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.

Brominated disinfection byproducts (DBPs), formed from the reaction of disinfectant(s) with natural organic matter and bromide in raw water, are generally more cytotoxic and genotoxic than their chlorinated analogues. Brominated DBPs have been intensively studied over the past 35 years, yet only a fraction of the total organic bromine formed during disinfection has been identified. A significant portion of the unaccounted total organic bromine may be attributed to polar/highly polar brominated DBPs. In this work, a method for fast selective detection of polar/ highly polar brominated DBPs in drinking water was developed using negative ion electrospray ionization-triple quadrupole mass spectrometry (ESI-tqMS) by setting precursor ion scans of m/z 79 and 81. This method was conducted without liquid chromatography separation. The results demonstrate that the ESI-tqMS precursor ion scan is an effective tool for the selective detection of electrospray ionizable bromine-containing compounds in a complex mixture. Many polar/ highly polar bromine-containing DBPs were tentatively found in two drinking water samples, and some of them may be new brominated DBPs that have not been previously reported. This method was also extended for the selective detection of polar bromine-containing compounds/contaminants in groundwater, surface water and wastewater.

This study reports results of sediment bioslurry treatment and earthworm bioaccumulation for polycyclic aromatic hydrocarbon (PAH) contaminants found in sediment dredged from Milwaukee Harbor. A significant finding was that bioslurry treatment reduced PAHs on the sediment clay/silt fraction but not on the sediment coal-derived fraction and that PAH reduction in the clay/silt fraction correlated with substantial reduction in earthworm PAH bioaccumulation. These findings are used to infer PAH bioavailability from characterization of particle-scale PAH distribution, association, and binding among the principal particle fractions in the sediment. The results are consistent with work showing that the sediment comprised two principal particle classes for PAHs, coal-derived and clay/silt, each having much different PAH levels, release rates, and desorption activation energies. PAH sorption on coal-derived particles is associated with minimal biodegradation, slow release rates, and high desorption activation energies, while PAH sorption on clay/silt particles is associated with significant potential biodegradability, relatively fast release rates, and lower desorption activation energies. These characteristics are attributed to fundamental differences in the organic matter to which the PAHs are sorbed. Although the majority of the PAHs are found preferentially on coal-derived particles, the PAHs on the clay/silt sediment fraction are more mobile and available, and thus potentially of greater concern. This study demonstrates that a suite of tests comprising both bioassays and particle-scale investigations provide a basis to assess larger-scale phenomena of biotreatment of PAH-impacted sediments and bioavailability and potential toxicity of PAH contaminants in sediments. Improved understanding of contaminant bioavailability aids decision-making on the effectiveness of biotreatment of PAH-impacted sediments and the likelihood for possible reuse of dredged sediments as reclaimed soil or fill.

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.

13The effect of natural organic matter (NOM) on arsenic adsorption by a com-

Hydroxyapatite (HAP) has been widely used to immobilize many cationic heavy metals in water and soils. Compared with its strong sorption for metal cations, the abilities of HAP to sorb metal anions, such as arsenic, are less significant. Improving HAP sorption for anionic arsenic species is important for expanding its application potential because the presence of arsenic in the environment has raised serious health concerns and there is need for cost-effective remediation methods. In this work, we report an innovative method of copper doping to improve a synthetic HAP sorption for arsenate, which is a primary aqueous arsenic species, in simulated groundwaters. The undoped HAP and copper doped HAP (CuHAP) were characterized with XRD, FTIR, N(2) adsorption, and SEM, and then evaluated as sorbents for arsenate removal tests. The experimental results suggest that copper doping changed the morphology and increased the surface area of HAP. The CuHAP sorbed 1.6-9.1x more arsenate than the undoped HAP did in a simulated groundwater at pH of 7.7-8.0. The improved arsenate sorption is presumably due to the increase in surface area of HAP as a result of copper doping. In addition to the copper doping level, the arsenate sorption to HAP and CuHAP can also be increased with increasing water pH and calcium concentration. The experimental data indicate that sorbent dissolution is an important factor governing arsenate sorption to HAP and CuHAP.

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