A review of the environmental fate, effects, and exposures of bisphenol A.

Bisphenol A (CAS 85-05-7) may be released into the environment through its use and handling, and permitted discharges. BPA is moderately soluble (120 to 300 mg/L at pH 7), may adsorb to sediment (Koc 314 to 1524), has low volatility, and is not persistent based on its rapid biodegradation in acclimated wastewater treatment plants and receiving waters (half-lives 2.5 to 4 days). BPA is "slightly to moderately" toxic (algal EC50 of 1000 micrograms/L) and has low potential for bioaccumulation in aquatic organisms (BCFs 5 to 68). The chronic NOEC for Daphnia magna is > 3146 micrograms/L. Surface water concentrations are at least one to several orders of magnitude lower than chronic effects, with most levels nondetected.

Bisphenol A concentrations in receiving waters near US manufacturing and processing facilities.

Bisphenol A (BPA) (CAS 80-05-7) was analyzed in receiving waters upstream and downstream of US manufacturers (1996 and 1997) and processors (1997) during seasonal low flow periods. BPA was not detected (< 1 microgram/l) in any surface water sample in 1996 or at six of seven sites in 1997. Concentrations near the seventh site ranged from 2 to 8 micrograms/l; however, its receiving stream had no measurable flow and concentrations represent undiluted effluent. All surface water concentrations from this and other studies were less than the freshwater predicted no effect concentration (PNEC) of 64 micrograms/l, suggesting that BPA discharges from manufacturing and processing facilities to surface water do not pose an environmental concern.

Biodegradation of bisphenol A in aquatic environments: river die-away.

The biodegradability of bisphenol A (BPA) was assessed in surface waters from seven different rivers across the United States and Europe. Rapid biodegradation of BPA was observed in all rivers following lag phases ranging from 2 to 4 d. Biodegradation half-lives for BPA were typically less than 2 d following the lag phase. Mineralization of BPA was observed in all river waters, with average carbon dioxide yields of approximately 76% of the theoretical maximum (range 59-103%) at the end of the incubation period (< or = 18 d). Short half-lives (0.5 to 3 d) were noted for BPA biodegradation in river waters regardless of geographic location, sampling site (i.e., upstream vs downstream of wastewater outfalls), sediment addition (< or = 0.05%), and initial test chemical concentration (50-5,500 microgram/L). Subsequent studies conducted at environmentally relevant concentrations (0.05 and 0.5 microgram/L) also indicated short half-lives (3-6 d) for BPA and support the extrapolation of the half-lives measured in this study over a wide range of environmental concentrations. The fact that BPA was degraded rapidly in surface waters taken from diverse locations in the United States and Europe as well as in studies recently conducted in Japan suggests that BPA degrading microorganisms are widely distributed in nature. These observations provide clear evidence that BPA is not persistent in the aquatic environment.

Biodegradation of [(14)C] ring-labeled nonylphenol ethoxylate.

Nonylphenol (NP) and the 9-mole ethoxylate of nonylphenol (NPE9) were synthesized with a uniform radioactive (14)C label in the aromatic ring. The [(14)C]NP isomer distribution and [(14)C]NPE9 oligomer distribution closely matched that of commercial NPE9. Biodegradation of [(14)C]NPE9 was examined under conditions simulating a river water environment, and changes in the oligomer distribution and mineralization to (14)CO(2) were monitored for 128 days. Over 40% of the [(14)C]NPE aromatic ring carbon was converted to (14)CO(2) and another 21% was incorporated into the biomass. Primary degradation of NPE (conversion to metabolites other than NP, NPE ethoxylates, and NPE carboxylates) was estimated to be 87-97%. NP was a minor metabolite, accounting for less than 0.4% of the initial NPE. These studies demonstrate that the phenolic ring of NPE is opened, metabolized, and mineralized in the aquatic environment.

Fate and effects of methylene chloride in activated sludge.

Activated sludge obtained from a municipal wastewater treatment plant was acclimated to methylene chloride at concentrations between 1 and 100 mg/liter by continuous exposure to the compound for 9 to 11 days. Acclimated cultures were shown to mineralize methylene chloride to carbon dioxide and chloride. Rates of methylene chloride degradation were 0.14, 2.3, and 7.4 mg of CH2Cl2 consumed per h per g of mixed-liquor suspended solids for cultures incubated in the presence of 1, 10, and 100 mg/liter, respectively. Concentrations of methylene chloride between 10 and 1,000 mg/liter had no significant effect on O2 consumption or glucose metabolism by activated sludge. A hypothetical model was developed to examine the significance of volatilization and biodegradation for the removal of methylene chloride from an activated sludge reactor. Application of the model indicated that the rate of biodegradation was approximately 12 times greater than the rate of volatilization. Thus, biodegradation may be the predominant process determining the fate of methylene chloride in activated sludge systems continuously exposed to the compound.

Kinetics of microbial growth on mixtures of pentachlorophenol and chlorinated aromatic compounds.

Batch experiments were conducted to examine the effects of several substrate analogs on the degradation of pentachlorophenol by an enrichment culture of pentachlorophenol-utilizing bacteria. The presence of substrate analogs which were unable to serve as a carbon source for growth of the culture (e.g., 3,5,6,-trichloro-2-pyridinol, 2,4-dichlorophenoxyacetic acid) decreased the rate of pentachlorophenol degradation. The presence of a utilizable substrate analog (e.g., phenol, 2,4,5-trichlorophenol) also inhibited the initial rate of pentachlorophenol degradation; however, the overall removal rate was accelerated due to an increase in cell mass concentration as a result of simultaneous growth on both substrates. These effects were shown to be predicted by a mathematical model based on a modified Monod equation. Kinetic parameters obtained from the results of laboratory studies can be used for further process analysis to define the optimal conditions for the biological treatment of complex mixtures of phenolic compounds.

Metabolism of dibenzo[1,4]dioxan by a Pseudomonas species.

Pseudomonas sp. N.C.I.B. 9816 strain 11, when grown on salicylate in the presence of dibenzo[1,4]dioxan, accumulated cis-1,2-dihydroxy-1,2-dihydrodibenzo[1,4]dioxan and 2-hydroxydibenzo[1,4]dioxan in the culture medium. Each metabolite was isolated in crystalline form and identified by a variety of conventional chemical techniques. Crude cell extracts prepared from the parental strain grown with naphthalene oxidized cis-1,2-dihydroxy-1,2-dihydrodibenzo[1,4]dioxan under both aerobic and anaerobic conditions to 1,2-dihydroxydibenzo[1,4]dioxan. Further degradation of this metabolite was not detected.

Metabolism of Dibenzo-p-Dioxin and Chlorinated Dibenzo-p- Dioxins by a Beijerinckia Species.

Whole cells of the parent strain of Beijerinckia, grown with succinate and biphenyl, oxidized dibenzo-p-dioxin and several chlorinated dioxins. The rate of oxidation of the chlorinated dibenzo-p-dioxins decreased with an increasing degree of chlorine substitution. A mutant strain (B8/36) of Beijerinckia oxidized dibenzo-p-dioxin to cis-1,2-dihydroxy-1,2-dihydrodibenzo-p-dioxin. The mutant organism also oxidized two monochlorinated dibenzo-p-dioxins to cis-dihydrodiols. No metabolites were detected from two dichlorinated dibenzo-p-dioxins. Growth of the parent strain of Beijerinckia on succinate was inhibited after 4 h when 0.05% dibenzo-p-dioxin was present in the culture medium. Resting cell suspensions of the parent organism, previously grown with succinate and biphenyl, oxidized dibenzo-p-dioxin to a compound identified as 1,2-dihydroxydibenzo-p-dioxin. Further degradation of this metabolite was not detected, as the compound was found to be a potent mixed-type inhibitor of two ring-fission oxygenases present in this organism.

Inhibition of catechol 2,3-dioxygenase from Pseudomonas putida by 3-chlorocatechol.

Partially purified preparations of catechol 2,3-dioxygenase from toluene-grown cells of Pseudomonas putida catalyzed the stoichiometric oxidation of 3-methylcatechol to 2-hydroxy-6-oxohepta-2,4-dienoate. Other substrates oxidized by the enzyme preparation were catechol, 4-methylcatechol, and 4-fluorocatechol. The apparent Michaelis constants for 3-methylcatechol and catechol were 10.6 and 22.0 muM, respectively. Substitution at the 4-position decreases the affinity and activity of the enzyme for the substrate. Catechol 2,3-dioxygenase preparations did not oxidize 3-chlorocatechol. In addition, incubation of the enzyme with 3-chlorocatechol led to inactivation of the enzyme. Kinetic analyses revealed that both 3-chlorocatechol and 4-chlorocatechol were noncompetitive or mixed-type inhibitors of the enzyme. 3-Chlorocatechol (Ki = 0.14 muM) was a more potent inhibitor than 4-chlorocatechol (Ki = 50 muM). The effect of the ion-chelating agents Tiron and o-phenanthrolene were compared with that of 3-chlorocatechol on the inactivation of the enzyme. Each inhibitor appeared to remove iron from the enzyme, since inactive enzyme preparations could be fully reactivated by treatment with ferrous iron and a reducing agent.

Kinetics of microbial growth on pentachlorophenol.

Batch and fed-batch experiments were conducted to examine the kinetics of pentachlorophenol utilization by an enrichment culture of pentachlorophenol-degrading bacteria. The Haldane modification of the Monod equation was found to describe the relationship between the specific growth rate and substrate concentration. Analysis of the kinetic parameters indicated that the maximum specific growth rate and yield coefficients are low, with values of 0.074 h-1 and 0.136 g/g, respectively. The Monod constant (Ks) was estimated to be 60 micrograms/liter, indicating a high affinity of the microorganisms for the substrate. However, high concentrations (KI = 1,375 micrograms/liter) were shown to be inhibitory for metabolism and growth. These kinetic parameters can be used to define the optimal conditions for the removal of pentachlorophenol in biological treatment systems.

Effects of dissolved oxygen concentration on biodegradation of 2,4-dichlorophenoxyacetic acid.

Batch experiments were conducted to examine the effects of dissolved oxygen concentration on the degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) by an enrichment culture of 2,4-D-utilizing bacteria. A modified Monod equation was found to describe the relationship between the specific growth rate and the concentrations of both the organic substrate and dissolved oxygen. Values for the maximum specific growth rate, yield, and Monod coefficient for growth on 2,4-D were 0.09 h-1, 0.14 g/g, and 0.6 mg/liter, respectively. The half-saturation constant for dissolved oxygen was estimated to be 1.2 mg/liter. These results suggest that dissolved oxygen concentrations below 1 mg/liter may be rate limiting for the biodegradation of chlorinated aromatic compounds such as 2,4-D, which have a requirement for molecular oxygen as a cosubstrate for metabolism.

Biodegradation of aircraft deicing fluids in soil at low temperatures.

The effects of substrate concentration and temperature on the biodegradation of five different aircraft deicing fluids was examined in soil samples obtained from an area adjacent to an airport runway. The principle organic constituents, which included ethylene, propylene, and diethylene glycols, were shown to be mineralized to carbon dioxide in soil microcosms incubated at temperatures ranging from -2 to 25 degrees C. No lag period was observed, and biological transformation of the test chemicals began immediately after addition to the soil. Glycol biodegradation was observed in soil at concentrations ranging from 392 to 5278 mg/kg, suggesting that high levels of the deicing fluids are unlikely to be inhibitory to soil microorganisms. All three glycols were readily degraded in soil at 8 and 25 degrees C, regardless of whether the compounds were present singly or as a component of a mixture. In addition, the biodegradation rates for the three compounds were very similar. Average rates were in the range of 19.7 to 27.0 mg/kg soil per day at 8 degrees C and 66.3 to 93.3 mg/kg soil per day for soil samples incubated at 25 degrees C. The soil biodegradation rates were reduced in soils at -2 degrees C to between 2.3 and 4.5 mg/kg per day. Based on these results, biodegradation is expected to play a major role in removing residual levels of glycols from soils adjacent to airport taxiways and runways.

Stable carbon isotope evidence for intrinsic bioremediation of tetrachloroethene and trichloroethene at area 6, Dover Air Force Base.

Area 6 at Dover Air Force Base (Dover, DE) has been the location of an in-depth study by the RTDF (Remediation Technologies Development Forum Bioremediation of Chlorinated Solvents Action Team) to evaluate the effectiveness of natural attenuation of chlorinated ethene contamination in groundwater. Compound-specific stable carbon isotope measurements for dissolved PCE and TCE in wells distributed throughout the anaerobic portion of the plume confirm that stable carbon isotope values are isotopically enriched in 13C consistent with the effects of intrinsic biodegradation. During anaerobic microbial reductive dechlorination of chlorinated hydrocarbons, the light (12C) versus heavy isotope (13C) bonds are preferentially degraded, resulting in isotopic enrichment of the residual contaminant in 13C. To our knowledge, this study is the first to provide definitive evidence for reductive dechlorination of chlorinated hydrocarbons at a field site based on the delta13C values of the primary contaminants spilled at the site, PCE and TCE. For TCE, downgradient wells show delta13C values as enriched as -18.0/1000 as compared to delta13C values for TCE in the source zone of -25.0 to -26.0/1000. The most enriched delta13C value on the site was observed at well 236, which also contains the highest concentrations of cis-DCE, VC, and ethene, the daughter products of reductive dechlorination. Stable carbon isotope signatures are used to quantify the relative extent of biodegradation between zones of the contaminant plume. On the basis of this approach, it is estimated that TCE in downgradient well 236 is more than 40% biodegraded relative to TCE in the proposed source area.