Particle-scale investigation of PAH desorption kinetics and thermodynamics from sediment.

Dredged sediment from Milwaukee Harbor showed two primary classes of particles in the <2 mm size range: a lighter-density coal- and wood-derived fraction with 62% of total PAHs and a heavier-density sand, silt, and clay fraction containing the remaining 38% of the PAHs. Room-temperature PAH desorption kinetic studies on separated sediment fractions revealed slow desorption rates for the coal-derived particles and fast desorption rates for the clay/silt particles. The effect of temperature on PAH release was measured by thermal program desorption mass spectrometry to investigate the desorption activation energies for PAHs on the different sediment particles. Three activated diffusion-based models and an activated first-order rate model were used to describe the thermal desorption of PAHs for four molecular weight classes. PAH binding with the coal-derived particles was associated with high activation energies, typically in the range of 115-139 kJ/mol. PAHs bound to the clay/silt material had much lower activation energy, i.e., in the range of 37-41 kJ/ mol for molecular weight 202. Among the desorption models tested, a spherical diffusion model with PAHs located like a rind on the outer 1-3 microm region best described the PAH thermal desorption response for coal-derived particles. This internal PAH distribution pattern on coalderived particles is based on prior direct measurement of PAH locations at the subparticle scale. These studies reveal that heterogeneous particle types in sediment exhibit much different amounts and binding of PAHs. PAHs associated with coal-derived particles aged over several decades in the field appear to be far from reaching an equilibrium sorption state due to the extremely slow diffusivities through the polymer-like coal matrix. These results provide an improved mechanistic perspective for the understanding of PAH mobility and bioavailability in sediments.

Succession of phenotypic, genotypic, and metabolic community characteristics during in vitro bioslurry treatment of polycyclic aromatic hydrocarbon-contaminated sediments.

Dredged harbor sediment contaminated with polycyclic aromatic hydrocarbons (PAHs) was removed from the Milwaukee Confined Disposal Facility and examined for in situ biodegradative capacity. Molecular techniques were used to determine the successional characteristics of the indigenous microbiota during a 4-month bioslurry evaluation. Ester-linked phospholipid fatty acids (PLFA), multiplex PCR of targeted genes, and radiorespirometry techniques were used to define in situ microbial phenotypic, genotypic, and metabolic responses, respectively. Soxhlet extractions revealed a loss in total PAH concentrations of 52%. Individual PAHs showed reductions as great as 75% (i.e., acenapthene and fluorene). Rates of (14)C-PAH mineralization (percent/day) were greatest for phenanthrene, followed by pyrene and then chrysene. There was no mineralization capacity for benzo[a]pyrene. Ester-linked phospholipid fatty acid analysis revealed a threefold increase in total microbial biomass and a dynamic microbial community composition that showed a strong correlation with observed changes in the PAH chemistry (canonical r(2) of 0.999). Nucleic acid analyses showed copies of genes encoding PAH-degrading enzymes (extradiol dioxygenases, hydroxylases, and meta-cleavage enzymes) to increase by as much as 4 orders of magnitude. Shifts in gene copy numbers showed strong correlations with shifts in specific subsets of the extant microbial community. Specifically, declines in the concentrations of three-ring PAH moieties (i.e., phenanthrene) correlated with PLFA indicative of certain gram-negative bacteria (i.e., Rhodococcus spp. and/or actinomycetes) and genes encoding for naphthalene-, biphenyl-, and catechol-2,3-dioxygenase degradative enzymes. The results of this study suggest that the intrinsic biodegradative potential of an environmental site can be derived from the polyphasic characterization of the in situ microbial community.

Biodegradation kinetics of naphthalene in nonaqueous phase liquid-water mixed batch systems: comparison of model predictions and experimental results.

A model is formulated to describe dissolution of naphthalene from an insoluble nonaqueous phase liquid (NAPL) and its subsequent biodegradation in the aqueous phase in completely mixed batch reactors. The physicochemical processes of equilibrium partitioning and mass transfer of naphthalene between the NAPL and aqueous phases were incorporated into the model. Biodegradation kinetics were described by Monod's microbial growth kinetic model, modified to account for the inhibitory effects of 1,2-naphthoquinone formed during naphthalene degradation under certain conditions. System parameters and biokinetic coefficients pertinent to the NAPL-water systems were determined either by direct measurement or from nonlinear regression of the naphthalene mineralization profiles obtained from batch reactor tests with two-component NAPLs comprised of naphthalene and heptamethylnonane. The NAPLs contained substantial mass of naphthalene, and naphthalene biodegradation kinetics were evaluated over the time required for near complete depletion of naphthalene from the NAPL. Model predictions of naphthalene mineralization time profiles compared favorably to the general trends observed in the data obtained from laboratory experiments with the two-component NAPL, as well as with two coal tars obtained from the subsurface at contaminated sites and composed of many different PAHs (polycyclic aromatic hydrocarbon compounds). The effects of varying the NAPL mass and the naphthalene mole fractions in the NAPL are discussed. It was observed that the time to achieve a given percent removal of naphthalene does not change significantly with the initial mass of naphthalene in a fixed volume of the NAPL. Significant changes in the mineralization profiles are observed when the volume (and mass) of NAPL in the system is changed.

Biodegradation of naphthalene in aqueous nonionic surfactant systems.

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.

Effects of nonionic surfactants on the solubilization and mineralization of phenanthrene in soil-water systems.

The solubilization and mineralization of (14)C-phenanthrene in soil-water systems was examined with several commercially available surface-active agents, viz., an alkyl ethoxylate C(12)E(4); two alkylphenol ethoxylate surfactants: C(8)PE(9.5) and C(9)PE(10.5); two sorbitan ethoxylate surfactants: the sorbitan monolaurate (Tween 20) and the sorbitan monooleate (Tween 80); two pairs of nonionic ethoxylate surfactant mixtures: C(12)E(4)/C(12)E(23) at a 1:1 ratio, and C(12-15)E(3)/C(12-15)E(9) at a 1:3 ratio; and two surfactants possessing relatively high critical micelle concentration (CMC) values and low aggregation numbers: CHAPS and octyglucoside. Surface tension experiments were performed to evaluate surfactant sorption onto soil and the surfactant doses required to attain the CMC in the soil-water systems. Surfactant solubilization of (14)C-phenanthrene commenced with the onset of micellization. The addition of surface-active agents was observed not to be beneficial to the microbial mineralization of phenanthrene in the soil-water systems and, for supra-CMC surfactant doses, phenanthrene mineralization was completely inhibited for all the surfactants tested. A comparison of solubilization, surface tension, and mineralization data confirms that the inhibitory effect on microbial degradation of phenanthrene is related to the CMC of the surfactant in the presence of soil. Additional tests demonstrated the recovery of mineralization upon dilution of surfactant concentration to sub-CMC levels, and a relatively high exit rate for phenanthrene from micelles. These tests suggest that the inhibitory effect is probably related to a reversible physiological surfactant micelle-bacteria interaction, possibly through partial complexing or release of membrane material with disrupting membrane lamellar structure. This study indicates that nonionic surfactant solubilization of sorbed hydrophobic organic compounds from soil may not be beneficial for the concomitant enhancement of soil bioremediation. Additional work is needed to address physicochemical processes for bioavailability enhancement, and effects of solubilizing agents on microorganisms for remediation and treatment of hydrophobic organic compounds and nonaqueous phase liquids.

Degradation of polycyclic aromatic hydrocarbon compounds under various redox conditions in soil-water systems.

This study evaluated the microbial degradation of naphthol, naphthalene, and acenaphthene, under aerobic, anaerobic, and denitrification conditions in soil-water systems. Chemical degradation of naphthol and naphthalene in the presence of a manganese oxide was also studied. Naphthol, naphthalene, and acenaphthene were degraded microbially under aerobic conditions from initial aqueous-phase concentrations of 9, 7, and 1 mg/liter to nondetectable levels in 3, 10, and 10 days, respectively. Under anaerobic conditions naphthol degraded to nondetectable levels in 15 days, whereas naphthalene and acenaphthene showed no significant degradation over periods of 50 and 70 days, respectively. Under denitrification conditions naphthol, naphthalene, and acenaphthene were degraded from initial aqueous-phase concentrations of 8, 7, and 0.4 mg/liter to nondetectable levels in 16, 45, and 40 days, respectively. Acclimation periods of approximately 2 days under aerobic conditions and 2 weeks under denitrification conditions were observed for both naphthalene and acenaphthene. Abiotic degradation of naphthalen and naphthol were evaluated by reaction with manganese oxide, a minor soil constituent. In the presence of a manganese oxide, naphthalene showed no abiotic degradation over a period of 9 weeks, whereas the aqueous naphthol concentration decreased from 9 mg/liter to nondetectable levels in 9 days. The results of this study show that low-molecular-weight, unsubstituted, polycyclic aromatic hydrocarbons are amenable to microbial degradation in soil-water systems under denitrification conditions.

Microbial degradation of acenaphthene and naphthalene under denitrification conditions in soil-water systems.

This study examined the microbial degradation of acenaphthene and naphthalene under denitrification conditions at soil-to-water ratios of 1:25 and 1:50 with soil containing approximately 10(5) denitrifying organisms per g of soil. Under nitrate-excess conditions, both acenaphthene and naphthalene were degraded from initial aqueous-phase concentrations of about 1 and several mg/liter respectively, to nondetectable levels (less than 0.01 mg/liter) in less than 9 weeks. Acclimation periods of 12 to 36 days were observed prior to the onset of microbial degradation in tests with soil not previously exposed to polycyclic aromatic hydrocarbon (PAH) compounds, whereas acclimation periods were absent in tests with soil reserved from prior PAH degradation tests. It was judged that the apparent acclimation period resulted from the time required for a small population of organisms capable of PAH degradation to attain sufficient densities to exhibit detectable PAH reduction, rather than being a result of enzyme induction, mutation, or use of preferential substrate. About 0.9% of the naturally occurring soil organic carbon could be mineralized under denitrification conditions, and this accounted for the greater proportion of the nitrate depletion. Mineralization of the labile fraction of the soil organic carbon via microbial denitrification occurred without an observed acclimation period and was rapid compared with PAH degradation. Under nitrate-limiting conditions the PAH compounds were stable owing to the depletion of nitrate via the more rapid process of soil organic carbon mineralization. Soil sorption tests showed at the initiation of a test that the total mass of PAH compound was divided in comparable proportions between solute in the aqueous phase and solute sorbed on the solid phase. The microbial degradation of the PAH compound depends on the interrelationships between (i) the desorption kinetics and the reversibility of desorption of sorbed compound from the soil, (ii) the concentration of PAH-degrading microorganisms, and (iii) the competing reaction for nitrate utilization via mineralization of the labile fraction of naturally occurring soil organic carbon.

Biological oxidation of organic constituents in tar-sand combustion-process water.

A study was performed to characterize a sample of reverse-forward, tar-sand combustion process water, and to conduct an initial evaluation of activated sludge treatment of the process water. No pretreatment of the wastewater was considered necessary prior to biological oxidation other than addition of ca. 0.006M caustic/L influent to maintain reactor pH in the desired range of 7.0-7.5. The process water was treated successfully by biological oxidation, achieving an 88% reduction of both COD and soluble organic carbon and a 97% reduction of BOD. The disposition of about 150 organic compounds was evaluated and it was shown that a variety of carboxylic acids and aromatic compounds were removed by treatment. Quinolines and certain higher molecular weight carboxylic acids were not removed as effectively as other compounds. These preliminary results should assist in the design of future investigations with tar-sand process water for purposes of optimizing process treatment and improving sample characterization.