm structures are highly organized and diverse on surfaces (Bitton, 1980; Bonet et al., 1993; Breznak, 1984; Caldwell et al., 1997; Costerton et al., 1978, 1994; Dalton et al., 1994; Davey and O’Toole, 2000; Freeman and Lock, 1995; Guezennec et al., 1998; Kelley-Wintenberg and 70 J.-D. Gu / International Biodeterioration & Biodegradation 52 (2003) 69 – 91 Montie, 1994; Lappin-Scott et al., 1992; L’Hostis et al., 1997; O’Toole et al., 2000; Whit6eld, 1988; Wimpenny and Colasanti, 1997; Wolfaardt et al., 1994; Zachary et al., 1980). The speci6c architectural structures and organization of microorganisms on a particular surface are generally materials and microorganisms speci6c, depending on the surface properties (Fletcher and Loeb, 1979; van Loosdrecht et al., 1987, 1990; Wiencek and Fletcher, 1995) and the ambient environmental conditions including externally supplied electrical current, cationic ions, ionic concentrations, solution chemistry, and hydrodynamic conditions (Caldwell and Lawrence, 1986; Korber et al., 1989; Lawrence et al., 1987; Lewandowski et al., 1995; Leyden and Basiulis, 1989; Little et al., 1986; Marshall et al., 1971; Martrhamuthu et al., 1995; Neu, 1996; Pendyala et al., 1996; Power and Marshall, 1988; Rijnaarts et al., 1993; Schmidt, 1997; Sneider et al., 1994; Stoodley et al., 1997). Because virtually all surfaces may act as substrate for bacterial adhesion and bio6lm formation (Busscher et al., 1990; Costerton et al., 1995; Geesey and White, 1990; Geesey et al., 1996; Marshall, 1980), attack of materials by microorganisms can take place either directly or indirectly, depending on the speci6c microorganisms, chemical and physical properties of the materials, and their environmental conditions (Gu et al., 2000d). More speci6cally, important factors a/ecting the rate of biodeterioration include material composition (Bos et al., 1999; Busscher et al., 1990; Gu et al., 2000b; Wiencek and Fletcher, 1995), molecular weights, atomic composition and the chemical bonds in the structure, the physical and chemical characteristics of the surfaces (Becker et al., 1994; Caldwell et al., 1997; Callow and Fletcher, 1994), the indigenous microNora, and environmental conditions. Using microorganisms capable of degrading speci6c organic pollutants, the bio6lms immobilized on material surfaces have important applications in degradation of toxic pollutants, wastewater treatment and bioleaching (Bryers, 1990, 1994; Gu, 2001; Gu et al., 2001c; Osswald et al., 1995; Sharp et al., 1998). In contrast, bio6lms are undesirable in food processing, drinking-water distribution systems, petroleum transport pipeline, water-cooling systems, on submerged engineering systems and structures, medical implant materials. On molecular level, bacterial attachment on surfaces is a process controlled by chemical signaling between bacteria (Davies et al., 1998; McLean et al., 1997; Reynolds and Fink, 2001) and the speci6c chemical molecules involved have been elucidated as N -(3-oxohexanoyl)-L-acylhomoserine lactones in Photobacterium ;sheri, N -(3-hydroxybutanoyl)-L-acylhomoserine in Vibrio harveyi, N -(3-oxododecanoyl)-L-acylhomoserine in Pseudomonas aeruginosa, N -(3-oxooctanoyl)-Lacylhomoserine in Agrobacterium tumefaciens, and -butyrolactone in Streptomyces spp. (Davies et al., 1998; Salmond et al., 1995; You et al., 1998). Biofouling is a process de6ned as the undesirable accumulation of microorganisms, their products and deposits including minerals and organic materials, and macro- organisms on substratum surfaces (Gu and Mitchell, 1995; Nefedov et al., 1988; Novikova and Zaloguyev, 1985; Solomin, 1985; Sunesson et al., 1995; Viktorov, 1994; Viktorov and Novikova, 1985; Viktorov and IIyin, 1992; Viktorov et al., 1993; Zaloguyev, 1985). The thin 6lm on fouled surfaces usually consists of microorganisms embedded in an organic matrix of biopolymers, which are produced by the microorganisms under natural conditions. In addition, microbial precipitates, minerals, and corrosion products may also coexist (Beveridge et al., 1997; Konhauser et al., 1994; Liken, 1981; Lovley, 1991; Pierson and Parenteau, 2000; Wilkinson and Stark, 1956; Zehnder and Stumm, 1988). Microfouling by microorganisms can serve as a prerequisite for the subsequent macrofouling by invertebrates such as Balanus amphitrite, Janua brasiliensis, Ciona intestinalis (Gu et al., 1997c; Maki et al., 1990). Industrial fouling is a complex phenomenon involving interactions between chemical, biological and physical processes resulting in enormous economic loss. To combat fouling and corrosion, large quantities of biocides have been used to control biofouling and as a result biocide resistance is an emerging problem to our society. Both metal and non-metallic materials immersed in aqueous environments or under high humidity conditions are equally susceptible to biofouling and biodeterioration (Characklis, 1990; Gu and Mitchell, 1995; Gu et al., 1998b, 2000d; Jones-Meehan et al., 1994a, b; Knyazev et al., 1986; Little et al., 1990; Thorp et al., 1994). Speci6c examples include medical implants (Dobbins et al., 1989; Gu et al., 2001a–c; McLean et al., 1995; Mittelman, 1996), water pipes (Rogers et al., 1994), arti6cial coatings (Edwards et al., 1994; Gu et al., 1998a; Jones-Meehan et al., 1994b; Stern and Howard, 2000; Thorp et al., 1997), rubber (Berekaa et al., 2000), ultrapure systems (Flemming et al., 1994; Mittelman, 1995), porous media (Bouwer, 1992; Cunningham et al., 1990, 1991; Mills and Powelson, 1996; Rittman, 1993; Vandevivere, 1995; Vandevivere and Kirchman, 1993; Williams and Fletcher, 1996), water and wastewater treatment (Bryers and Characklis, 1990; Gillis and Gillis, 1996; Rethke, 1994; Tall et al., 1995), oil6eld (Lynch and Edyvean, 1988), space station (Gazenko et al., 1990; Meshkov, 1994; Novikova et al., 1986; Pierson and Mishra, 1992; Stranger-Joannesen et al., 1993; Zaloguyev, 1985) and magnetic diskettes (McCain and Mirocha, 1995). Generally, biodeterioration is the undesirable degradation of materials including both metals and polymers in the presence of and by microorganisms. Damage of materials may result in an early and unexpected consequence and the problem is often translated to system failure and economic loss. The term biodeterioration also implicitly includes both biocorrosion and biodegradation in this review. All three terms, corrosion, degradation and deterioration are used in this review. In the following sections, microbial deterioration and degradation of polymeric materials are discussed for several groups of materials. it should be pointed out that concurrent abiological and biological processes may facilitate the degradation of polymers.. 2000b). slow-release capsules. In service. dimers.. and H2 O as the 6nal products (Fig.1. CH4 and H2 O under methanogenic conditions (Barlaz et al. Since chemically synthesized polymeric materials have become an important part of our human society and have more diversi6ed applications than traditional metals. Narayan. 1977. Very small variations in the chemical structures may result in large di/erences in term of biodegradability. 1993). Polymers like cellulose. disintegration. 1993. Atlas and Bartha. Hespell and O’Bryan-Shah. aviation and space industries. an increase in molecular weight results in a decline of polymer degradability by microorganisms. telecommunication. 1992. In addition. sporting and recreational equipment. protective coatings. In contrast. anaerobic consortia of microorganisms are responsible for polymer deterioration. L?uthi et al. 1985. It is important to note that biodeterioration and degradation of polymer substrate can rarely reach 100% and the reason is that a small portion of the polymer will be incorporated into microbial biomass.-D. At least two categories of enzymes are actively involved in biological degradation of polymers: extracellular and intracellular depolymerases (Doi. insulation.. CO2 . 1977. 1993. and deterioration over time (Lemaire et al. smaller molecules. 1992. the degradation is called mineralization.. The reason is probably due to the recent development and manufacture of this class of materials and the relatively slow rate of degradation in natural environments.. 1997. and monomers. the easier it is to be degraded and mineralized. b. 1990a.g. Yoshizako et al. resulting in aging... with microbial biomass. CO2 . Hass et al. 1993. or CH4 . physical forms. 2000b).. 1991. Biodeterioration of polymeric materials Microorganisms are involved in the deterioration and degradation of both synthetic and natural polymers (Gu et al.. The process is called depolymerization. 1988.J. oligomers. Byrom. 1987.. When the end products are inorganic species. Dominant groups of microorganisms and the degradative pathways associated with polymer degradation are often determined by the environmental conditions... 1). 1993. monomers. Gunjala and SulNita. 1992). Gu et al. High versatility of the carbon to carbon and carbon to non-carbon (C–C. Hamilton et al. A commonly recognized rule is that the closer the similarity of a polymeric structure to a natural molecule. and very little is known about the biodegradation of synthetic polymeric materials. dimers. 1983. CO2 .. 1988. 1). MacDonald et al. mechanical properties and applications. 1. Because of this structural versatility. Nakanishi et al. pullusan. Polymer biodegradability depends on molecular weight. 2000. 2000b). medical implants.g. Generally. e. Gujer and Zehnder. 1995). Sonne-Hansen et al. Microorganisms and general degradation Polymers are potential substrates for heterotrophic microorganisms including bacteria and fungi. Frazer. CO2 . b. under anoxic conditions. crystallinity and physical forms (Gu et al. and then to be utilized as carbon and energy sources (Fig. Schematic diagram of polymer degradation under aerobic and anaerobic conditions. 1992. and oligomers of a polymer’s repeating units are much easily degraded and mineralized. 1993. Gamerith et al. Wong et al. 1990. Polymeric materials are very unique in chemical composition.. 3. The primary products will be microbial biomass. C–R and C–H) bonds and substituent groups. Under such conditions. drug delivery carriers. exoenzymes from microorganisms break down complex polymers yielding short chains or 71 Polymer Depolymerases Oligomers Dimers Monomers Aerobic Microbial Biomass CO2 H2O Anaerobic Microbial Biomass CH4/H2S CO2 H2O Fig. electronic insulation. 1987a. When O2 is available. Sternberg et al. Fenchel and Finlay. issues related to polymer deterioration and protection will receive increasingly attention in the time to come. 1985. High molecular weights result in a sharp decrease in solubility making them unfavorable for microbial attack because bacteria require the substrate be assimilated through the cellular membrane and then further degraded by cellular enzymes. Lee et al.. humus and other natural products (Alexander. chitin. Pitt.. stereochemistry and orientation provide basis for variations of chemical structures and stereochemistry (Odian. 1992). 1985. building consolidants. 1995... MacKenzie et al.. 1994. and PHB are all biologically synthesized and can be completely and rapidly biodegraded by heterotrophic microorganisms in a wide range of natural environment (BQerenger et al. Gu / International Biodeterioration & Biodegradation 52 (2003) 69 – 91 3. H2 O. CH4 and H2 O. In contrast. Chahal et al. T?orr?onen et al. 1992. Kormelink and Voragen.. natural conditions also include environments where anaerobic processes are the leading ones (Brune et al. the possible con6gurations. However.. aerobic microorganisms are mostly responsible for destruction of complex materials. the complete decomposition of a polymer will produce organic acids. they are widely used in product packaging. etc. 1992. structural components. During degradation. . 1991). that are smaller enough to pass the semi-permeable outer bacterial membranes.. e.. they are constantly exposed to a range of natural and arti6cial conditions often involving microbial contamination. . 1991). 1998b. 1988. compost (Gilmore et al. 1995). 2001. Under condition of nutrient limitation. Kim et al. Lemoigne. A general rule is that biologically synthesized polymers are readily biodegradable in natural environments and synthetic polymers are either less biodegradable or degraded very slowly.. Szycher.. 1990.g.. El-Sayed et al. 3.1.. 1978. Stenb?uchel. 1987. 1988. Brandl et al. the sequence of enzymatic hydrolysis is [P(HB-co-16% HV)]¿[P(HB-co-32% HV)]¿PHB (Parikh et al. e. Gu et al. It is known that aerobic processes yield much more energy and are capable of supporting a greater population of microorganisms than anaerobic processes because thermodynamically O2 is a more eScient electron acceptor than SO2− and CO2 . Poly(-hydroxyalkanoates) Bacterial poly(-hydroxyalkanoates) are formed during nutrient limited growth when the carbon source is in excess. Choi and Yoon. Examples of the former include the poly(hydroxyalkanoate)s (PHAs) (Anderson and Dowes. 2000b. 1). c.. Similarly. 1991). 1993b). which provide potential for commercial production in the future. Sullivan et al.3 and 1:0 m (Stenb?uchel.2. 1993a–c. 1993. such as polysaccharides. 1985. These conditions are widely found 4 in natural environments and can be simulated in the laboratory with appropriate inocula. Microbial degradation of polymers depends on their molecular compositions.. Gu / International Biodeterioration & Biodegradation 52 (2003) 69 – 91 1989a... crystallinity and stereochemistry of polymers also a/ect the rate of degradation signi6cantly. 1986).. However. 1990. 1992) and seawater (Andrady et al. 1992b.. polyethers (Kawai. C/N 10.. This polymer is a microbial intracellular inclusion in the cytoplasmic Nuid in the form of granules with diameters between 0. 1993).. 1985. structures and con6guration as well as the participating microorganisms and the environmental conditions.. 1987. Brandl et al. 1991. 1995. PHB is thermoplastic with a melting temperature around 180◦ C. 1998. cellulose acetates with degree of substitution values lower than 2. 1989). Stenb?uchel. lignin. Filip. the rate of degradation is largely a/ected by the chemical structure. 2000e. Kawai and Moriya. 1990. PHB and co-polymers have also been produced in genetic engineered plants (John and Keller. In this review. 1992.. the rate of hydrolytic chain cleavage of ester bonds in the following polymers is dependent on the co-polymer composition: poly(3-hydroxybutyrate-co-27% 4-hydroxybutyrate) [P(3HB-co-27% 4HB)]¿[P(3HB-co-17% 4HB)]¿ [P(3HB-co-10% 4HB)]¿ poly(3-hydroxybutyrate-co45% 3-hydroxybutyrate [P(3HB-co-45% 3HV)]¿[P(3HBco-71% 3HV)] (Doi... 2001) or H2 S. 1991). but is rarely taken into account (Budwill et al. 1993).2. these materials can be depolymerized and utilized by microorganisms. Some can be almost completely utilized as a source of carbon and energy while others are only partially degraded. 1993. Variovorax paradoxus. etc. e. 1966) and A... 1991... Mitchell et al... Tsao et al.. 1993. molecular weights. and (3) resistant. This characteristic of molecules and its e/ects on degradation has received attention recently (Kohler et al. 1993).. 1992b.e). 1996) and through chemical synthesis (Kemnitzer et al.g. Imam et al. Tanio et al. proteins and DNAs. Gu and Mitchell. Extracellular PHB depolymerases have been isolated from Pseudomonas lemoignei (Lusty and Doudoro/. 1995. 1994b). Doi.. Mas-CastellVa et al. Stuart et al. 2000... In addition. polysaccharides (Linton et al. Both aerobic and strictly anaerobic microorganisms are involved in the degradation of polymers. unpublished data). making it a good candidate for thermoprocessing. 1995. Gu et al. silk (Kaplan et al. 1996. 1996. 1991). Both homopolymers and co-polymers can be degraded under biologically active environments.72 J. 1999.. Wirsen and Jannasch. Crabbe et al. Imam et al. Kawai and Yamanaka... 1994. Natural polymers. sludge. Biodeterioration of polymers 3. 1990.. 1982). 1990). . cellulose. 2000). the C–C and other types of bonds... Gillatt. b. Nakajima-Kambe et al. river water (Andrady et al. polylactide (Gu et al. 1994.5 (Buchanan et al. 3.-D.. Tanio et al. 1995. 1992. 1995. For example. Nakayama et al. Stenb?uchel. and polysaccharides. Chemical structure of a polymer determines the extent of biodegradation. This widely accepted rule suggests that the degradation processes have evolved through time and complexity of biochemical pathways may increase with the structure diversi6cation of polymeric materials. high C/N ratio. They consist of homo or co-polymers of [R]--hydroxyalkanoic acids.. The polymer has been isolated from Bacillus megaterium by extraction in chloroform and has a molecular weight of approximately 105 –106 with more than 50% in crystalline form (Gu et al. 1990..g. Furthermore.. soil (Albertsson et al. faecalis (Saito et al.g. 1993. are excluded. 1995). Unlike other biopolymers. polyurethanes (Blake et al. chitin. 1992. Gu et al.2. Heisey and Papadatos... CO2 and H2 O under sul6dogenic conditions (Fig. 1982)..2. 1989. Gross et al. 1995. 1993. e.c).. Doi. e. Holmes et al. 1993.. and natural rubbers (Berekaa et al. e. as energy storage materials (Anderson and Dowes. Gross et al. 1993). Biopolymers may comprise as much as 30 –80% of the total cellular biomass. 1926. (2) slowly degradable. molecular weights and the presence of speci6c microorganisms on surfaces of materials. High molecular weight polymers are less biodegradable or degraded at a slower rate than those with low molecular weights.g. 1990. 1993. Gu et al. Gu et al. -poly(glutamic acid) (Cromwick and Gross.. Other bacteria capable of degrading these polymers include Acidovorax facilis. synthetic polymers are divided into three groups: (1) degradable. 1991).. Microbiologically synthesized polymers Microorganisms are capable of manufacturing a range of complex polymers under conditions when excessive carbon source is available. chitosan. The polymers include a diverse class of polyesters (Doi. 3. theoretically they can carry substitution values from as low as near zero to as high as 3. 1993a–c. 5 m).ed natural polymers 3. 1987). 1994b) or transformed to solvents through biological catalyzed reactions (Downing et al. Bacillus megaterium. 1992b. Apparently. it is clear that slightly deviation from the natural structures will lead to increasing resistance to deterioration and degradation. Scanning electron micrographs of (a) aerobic soil bacteria growing on surface of poly--hydroxybutyrate (PHB) (scale bar. Cytophaga johnsonae.-D. 10 m) and (b) bacteria surrounding a PHB granule after incubation under mesophilic conditions (35◦ C) (scale bar. 1993). and the rate of surface erosion is highly dependent on both the molecular weight (degree of polymerization).. crystallinity and the dominant species of bacteria. Pseudomonas syringae subsp.. 2). CA degradation occurs more rapidly under oxic conditions than anoxic conditions. The enzymatic degradation occurs initially at the surfaces of the polyester 6lm after microbial colonization (Fig. 2. Gu et al. 1995. Current knowledge is that CAs with a degree of substitution values less than 2.J. Gu / International Biodeterioration & Biodegradation 52 (2003) 69 – 91 73 Fig. savastanoi.5 can be degraded in thermophilic compost (Gross et al. Cellulose acetates (CAs) Cellulose acetates (CAs) are a class of natural polymers with chemical modi6cation to improve their processibility and mechanical properties for di/erent applications (Bogan and Brewer.. increasing the DS value makes the polymers less degradable. (Mergaert et al. and Streptomyces spp.3. which releases the .0. composition of the polyester. Comamonas testosteroni. 1993. Modi. As discussed above. 3. B. c.1.. The mechanisms of initial degradation reaction are de-acetylation. polymyxa. Because the backbone is natural cellulose. 1985). In a co-culture of aerobic Flavobacterium and Pseudomonas species. 2002. degradation of PEGs with molecular weights up to 20. Scanning electron micrograph showing bacteria growing on surfaces of cellulose acetate.7 from a composting bioreactor containing CA 6lms (Gross et al.1. 1992. They are used in pharmaceuticals. 1987. Kawai and Moriya. c. both molecular weight and degree of substitution decreased. followed by breaking of the polymer carbon–carbon bonds (Reese. All of them . Current results showing degradation of CA indicated that CA degradation has been observed with DS values as high as 2. 2002). inks. PEG-aldehyde dehydrogenase.. During degradation of CA.4.4. and PEG-carboxylate dehydrogenase (ether-cleaving) are all required. 3. The ability of a microNora to degrade PEG molecules with high molecular weights is dependent primarily on the ability of a syntrophic association of di/erent bacteria to metabolize the chemicals (Fig. Kawai and Yamanaka. 1992b. 1986) and anoxic conditions (Dwyer and Tiedje. Gross et al. PEG degradation proceeds through dehydrogenation to form an aldehyde and a further dehydrogenation to a carboxylic acid derivative (Kawai. and surfactants. a/ects the degradation kinetics remarkably. 1992b. 3. However.. cellulose acetate (CA) with a lower degree of substitution (DS) value is more quickly degraded than those with higher substitution values under both oxic and anoxic conditions (Buchanan et al. Gu / International Biodeterioration & Biodegradation 52 (2003) 69 – 91 Fig.. 1995. 1993a–c). substituted groups. PEG dehydrogenase. Earlier data also suggested that CA with DS values greater than 0.. 1983. 3). suggesting that de-acetylation and decomposition of the polymer backbone proceed simultaneously (Gu et al.. Cellular contact between them seems to be essential for e/ective activity (Kawai. One bacterium Pseudomonas paucimobilis was isolated for ability to degrade CA with DS value 1. It is also demonstrated recently that the decrease of molecular weight by cleavage of C–C chain and de-acetylation proceed simultaneously during degradation after CA reaches to a critical value of substitution of approximately 1. 1993. In the investigated Flavobaterium sp. cosmetics. In this case. Flavobacterium sp. 1993c). fungi and selective bacteria (Gross et al. For example. three enzymes are involved in the complete degradation of PEG (Kawai. c.74 J. lubricants. Molecules with molecular weights higher than 1000 have been considered resistant to biodegradation (Kawai.5. Synthetic polymers 3. 4).000 has been reported (Kawai and Yamanaka. Contamination of natural waters. 1987. 1993). The central pathway of PEG degradation is cleavage of an aliphatic ether linkage.-D. Gu et al. and their numbers per repeating unit. and Pseudomonas sp. 1987). Polyethers One of the most commonly used synthetic polymers with wide application and usage is polyethers. It is important to note that either of the two bacteria in pure culture cannot degrade PEG alone. Microorganisms capable of CA degradation are mostly actinomyces. 1957). The polymers in- clude polyethylene glycols (PEGs). system. Kawai and Yamanaka. Gu et al. Frings et al. 1995. Structural substitution groups. Their degradability is highly dependent on molecular weight. 1987). 1994b) (Fig. 1987). polypropylene glycols (PPGs) and polytetramethylene glycol (PTMGs). including coastal waters and streams where wastewater is discharged have been reported (Kawai. Degradability of this class of polymers has been studied under both oxic (Kawai.82 are recalcitrant to biodegradation and that the limiting step is de-acetylation. 1983). CAs with lower substitution values (∼ = 0:82) also show relatively higher solubility which is favored by microbial metabolism. For example. 1991. Schink and Stieb..0. During degradation. 1989).. 1993a–c.. 1993. can form an e/ective association and mineralize PEG completely. 1993. 1986). PEG molecules are reduced by one glycol unit after each oxidation cycle. substituting group has a strong inNuence on the degradability of polymer. followed by cleavage of the C–C backbone. 1987. and Pseudomonas sp. furnishings. 1996b. Our studies showed that the dielectric properties of polyimides could be altered drastically following growth of a microbial bio6lm (Ford et al. chasses. insulation tapes. Though bacteria were isolated from culture containing the deteriorated polyimides.g. However. Polyimides are also widely used in load bearing applications. 1995a. They are susceptible to deterioration by fungi (Fig. 1998a. struts. e. the ether cleavage is extremely sensitive to the presence of glycoxylic acid. greases. PEG can also be degraded (Dwyer and Tiedje. adhesives. 1995). 1993. and fats. 1985.-D. Thermosetting polyimides are major class in this application (Brown. 5) (Ford et al.. 1987) emphasized the need to apply these polymers in the electronic industries because data acquisition. Mitton et al. c. In addition. 1996. Scanning electron micrograph showing a pure culture of bacteria capable of utilizing polyethylene glycol as a source of carbon and energy. 1995. 1983) but only one bacterium Pelobacter venetianus was reported (Schink and Stieb. advanced composite structures. though not directly involved in the degradation. The National Research Council (NRC. 1989. the deterioration processes can be accelerated in humid conditions or in enclosed environments..g. while only PEG-carboxylate dehydrogenase is present in Pseudomonas sp. Electronic packaging polyimides are particularly useful because of their outstanding performance and engineering properties.. Pseudomonas sp. 1995. Other possible uses may include 6bers for protective clothing. Very small changes of . 1995) has drawn attention to the stability of these materials. 1983). 1982. Gu / International Biodeterioration & Biodegradation 52 (2003) 69 – 91 75 Fig..5. cookingware. Lai.. 1996b. due to their Nexibility and compressive strength. 1994a. submarines. 1987. Gu et al. b. Using PEG 6000 as a sole substrate no degradation can be observed with either of the two bacteria alone. and food packaging because of their chemical resistance to oils. 1998). Verbiest et al. Gu et al. the Nammability resistance of this class of polymers may provide a halogen-free Name-retardant material for aircraft interiors. 4 -diaminodiphenyl ether with molecular weight (Mw of 2:5 × 105 ) (Ford et al. Mitton et al. They are also used in appliance construction. is capable of utilizing the toxic metabolite that inhibits the activity of the Flavobacterium sp.. 3. 1998). are found in Flavobaterium sp. especially as high temperature insulation materials and passivation layers in the fabrication of integrated circuits and Nexible circuitry. This form of deterioration may be slow under ambient conditions....5. 1998). and brackets in automotive and aircraft structures. 1994a. The interlayering of polyimides and electronics in integrated circuits prompted several studies on the interactions between these two materials (Hahn et al. However. 1988. Under anaerobic condition. 1993. This connection appears to be the essential link for their closely syntrophic association in achieving completely degradation of PEG. 1995. and optics operating at high temperatures (Verbiest et al. and other closed facilities. and wire insulation. It is only recently that biodeterioration of these polymers was investigated using pyromellitic dianhydride and 4. 1995a. 1993. Mitton et al. 4. Gu et al... further tests did not show comparable degradation by bacteria.. e.J. Kelley et al. Electronic insulation polyimides Polymers used in electronic industries are chemically synthesized with the objective of high strength and resistance to degradation. microwave transparency..1. information processing and communication are critically dependent on materials performance.. In addition. 1982). 1987). Verbicky. 1995a. foam. and thermal resistance.. Their electrical insulation properties are ideally suited for use in the electrical and electronics markets. Recalcitrant polymers 3. Jensen. space vehicles. 1996b. EG. aircraft.. Wide acceptance of polyimides in the electronics industry (Brown. This is followed by further deterioration of the polymer by activity of the fungi. e. The increasing usage of FRPCMs as structural components of public structures and particularly in aerospace application has generated an urgent need to evaluate the biodegradability of this class of new materials.76 J. It was suggested that impurities and additives that can promote microbial growth are implicated as potential sources .2. 1997a. Agrobacterium radiobacter.cans. These bacteria were not capable of degrading the polymer after inoculation while fungi were more e/ective in degrading the polyimides. Fungi involved include Aspergillus versicolor. Pseudomonas spp. 1996a. b. Alcaligenes denitri. fungal growth on polyimides have been shown to yield distinctive EIS spectra. 5. (Gu et al. In the degradation processes. Gu / International Biodeterioration & Biodegradation 52 (2003) 69 – 91 (a) (b) Fig. Photograph and scanning electron micrograph showing: (a) the visible colonization of microorganisms in the inoculated cell containing polyimides and (b) the microorganisms colonizing and growing on the surface of polyimides.. Using electrochemical impedance spectroscopy (EIS) (Mansfeld.. 1997b). The data support the hypothesis that polyimides are susceptible to microbial deterioration and also con6rm the versatility of EIS as a method in evaluation of the biosusceptibility of polymers. 1994). 1995a–d. Fiber-reinforced polymeric composite materials Fiber-reinforced polymeric composite materials (FRPCMs) are newly developed materials important to aerospace and aviation industries (Gu et al. 1998a). Cladosporium cladosporioides. and Vibrio anguillarum.. Comamonas acidovorans. FRPCMs are also susceptible to attack by microorganisms (Gu et al. 1995a. 1995. two steps are involved during degradation: an initial decline in coating resistance is related to the partial ingress of water and ionic species into the polymer matrices. resulting in a large decrease in resistivity.5. b. indicative of failing resistivity. 3. and Chaetomium sp. Bacteria include Acinetobacter johnsonii.. 1994a.-D. a very sensitive technique for monitoring dielectric constant of polymers. Wagner et al. material insulation properties may result in serious and catastrophic consequences of communications and control systems.. 1997a. Initial isolation of microorganisms associated with deterioration of polyimides indicated the presence of both fungi and bacteria. 1996). 1996a. Wagner. van Westing et al. Polyimide deterioration occurs through bio6lm formation and subsequent physical changes in the polymer. 1995. The fungal consortium consisted of Aspergillus versicolor. 1995b.. 1995b).-D.. 1997a. 1997a. Phthalate and phthalate esters are the largely groups of chemicals used as plasticizers in plastics manufacturing. 1996a).. In this area of research. (1994a. poly(ether-ether-ketone) (PEEK)/graphite 6bers. of carbon and energy for the environmental microorganisms (Fig. two groups reported microbial degradation of FRPCMs (Gu and Mitchell. and a Chaetomium sp.. 1994a. 1996). 1997b.. b. 1997a. However.J. 1996a–c. Cladosporium cladosorioides. Scanning electron micrographs showing colonization of surfaces of: (a) 6ber-reinforced polymeric composite by both bacteria and fungi and (b) graphite carbon 6bers by mostly fungi.. 2002) and degraded by aerobic microorganisms quickly (Fan et al. A mixed culture of bacteria including a sulfate-reducing bacterium was used to show the material deterioration (Wagner et al. 1996a. Thorp et al. Gu et al. bismaleimide/graphite 6bers. 1994). 6). 1995. . It was also found that plasticizers are biodegradable and utilized by natural microorganisms as source of carbon and energy (Gu et al. In contrast. 6. 1996). 1995b–d. and epoxy/graphite 6bers (Gu et al. Wagner et al. Gu / International Biodeterioration & Biodegradation 52 (2003) 69 – 91 77 Fig. b) used a fungal consortium originally isolated from degraded polymers and a range of material composition including Nuorinated polyimide/glass 6bers. Both bac- teria and fungi are capable of growing on the graphite 6bers of FRPCMs... Wang et al. 2003). the resins were actively degraded.. they are also detected at high concentrations in land6ll leachate (Mersiosky. but only fungi have been shown to cause deterioration detectable over more than 350 days (Gu et al. 2001. Gu et al. Physical and mechanical tests were not suSciently sensitive to detect any signi6cant physical changes in the materials after the duration of exposure (Gu et al. b).. 1996). unpublished data). The bacteria are believed to be introduced onto the polymers during production. Polyurethane-degrading microorganisms including Fusarium solani. bacteria are less e/ective in degrading the composites than fungi (Gu et al. Corrosion protective polymers Corrosion protective coatings also have wide application because the development of metallic materials and susceptibility to corrosion both environmentally and microbiologically (Mitchell et al.. 1992)..-D. Similarly.5. including epoxy and polyamide primers and aliphatic polyurethanes (Blake et al. 1978. However... 1996). Similar to the microorganisms isolated from polyimides. 1997) (Fig. surface treatment chemicals and impurities. 1996a). 1998b.. Clear di/erences resulting from bio6lm development were detected on FRCPMs used in aerospace applications (Gu et al. Aliphatic polyurethane-degrading bacteria have been isolated and one of them is Rhodococcus globerulus P1 base on 16S rRNA sequence (Gu.. Natural bacterial populations were found to readily form microbial bio6lms on surfaces of coating materials. Polymeric coatings are designed to prevent contact of the underlying materials with corrosive media and microorganisms.. both primers and aliphatic polyurethane top-coatings were monitored for their response to biodegradation by bacteria and fungi... lignopolystyrene graft copolymers were also susceptible to attack by fungi (Milstein et al. 1995b). The degradation process has similar mechanisms as polyimides and FRPCMs as mentioned above. 1995d).. 1998b). (1994) attempted to determine mechanical changes in composite coupons after exposure to a fungal culture. Further study indicated that many fungi are capable of utilizing chemicals. Degradation of composites were detected using electrochemical impedance spectroscopy. the resistivity of FRPCMs was found to decline signi6cantly after the initial 3 months during a year of monitoring using EIS (Gu et al. Results indicated that primers are more susceptible to degradation than polyurethane (Gu et al. Typical example includes the corrosion of underground storage tanks.. Scanning electron micrograph of a pure culture of bacteria capable of degrading water-soluble polyurethane. Natural populations of microorganisms are capable of growth on surfaces of FRCPM coupons at both relatively high (65 –70%) and lower humidity conditions (55 – 65%) (Gu et al. It has become clear that FRPCMs are not immune to adhesion and attack by microorganisms (Ezeonu et al. 3. Stern and Howard..3. Surprisingly. 1997b). It is clear that both 6ber surface treatment and resin processing supply enough carbon for microbial growth (Gu et al. 1998b). No signi6cant mechanical changes could be measured after 120 days exposure.. 1998.. microbial degradation of coatings may accelerate and severely damage the underlying metals. 7. 1998b. Thorp et al.. the addition of biocide diiodomethyl-p-tolylsulfone into polyurethane coatings did not inhibit bacterial attachment or growth of bacteria e/ectively due to development of bio6lm and bacterial resistance (Gu et al. A critical question remains about the e/ect of FRPCM deterioration on mechanical properties of the composite materials.. 1996a). Filip. indicating that the materials were at risk of failure. Gu et al. Acoustic techniques have also been proposed as a means of detecting changes in the physical properties of the FRPCMs (Wagner et al. 1996).. plasticizers.b. The accumulation of fungi on surfaces of composites develops into a thick bio6lm layer and decreases the resistance to further environmental changes.g.78 J.. Curvularia senegalensis. e. They suggested that methodologies suSciently sensitive to detect surface changes need to be utilized. introduced during composite manufacture as carbon and energy sources (Gu et al. 1996c. 1997b). 2000. 1994a. However. Mitchell et al. Thorp et al... 1998b. Gu et al. 7). Many bacteria were capable of growth on surfaces of FRPCMs and resins (Gu et al. Aureobasidium pullulans and Cladosporidium sp were isolated (Crabbe . Gu / International Biodeterioration & Biodegradation 52 (2003) 69 – 91 Fig. Mitchell et al. 1996). Using EIS. . R?olleke et al. Pseudomonas cepacia. which have been held in museum condition.. animal bones and shells. an increase of double bonds was observed when polymers showed weight loss resulting from biodegradation (Albertsson et al. molecular weight.. PE pipes used in gas distribution systems may fail due to cracking. 1995). and modern books from library in tropic region. and the hazard they present to freshwater and marine animals. Their degradability in natural environments poses serious environmental concerns due to their slow degradation rates under natural conditions. aldehydes. 1988). ketones. 1980. Fig. and (d) books with molding development from a library in the tropical region.. Prior exposure of PEs to UV promotes polymer degradation. and plasticizers may signi6cantly alter the biodegradability of the parent polymers (Karlsson et al. However. It was proposed that microbial PE degradation is a two-step process involving an initial abiotic photooxidation. Crystallinity. 1974). 1988). PE was claimed to be degraded. Florian. 2001. and mummi6ed bodies. 1993. lacquer. 1992.1. senegalensis.. The mechanism may involve the formation of hydroperoxides which destabalize the polymeric carbon chain to form a carbonyl group (Cacciari et al.. and may accelerate the process.. 1991.. It is believed that polymer additives. Abiotic degradation of PE is evident by the appearance of carbonyl functional groups in abiotic environments. and microbial metabolites may contaminate the PE surfaces and could be interpreted as degradation products of the parent PE. coloring agents. antioxidants. 1996). and surfactants are all factors a/ecting the fate and rate of PE degradation. In addition. Lauwers and Heinen. 4. Severini et al.. Breslin. wood (Blanchette. Gu / International Biodeterioration & Biodegradation 52 (2003) 69 – 91 79 et al. Arthrobacter globiformis. followed by formation of carboxylic acid. extracellular concentrates of three Streptomyces species cultures were inoculated to starch containing PE 6lms (Pometto et al. However.. silk. 1996... papers (Adamo et al. Photographs showing the: (a) ancient writing script. A Comamonas acidovoran TB-35 was also reported (Akutsu et al.. Other data describing degradation of PE containing starch is questionable. 2000.-D. Polyethylene Polyethylenes (PEs) of high and low density are primarily used in product packaging as sheets and thin 6lms. 1993.. jade.J. 8. additives. 1998). 1995. Arai..6. the mechanism of the second step needs extensive analysis before plausible conclusions can be drawn con6dently. sensitizers. 8 shows ancient script on paper and textile. 1994) and esterase activity was detected with C. In contrast. Pseudomonas putida. (c) bronze. For example. 1998. Zyska. Nakajima-Kambe et al. These materials are either in need . surface treatment. Biodeterioration of cultural heritage materials Other materials of interest and importance to society for protection from biodeterioration are cultural objects with historical and cultural value. degradation is very slow. 3. Pseudomonas aeruginosa. 1995. and two other Pseudomonas-like species (El-Sayed et al. Degradation rates may be increased by 2– 4% following photosensitizer addition. 3. estimated in decades. 1991. and carboxylic acids are formed abiotically in 6 weeks (Albertsson et al. 1990). Fabbri et al. It is unlikely that biological processes are involved (Zhou and Brown.. conclusion on PE degradation should be treated with caution.6. Fig. such as starch. Realizing that degradation may occur and the extent could be extremely small.. 1997). 1997. Wu et al. 1996). paintings (Fabbri et al.6. 1994). 1993. Pseudomonas chlororaphis was isolated and encoded a lipase responsible for the degradation (Stern and Howard.. At higher temperatures. Imam and Gould. 1993. Lower molecular weight PEs including paraSn can be biodegraded and paraSn undergoes hydroxylation oxidatively to form an alcohol group. Subsequently. 1993). Degradation of PPs results in a decrease of their tensile strength and molecular weight. Biodegradation of PEs has been studied extensively earlier (Albertsson. 1972). alcohols. 1992. 1997. A number of bacteria were also claimed to be capable of degrading polyurethane and they are four stains of Acinetobacter calcoaceticus. Polypropylenes Polypropylenes (PPs) are also widely utilized as engineering pipes and containers. Resistance polymers 3. 2000). 1998. Zou et al. but the results were based on PE blent with starch. Pi˜nar et al. 1994). ceramic and glass (Fuchs et al.2.. lactones. followed by a cleavage of the polymer carbon backbone. King and Eggins. Examples of these materials are bronze (Wang et al. (b) textile. Degradability of pure and high molecular weight PPs is still an open question. 1994). Breslin and Swanson. Tilstra and Johnsonbaugh. Conservation and preservation of them are a major task in all museums worldwide and integrated research e/ort deserves more attention in understanding the processes contributing to the problem and proposing preventive measure or solution. polyurethane. lowering humidity is a very e/ective means to slow down the growth of microorganisms on surfaces in an enclosed environment (Gu et al. unpublished data) and guidelines are needed for systematic evaluation of candidate polymers and their suitability in speci6c applications. 1994. and to decrease chance of contamination. organic polymers are widely used in consolidation of monuments and repairing of art works (Selwitz. the e/ectiveness of the addition is questionable from our past experience (Fig. 1994).. Preventive measures Microbial growth and propagation on material surfaces can be controlled by physical and chemical manipulations of the material and the arti6cial environments. Prevention and detection of biodeterioration 5. for protection or su/er from potential biodeterioration due to the growth of microorganisms which have been established their population on surfaces of materials. 1984. 1998b) and prevention against potential contamination will prolong the life time of the objects. culture. Basic measures in control of biodeterioration should be focused on the surface especially the initial population of organisms. Apparently. 4. polymer additives and other constituents are more likely to serve as a source of carbon and energy for microbial growth when temperature and moisture (humidity) are favorable for the proliferation of microorganisms (Gu et al.1. Signi6cant importance for protection and preservation of them is on the social. 2000b. Staley et al. 1992)... such understanding and the preventive measure can only be achieved by collective research e/ort from biologists. Consolidant polymers In addition to the polymers and applications described above. 9). 1993). This problem will be more serious than expected when eradication of microorganisms becomes harder using these chemicals due to resistant development in microorganisms after exposure (Bingaman and Willingham. Sneath et al.. Since these polymers are mostly commercial products. 5. These physical conditions are generally available particularly in developing countries where resource is limited for preservation and conservation. 9. chemists and conservators. Gu / International Biodeterioration & Biodegradation 52 (2003) 69 – 91 Fig. Though application of biocides becomes a routine practice in the con- servation of art works. Mansfeld. 1994.1. Utilization of these materials by common Nora of microorganisms transported in the atmosphere has been documented (Gu and Mitchell. 1992. 1989). and epoxies. sensitive art pieces should be carefully protected environmentally and the numbers of visitors should also be controlled to maintain a relatively constant temperature and humidity. Without a better understanding of what is on the surface. 2000) and microbiological manuals (Balow et al. Even organic pollutants can be degraded by natural microorganisms (Gu and Berry... Scamans et al..g. As a control measure. none of them is resistance to microbial colonization (Gu. 1992a).. Young. 1986. 1992. 1994.. Prevention against biodeterioration include surface engineering so that attachment by and susceptibility to microorganisms and then the fouling organisms can be reduced greatly (Gu and Cheung. 1998b.-D. and archaeological and historical value and scholarly meaning for future study. 1989. Williams et al. Among several consolidants including acryloids. Matamala et al. 1991. Basic information on microorganisms are widely available from textbook (e. 2001. unpublished data). Madigan et al. Under museum conditions. Gu et al. Photograph showing inhibition of microorganisms on surface of agar plates by a biocide in the discs placed on the agar plates.. 1989.. 1948).80 J. Krieg and Holt. Williamson. subsequent protection measure cannot be tar- . . In addition to their environmental unacceptability most of the time because of toxicity. 1998. L?u et al. 1993a–c. McFeters et al. 1995. 1994.-D. Highly sensitive and quantitative method has also been introduced in evaluation of polymer integrity using EIS (Gu et al. 1994. biocides can be e/ective in controlling bio6lms and subsequent deterioration of materials to some extent (Bell and Chadwick. Xu et al. No solution to these problems is currently available and alternative biocides have been screened from natural products (Abdel-Hafez and El-Said. cleaning and maintenance of artworks.. by heterotrophic bacteria (Padival et al. 1984.. 1992. 1998b. By modi6cation of the microbial community. Stewart et al... 1990.. All of these e/orts have met with limited success.. 1998. 1998b.. More methods are now becoming available for test the biodeterioration and biodegradation of organic materials. Simulation testing of microbial growth on materials includes only a small selection of fungal species (ASTM.. 1996) and conservation of art (Bianchi et al. These chemicals have been shown to be ine/ective in killing bio6lm bacteria (Gu et al.. 1994). future tests should be focused on the dynamics of bio6lm and quanti6cation than descriptively showing bio6lm of scanning electron micrographs. 1992. Current research by materials scientists is focused on the prevention of adhesion of corrosive microorganisms to surfaces through surface treatments and modi6cation (Costerton et al. 1997). Since bacteria are capable of forming bio6lms on surfaces of materials. Prevention against bio6lm formation and biodeterioration include surface engineering so that attachment and susceptibility to microorganisms and the fouling organisms can be reduced greatly (Mansfeld. biocides induce the development of bio6lms that are highly resistant to the levels of chlorine normally utilized to prevent biocorrosion.. Matamala et al. 1988. 1996.. Testing methodologies Another critical issue in this area is the standardization of test methodologies. 1997. Suci et al. Bell and Chadwick. Current available methods are certainly not representative of the actual conditions for each individual case. and displacement of Thiobacillus sp.. Early detection is an important component in diagnosis and prevention of severe deterioration of materials (Li et al. Other attempts at community modi6cation include precipitation of microbially produced H2 S by ferrous chloride (FeCl2 ) (Morton et al.. 1995a–d. 6. This major discrepancy has not fully been resolved. Actually. so that data generated on the materials will be a quantitative description of the biological deterioration potential. New initiative is needed for innovative methodology to assess biocidal e/ects using surface oriented assays.. Young. 1995). 1994.. Williamson. 1996. Cargill et al. 1989. Reinsel et al. Stewart et al. Use of biocides Biocides are commonly applied in repairing. Scamans et al. 5. c. 9). 1995.3. better results can be achieved. 1994. 1995). Organic biocides..2. Liu et al. 1994. but very little Nexibility is o/ered in the methods. 1993. Bell et al. 1995). 1995. Gu / International Biodeterioration & Biodegradation 52 (2003) 69 – 91 get speci6c. Moore and Postle. DNA probes and microarray (Raychaudhuri et al. 1980. 1992. 2001. Conclusions Microorganisms are involved in the degradation and deterioration of polymers under both aerobic and anaerobic . 2000b. Koenig et al. Because bio6lm bacteria are more resistance to antibiotics and biocides. test 81 of assaying eScacy of biocide should be conducted based on bio6lm condition than liquid culture eScacy (Gu et al.... In particular. 1992b. 1997. Coupling the understanding of surface microbial ecology using molecular techniques and then controlling measure. 1998a. used to prevent bacterial growth in industrial systems. 1996. d). With the latest advances.. (1991) proposed oxygenation as a means of alleviating the propagation of SRBs under anoxic conditions.. new techniques should be adopted in tests according to the characteristics of materials and their application environments. 1996. Pyle et al. 1980). It should also be pointed out that new detection technologies including optical 6ber (Bacci. 2000) will 6nd valuable applications in this exiciting 6eld of research and development in the near future.. Wake6eld. 1994. iodine and other organic biocidal compounds are used widely and routinely in controlling bio6lms which cause corrosion and deterioration of a wide range of materials in industries (Bloom6eld and Megid. 1996. Keevil and Mackerness. Rossmoore and Rossmoore.J. Furthermore. 1992. Bell et al. 1991. Stewart. 1994... 2000d).. 1997). 1989. particularly polymers in various chemical composition and degradability (Gross et al. biodeterioration assessment has hardly been quantitative because presence of bacteria or fungi on surface of materials has generally been assumed as biodeterioration (Zachary et al.... 1988). recent development in molecular technique involving DNA based information allows a better examination of any surface due to the shortcomings with traditional microbiological techniques (Amann et al. 1994). 1993). Br?ozel and Cloete. Myers. Huang et al. 1995. 5. 1948). 1993a–e) while deterioration under natural environment is hardly carried out by those species. tests based on planktonic cells are not truly representative of their actual conditions on surfaces of materials. Both gravimetric method and respirometry have been tested and used successfully with CAs and PHB as testing polymers. 2000b). the interpretation is about the potential for biodeterioration not actually biodeterioration and biodegradation. At the same time. 1996.. may selectively enrich population of microorganisms capable of biocide resistance (Fig. Chen and Stewart. In this area. Bingaman and Willingham. Srinivasan et al. Gu et al.. Salama et al. Yu and McFeters. Sand et al. 1991). 1993. McFeters. 1994b. Wake6eld. Chlorine. A.-C... Standard practice for determining resistance of plastics to bacteria. H. Acta Polymers 45. pp. In: 1993 Annual Book of ASTM Standards. 1992. Geesthacht. J. 635–643. 527–529. Anderson.. In: 1993 Annual Book of ASTM Standards. Applied and Environmental Microbiology 64. ASTM (American Society for Testing and Materials). T. Z. 1994...L. A.. E/ect of pretreatment of rubber material on its biodegradability by various rubber degrading bacteria. Ham. 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