Abstract: 1. Why Biodegradable Polymers? G. Scott. 2. An Overview of Biodegradable Polymers and Biodegradation of Polymers S.H. Huang. 3. Degradation and Stabilization of Carbon-Chain Polymers G. Scott. 4. Techniques and Methods of Polymer Degradation S. Karlsson, A.-C. Albertsson. 5. Biodegradation of Aliphatic Polyesters Suming Li, M. Vert. 6. Starch-Polymer Composites C. Bastioli. 7. Polymers from Renewable Sources E. Chiellini, et al. 8. Sustainable Poly(Hydroxyalkanoate) (PHA) Production G. Braunegg. 9. Polyhydroxyalkanoates: Properties and Modification for High Volume Application I. Chodak. 10. Biodegradable Polymers in Medicine E Piskin. 11. Environmentally Biodegradable Water-Soluble Polymers G. Swift. 12. Plastics and the Environment J. Guillet. 13. Degradable Hydrocarbon Polymers in Waste and Litter Control G. Scott, D.M. Wiles. Subject Index.

Abstract: Toxic aromatic pollutants, concentrated in industrial wastes and contaminated sites, can potentially be eliminated by low cost bioremediation systems. Most commonly, the goal of these treatment systems is directed at providing optimum environmental conditions for the mineralization of the pollutants by naturally occurring microflora. Electrophilic aromatic pollutants with multiple chloro, nitro and azo groups have proven to be persistent to biodegradation by aerobic bacteria. These compounds are readily reduced by anaerobic consortia to lower chlorinated aromatics or aromatic amines but are not mineralized further. The reduction increases the susceptibility of the aromatic molecule for oxygenolytic attack. Sequencing anaerobic and aerobic biotreatment steps provide enhanced mineralization of many electrophilic aromatic pollutants. The combined activity of anaerobic and aerobic bacteria can also be obtained in a single treatment step if the bacteria are immobilized in particulate matrices (e.g. biofilm, soil aggregate, etc.). Due to the rapid uptake of oxygen by aerobes and facultative bacteria compared to the slow diffusion of oxygen, oxygen penetration into active biofilms seldom exceeds several hundred micrometers. The anaerobic microniches established inside the biofilms can be applied to the reduction of electron withdrawing functional groups in order to prepare recalcitrant aromatic compounds for further mineralization in the aerobic outer layer of the biofilm. Aside from mineralization, polyhydroxylated and chlorinated phenols as well as nitroaromatics and aromatic amines are susceptible to polymerization in aerobic environments. Consequently, an alternative approach for bioremediation systems can be directed towards incorporating these aromatic pollutants into detoxified humic-like substances. The activation of aromatic pollutants for polymerization can potentially be encouraged by an anaerobic pretreatment step prior to oxidation. Anaerobic bacteria can modify aromatic pollutants by demethylating methoxy groups and reducing nitro groups. The resulting phenols and aromatic amines are readily polymerized in a subsequent aerobic step.

Abstract: A study to quantify the effect of rhamnolipid biosurfactant structure on the degradation of alkanes by a variety of Pseudomonas isolates was conducted. Two dirhamnolipids were studied, a methyl ester form (dR-Me) and an acid form (dR-A). These rhamnolipids have different properties with respect to interfacial tension, solubility, and charge. For example, the interfacial tension between hexadecane and water was decreased to <0.1 dyne/cm by the dR-Me but was only decreased to 5 dyne/cm by the dR-A. Solubilization and biodegradation of two alkanes in different physical states, liquid and solid, were determined at dirhamnolipid concentrations ranging from 0.01 to 0.1 mM (7 to 70 mg/liter). The dR-Me markedly enhanced hexadecane (liquid) and octadecane (solid) degradation by seven different Pseudomonas strains. For an eighth strain tested, which exhibited extremely high cell surface hydrophobicity, hexadecane degradation was enhanced but octadecane degradation was inhibited. The dR-A also enhanced hexadecane degradation by all degraders but did so more modestly than the dR-Me. For octadecane, the dR-A only enhanced degradation by strains with low cell surface hydrophobicity.

Abstract: A detailed field investigation has been completed at a gasoline-contaminated aquifer near Rocky Point, NC, to examine possible indicators of intrinsic bioremediation and identify factors that may significantly influence the rae and extent of bioremediation. The dissolved plume of benzene, toluene, ethylbenzene, and xylene (BTEX) in ground water is naturally degrading. Toluene and o-xylene are most rapidly degraded followed by m-, p-xylene, and benzene. Ethylbenzene appears to degrade very slowly under anaerobic conditions present in the center of the plume. The rate and extent of biodegradation appears to be strongly influenced by the type and quantity of electron acceptors present in the aquifer. At the upgradient edge of the plume, nitrate, ferric iron, and oxygen are used as terminal electron acceptors during hydrocarbon biodegradation. The equivalent of 40 to 50 mg/l of hydrocarbon is degraded based on the increase in dissolved CO{sub 2} relative to background ground water. Immediately downgradient of the source area, sulfate and iron are the dominant electron acceptors. Toluene and o-xylene are rapidly removed in this region. Once the available oxygen, nitrate, and sulfate are consumed, biodegradation is limited and appears to be controlled by mixing and aerobic biodegradation at the plume fringes.

Abstract: The principal objective of this study was to quantify the bioavailability of micelle-solubilized naphthalene to naphthalene-degrading microorganisms comprising a mixed population isolated from contaminated waste and soils. Two nonionic surfactants were used, an alkylethoxylate, Brij 30 (C12E4), and an alkylphenol ethoxylate, Triton X-100 (C8PE9.5). Batch experiments were used to evaluate the effects of aqueous, micellized nonionic surfactants on the microbial mineralization of naphthalene and salicylic acid, an intermediate compound formed in the pathway of microbial degradation of naphthalene. The extent of solubilization and biodegradation under aerobic conditions was monitored by radiotracer and spectrophotometric techniques. Experimental results showed that surfactant concentrations above the critical micelle concentration were not toxic to the naphthalene-degrading bacteria and that the presence of surfactant micelles did not inhibit mineralization of naphthalene. Naphthalene solubilized by micelles of Brij 30 or Triton X-100 in liquid media was bioavailable and degradable by the mixed culture of bacteria.

Abstract: The biodegradation of the fuel oil hydrocarbons contained in drilling cuttings was studied in soil microcosms during a 270-day experiment. Concentration and chemical composition of residual hydrocarbons were periodically monitored by quantitative capillary gas chromatography. The decrease in hydrocarbon concentration was logarithmic with time. At the end of the experiment, the fuel oil was 75% degraded. In the saturated fraction, normal and branched alkanes were almost totally eliminated in 16 days ; 22% of the cycloalkanes were not assimilated. The aromatic fraction was 71% degraded ; some polycyclic aromatics were persistent. The resin fraction (10% of the initial weight) was completely refractory to biodegradation. The inorganic part of drilling cuttings had no influence on the biodegradation rates of hydrocarbons. Biogenic hydrocarbons and traces of degradable fuel oil hydrocarbons were protected from microbial activity by the soil and cuttings matrix. Enumerations of total heterotrophic bacteria and hydrocarbon-utilizing bacteria showed a strong stimulation in both populations. Hydrocarbon-degrading strains of bacteria and fungi were isolated and identified at the generic or specific level.

Abstract: Copolyesters composed of aliphatic and aromatic compounds were synthesized by the polycondensation of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, sebacic acid, adipic acid, and terephthalic acid. By applying an appropriate ratio of aliphatic to aromatic acids, the synthesized materials proved to be biodegradable, as was verified by several degradation test methods such as aqueous polymer suspension inoculated by a soil eluate (Sturm test), a soil burial test (at ambient temperature), and a composting simulation test at 60°C. The degradability of the polyester-copolymers (measured as weight loss) was investigated with respect to the aliphatic monomer components and the fraction of terephthalic acid. Excellent biodegradability was observed even for copolymers with a content of terephthalic acid up to 56 mol% (of the acid fraction) and melting points in the range up to 140°C. Degradation by chemical hydrolysis of the polyesters was determined independently and was found to facilitate microbial attack significantly only at higher temperatures. The findings demonstrate that biodegradable polymers with advantageous usage properties can easily be manufactured by conventional techniques from commodity chemicals (adipic acid, terephthalic acid, and ethylene glycol or 1,4-butanediol).

Abstract: Biodegradation is increasingly being considered as a less expensive alternative to physical and chemical means of decomposing organic pollutants. Pathways of biodegradation have been characterized for a number of heterotrophic microorganisms, mostly soil isolates, some of which have been used for remediation of water. Because cyanobacteria are photoautotrophic and some can fix atmospheric nitrogen, their use for bioremediation of surface waters would circumvent the need to supply biodegradative heterotrophs with organic nutrients. This paper demonstrates that two filamentous cyanobacteria have a natural ability to degrade a highly chlorinated aliphatic pesticide, lindane (gamma-hexachlorocyclohexane); presents quantitative evidence that this ability can be enhanced by genetic engineering; and provides qualitative evidence that those two strains can be genetically engineered to degrade another chlorinated pollutant, 4-chlorobenzoate.

Abstract: Chlorinated solvents and their natural transformation products are the most frequently observed groundwater contaminants in the United States. In situ bioremediation using anaerobic or aerobic co-metabolic processes is a promising means of cleaning up contaminated aquifers. Studies show that under natural conditions trichloroethylene can be anaerobically degraded to dichloroethylene, vinyl chloride, and ethylene. Pilot scale field studies of in situ aerobic co-metabolic transformations have shown that indigenous microbes grown on phenol are more effective at degrading trichloroethylene and cis-1,2-dichloroethylene than microbes grown on methane. Modeling studies support field observations and indicate that the removal of trichloroethylene and cis-dichloroethylene results from the biostimulation of an indigenous microbial population. Field tests and modeling studies indicate that, at high TCE concentration, degradation becomes stoichiometrically limited.

Abstract: Since the early 1970s, it has been known that exposure of poly(caprolactone) (PCL) to a variety of microorganisms results in biodegradation of this polymer. Besides the ability of PCL to be utilized as a carbon source for microorganisms, it has been demonstrated that, during degradation, carbon dioxide is generated. Soil burial and compost experiments have shown that chain scission of the PCL backbone occurs, mechanical properties of articles prepared from PCL are reduced rapidly, and significant weight loss occurs in a short time period. This inherent biodegradability of PCL, in combination with its ability to be converted by conventional extrusion equipment, allows for the preparation of biodegradable articles that have utility.

Abstract: A laboratory study was conducted to determine whether commercial surfactants enhance the bioremediation of PAH-contaminated sediments. Phenanthrene was chosen as a representative PAH; an inoculum of PAH-degrading microorganisms, enriched from an aquatic sediment, was used in sediment-water slurry microcosm biodegradation experiments. Of seven non-ionic surfactants tested, only one (Triton X-100) did not inhibit phenanthrene mineralization at concentrations above the critical micelle concentration (CMC). Temporal studies on Triton X-100 revealed that while it initially inhibited mineralization in sediment-free microcosms, after 1 week Triton X-100 slightly improved phenanthrene biotransformation and mineralization in microcosms with and without sediment. For all treatments, phenanthrene disappearance was complete after 9 d, and mineralization reached 50 to 65% after 12 d. Sorption to the sediment appears to have reduced the free aqueous surfactant concentration, thereby reducing surfactant toxicity to the microorganisms. These results suggest that many surfactants are toxic to PAH-degrading microorganisms, and while surfactant addition may not always have adverse effects on biodegradation, the use of surfactants might not be desirable to achieve complete contamination removal.

Abstract: A group of five mesocosms (3.5 m3 each) located at Pointe-au-Pere (St. Lawrence Estuary), Canada, was used to study the biodegradation of crude oil dispersed in cold and icy seawater (−1.8 to 5.5°C) under various environmental conditions. Experiments took place during autumn, winter, and spring and lasted from 2 weeks to 2 months. The bacterial response to the oil was assessed by recording the growth of total bacteria, viable heterotrophic bacteria, and oil-degrading bacteria. Some hydrocarbon ratios were calculated from gas chromatography in aliphatic and aromatic oil fractions and were used as biodegradation indices. A “Combined Index of Biodegradation” is proposed for assessing the overall biodegradation advancement. The winter period appeared critical for an oil spill in arctic/subarctic environments because of the reduced biodegradation under icy conditions. Crude oil adsorbed onto a substrate was found more degraded on its immersed part than on the emerged section exposed to winter conditions. Under more favorable environmental conditions (temperatures >0°C, effective chemical dispersion, oil release, spring microalgal bloom), the bacterial degradation would significantly alter the dissolved/dispersed oil within a few days. Under such conditions, half-life times of dissolved petroleum PAH ranged from 1.5–1.7 days (naphthalene) to 2.4–7.5 days (dimethylphenanthrenes), depending on the contamination level. In microenvironments where oil residues accumulated with biological detritus (surface microlayer, settling matter), the oil biodegradation was naturally enhanced. In contrast, water-in-oil emulsions recovered at the surface of mesocosms were unaltered after one month exposure in autumn.

Abstract: Bacteria able to grow on purified natural rubber in the absence of other organic carbon sources were isolated from soil. Ten isolates reduced the weight of vulcanized rubber from latex gloves by >10% in 6 weeks. Scanning electron microscopy clearly revealed the ability of the microorganisms to colonize, penetrate, and dramatically alter the physical structure of the rubber. The rubber-metabolizing bacteria were identified on the basis of fatty acid profiles and cell wall characteristics. Seven isolates were strains of Streptomyces, two were strains of Amycolatopsis, and one was a strain of Nocardia.

Abstract: The mechanism of phenanthrene transfer to the bacteria during biodegradation by a Pseudomonas strain was investigated using a sensitive respirometric technique (Sapromat equipment) allowing the quasi-continuous acquisition of data on oxygen consumption. Several systems of phenanthrene supply, crystalline solid and solutions in non-water-miscible solvents (silicone oil and 2,2,4,4,6,8,8-heptamethylnonane) were studied. In all cases, analysis of the kinetics of oxygen consumption demonstrated an initial phase of exponential growth with the same specific growth rate. In order to analyze the second phase of growth and phenanthrene degradation, a study of the kinetics of phenanthrene transfer to the aqueous phase was conducted by direct experimentation, with the crystal and silicone oil systems, in abiotic conditions. The data allowed the validation of a model based on phase-transfer laws, describing the variations, with substrate concentrations, of rates of phenanthrene transfer to the aqueous phase. Analysis of the biodegradation curves then showed that exponential growth ended in all cases when the rates of phenanthrene consumption reached the maximal transfer rates. Thereafter, the biodegradation rates closely obeyed, for all systems, the transfer rate values given by the model. These results unambiguously demonstrated that, in the present case, phenanthrene biodegradation required prior transfer to the aqueous phase. With the silicone oil system, which allowed high transfer and biodegradation rates, phenanthrene was directed towards higher metabolite production and lower mineralization, as shown by oxygen consumption and carbon balance determinations.

Abstract: Three lab scale, two stage reactor systems were used to study mineralization of three select sulfonated azo dyes. The dyes used in the study were Acid Orange 10, Acid Red 14, and Acid Red 18. The two stage reactor systems consisted of an anaerobic fixed‐film fiuidized bed reactor followed by an aerobic suspended growth activated sludge reactor. Results indicate dye decolorization levels of greater than 90% in the first stage for the two red dyes and greater than 65% decolorization for Acid Orange 10. There was very little additional decolorization in the second stage. Analysis of the metabolic intermediates indicate extensive (>99%) metabolite removal in the first stage for all three reactors. COD removal in all three reactors reached a steady state of approximately 85% in the first stage, with very little additional COD removal in the second stage.

Abstract: For investigation of the microbial accessibility of polyesters based on 1,3-propanediol, a series of different polymer structures (homo, random, and block copolymers) were synthesized by polycondensation of terephthalic acid, adipic acid, sebacic acid, and 1,3-propanediol. The alcohol component, 1,3-propanediol, can be obtained from a biotechnological process from glycerol, a surplus product of the oleochemical industry. Aliphatic dicarbonic acids can be derived from vegetable oils. Biodegradation was performed in different test systems. 1) Polyester films were exposed to an aerated liquid medium inoculated with eluates from soil. 2) For this test system, polymer films were buried in soil. Copolyesters exhibited significant differences in both tests. Furthermore, a clear influence of the polymeric structure as well as of the chain length of the aliphatic dicarbonic acids on the microbial accessibility was observed.

Abstract: Degradation of tetrachloroethene (perchloroethylene, PCE) was investigated by combining the metabolic abilities of anaerobic bacteria, capable of reductive dechlorination of PCE, with those of aerobic methanotrophic bacteria, capable of co-metabolic degradation of the less-chlorinated ethenes formed by reductive dechlorination of PCE. Anaerobic communities reductively dechlorinating PCE, trichloroethene (TCE) and dichloroethenes were enriched from various sources. The maximum rates of dechlorination observed for various chloroethenes in these batch enrichments were: PCE to TCE (341 mumol l-1 day-1), TCE to cis-dichloroethene (159 mumol l-1 day-1), cis-dichloroethene to chloroethene (99 mumol l-1 day-1) and trans-dichloroethene to chloroethene (22 mumol l-1 day-1). A mixture of these enrichments was inoculated into an anoxic fixed-bed upflow column. In this column PCE was converted mainly into cis-1,2-dichloroethene, small amounts of TCE and chloroethene, and chloride. Enrichments of aerobic methanotrophic bacteria were grown in an oxic fixed-bed downflow column. Less-chlorinated ethenes, formed in the anoxic column, were further metabolized in this oxic methanotrophic column. On the basis of analysis of chloride production and the disappearance of chlorinated ethenes it was demonstrated that complete degradation of PCE was possible by combining these two columns. Operation of the two-column system under various process conditions indicated that the sensitivity of the methanotrophic bacteria to chlorinated intermediates represented the bottle-neck in the sequential anoxic/oxic degradation process of PCE.

Abstract: A nonaqueous-phase liquid (NAPL) may sequester a large fraction of a hydrophobic pollutant away from the aqueous phase. A study was conducted to determine whether the low aqueous concentrations of the compound may be associated with the absence of biodegradation. A phenanthrene-degrading mixed culture did not mineralize phenanthrene when initially dissolved in di-2-ethylhexyl phthalate (DEHP) at concentrations of 0.6-20 μg/mL. Under these conditions, the concentration of phenanthrene in water at equilibrium was less than 1 ng/mL. Such a threshold was not observed when a strain of Pseudomonas or a sample of subsoil was used as the inoculum or when the NAPL added was 2,2,4,4,6,8,8-heptamethylnonane. However, the biodegradation rates by all three populations at the low concentrations of phenanthrene in the NAPLs were slow and far less than expected from the rates at higher concentrations. At high concentrations, the rates of mineralization were higher than the rates of partitioning of phenanthrene to water, whereas mineralization was much slower than partitioning at low concentrations. We suggest that some NAPLs may sequester hydrophobic compounds away from the aqueous phase to an extent that the concentration falls below the threshold for biodegradation or to a level that results in unexpectedly slow biodegradation.