Evidence for multiple removal pathways in low-temperature (200-400 °C) thermal treatment of pentachlorophenol-laden soils.

Polychlorinated aromatic compounds (PCACs) pose significant remediation challenges, since their high soil affinities preclude mobile-phase partitioning and subsurface extraction. To enhance partitioning and desorption, subsurface temperatures are raised using a technique called thermal conduction heating-soil vapor extraction (TCH-SVE). While this technique improves PCAC partitioning, it can also promote several degradation reactions under temperatures typical of low-temperature TCH-SVE (200-400 °C).

Importance of doping, dopant distribution, and defects on electronic band structure alteration of metal oxide nanoparticles: Implications for reactive oxygen species.

Metal oxide nanoparticles (MONPs) are considered to have the potency to generate reactive oxygen species (ROS), one of the key mechanisms underlying nanotoxicity. However, the nanotoxicology literature demonstrates a lack of consensus on the dominant toxicity mechanism(s) for a particular MONP. Moreover, recent literature has studied the correlation between band structure of pristine MONPs to their ability to introduce ROS and thus has downplayed the ROS-mediated toxicological relevance of a number of such materials.

Distribution of Fullerene Nanoparticles between Water and Solid Supported Lipid Membranes: Thermodynamics and Effects of Membrane Composition on Distribution.

The distribution coefficient (Klipw) of fullerene between solid supported lipid membranes (SSLMs) and water was examined using different lipid membrane compositions. Klipw of fullerene was significantly higher with a cationic lipid membrane compared to that with a zwitterionic or anionic lipid membrane, potentially due to the strong interactions between negative fullerene dispersions and positive lipid head groups. The higher Klipw for fullerene distribution to ternary lipid mixture membranes was attributed to an increase in the interfacial surface area of the lipid membrane resulting from phase separation.

Mercury speciation during in situ thermal desorption in soil.

Metallic mercury (Hg(0)) and its compounds are highly mobile and toxic environmental pollutants at trace level. In situ thermal desorption (ISTD) is one of the soil remediation processes applying heat and vacuum simultaneously. Knowledge of thermodynamic mercury speciation is imperative to understand the fate and transport of mercury during thermal remediation and operate the treatment processes in a cost-effective manner.

Development of a fluorescence model for the determination of constants associated with binding, quenching, and Förster resonance energy transfer efficiency.

Determining accurate dissociation constants for equilibrium processes involving a fluorescent mechanism can prove to be quite challenging. Typically, titration curves and nonlinear least squares fitting of the data using computer programs are employed to obtain such constants. However, these approaches only consider the total fluorescence signal and often ignore other energy transfer processes within the system.

Surface complexation modeling of Hg(II) adsorption at the goethite/water interface using the charge distribution multi-site complexation (CD-MUSIC) model.

Hypothesis: Previous attempts to describe Hg(II) adsorption onto mineral surfaces using surface complexation models (SCMs) have proven unsuccessful and/or require the use of hypothetical surface species. Given that metal ion adsorption at the mineral-water interface is greatly influenced by mineral surface heterogeneity and the presence of competing adsorbates in solution, it stands to reason that estimating the crystal face composition (CFC) of the mineral surface and the extent of carbonate contamination in the experimental system will improve SCM predictions.

Experiments: The Charge Distribution Multi-Site Complexation (CD-MUSIC) model was used to simulate experimental Hg(II) adsorption data, collected on the iron hydroxide mineral goethite, in the presence and absence of competing adsorbates and complexing ligands as a function of pH and ionic strength.

Effects of lipid composition on partitioning of fullerene between water and lipid membranes.

Fullerene partition coefficients (Klipw) between water and solid supported lipid membranes were determined for membranes of various lipid types and composition over a range of temperatures. The log Klipw (L/kg) values for fullerene, which range from 3.1 to 5.

Temperature effects on alkaline earth metal ions adsorption on gibbsite: approaches from macroscopic sorption experiments and molecular dynamics simulations.

Two approaches, macroscopic adsorption experiments and molecular dynamics simulations, were employed to study the effect of temperature on alkaline earth metals adsorption on gibbsite surfaces. Increased reaction temperature enhanced the extent of metal ion adsorption for all of the alkaline earth metals studied. Whereas Mg(2+) and Sr(2+) adsorption displayed dependence on ionic strength, Sr(2+) adsorption exhibited less dependence on background ionic strength regardless of temperature.

A 'turn-on' FRET peptide sensor based on the mercury binding protein MerP.

A new fluorescent peptidyl chemosensor based on the mercury binding MerP protein with fluorescence resonance energy transfer (FRET) capabilities has been synthesized via Fmoc solid-phase peptide synthesis. The metal chelating unit, which is flanked by the fluorophores tryptophan (donor) and dansyl (acceptor), contains amino acids from MerP's metal binding loop (sequence: dansyl-Gly-Gly-Thr-Leu-Ala-Val-Pro-Gly-Met-Thr-Cys-Ala-Ala-Cys-Pro-Ile-Thr-Val-Lys-Lys-Gly-Gly-Trp-CONH(2)). A FRET enhancement or 'turn-on' response was observed for Hg(2+) as well as for Zn(2+), Cd(2+) and Ag(+) in a pure aqueous solution at pH 7.

Partitioning thermodynamics of selected endocrine disruptors between water and synthetic membrane vesicles: effects of membrane compositions.

The thermodynamics of partitioning of selected endocrine disruptors between water and synthetic membrane vesicles were investigated. For most of the chemicals investigated, partitioning is dominated by the enthalpy change for unsaturated lipid membrane vesicles and by the entropy contribution for saturated lipid membrane vesicles. The contribution of the entropy terms in determining the free-energy change becomes more important compared with the enthalpy terms with increased branching of p-substituted phenols.

Modeling binding equilibrium in a competitive estrogen receptor binding assay.

Although the free concentration is more significant in the environmental chemistry and toxicology of receptor-mediated toxicants, few studies have been conducted to use it as a dose-metric. The relative binding affinity of three model endocrine disrupting compounds, diethylstilbestrol (DES), ethynylestradiol (EE2), and bisphenol A (BPA), were evaluated using a competitive ELISA with human estrogen receptor alpha. After measuring the available receptors and the dissociation constant for 17beta-estradiol, binding inhibition curves using the free concentration as the dose-metric were obtained by assuming species equilibrium in the ELISA system and compared with apparent inhibition curves generated using the nominal concentration as the dose-metric.

Methyl bromide as a building disinfectant: interaction with indoor materials and resulting byproduct formation.

Several buildings were contaminated with Bacillus anthracis in the fall of 2001. These events required consideration of how to disinfect large indoor spaces for continued worker occupation. The interactions of gaseous disinfectants with indoor materials may inhibit the disinfection process, cause persistence of the disinfectant, and lead to possible byproduct formation and persistence.

Use of a parallel artificial membrane system to evaluate passive absorption and elimination in small fish.

A parallel artificial lipid membrane system was developed to mimic passive mass transfer of hydrophobic organic chemicals in fish. In this physical model system, a membrane filter-supported lipid bilayer separates two aqueous phases that represent the external and internal aqueous environments of fish. To predict bioconcentration kinetics in small fish with this system, literature absorption and elimination rates were analyzed with an allometric diffusion model to quantify the mass transfer resistances in the aqueous and lipid phases of fish.

Partitioning of moderately hydrophobic endocrine disruptors between water and synthetic membrane vesicles.

The partition coefficient between water and lipid membrane vesicles (Klipw) has been used as an alternative to the 1-octanol-water partition coefficient (Kow) between water and organic solvent, because it more closely represents actual biological membranes. Despite theoretical differences, log Klipw correlates well with log Kow for conventional nonpolar organic pollutants. In the present study, Klipw values of 11 structurally diverse endocrine-disrupting chemicals (EDCs) were measured for three different types of lipid membrane vesicles from dipalmitoylphosphatidylcholine (DPPC), DPPC/cholesterol, and palmitoyloleoylphosphatidylcholine.

Chemical mass balance model with fractionation for apportioning PM2.5: a test case for Los Angeles traffic sources.

Chemical mass balance receptor models (CMBs) use measured pollutant concentrations, along with source information, to apportion the contributions of primary sources to the measured concentrations. CMBs can be used to evaluate the accuracy of the emission inventories that underlie State Implementation Plan (SIP) modeling, by providing an allocation of emissions to individual source categories. CMBs, however, traditionally have not accounted for the chemical reaction and differential deposition or fractionation that occur between the source and receptor.

Effects of dissolved organic matter surrogates on the partitioning of 17beta-estradiol and p-nonylphenol between synthetic membrane vesicles and water.

Partition coefficients of two estrogenic compounds, 17beta-estradiol (E2) and p-nonylphenol (NP), between synthetic membrane vesicles (K'lipw values) and water were determined using equilibrium dialysis to evaluate the potential biological uptake of these compounds with and without the presence of dissolved natural organic matter (DOM) surrogates, Suwannee River fulvic acid, dialyzed Aldrich humic acid, and polyphenolic tannic acid. Overall, K'lipw values for E2 and NP reduced by 20-30% with the increase of DOM concentration from 0 to approximately 4 mg of C/L, a typical DOM concentration in the aquatic environment. This trend for E2 and NP is similar to that obtained by other researchers for moderately hydrophobic compounds including polycyclic aromatic hydrocarbons with three or four rings.

Partitioning of selected estrogenic compounds between synthetic membrane vesicles and water: effects of lipid components.

Partition coefficients of the steroid estrogens 17beta-estradiol, estriol, estrone, and 17alpha-ethynylestradiol and the industrial estrogenic compounds p-nonylphenol, p-(tert)octylphenol, bisphenol A, butylbenzylphthalate, and dibutylphthalate between liposome membrane vesicles and water (K(lipw) values) were determined using equilibrium dialysis. A moderate linear correlation with R2 values of as low as 0.679 were found for the relationship between log K(lipw) and log K(ow) for these compounds.

Effects of physical-chemical characteristics on the sorption of selected endocrine disruptors by dissolved organic matter surrogates.

Sorption coefficients (K(oc) values) of selected endocrine disruptors for a wide variety of dissolved organic matter (DOM) were measured using fluorescence quenching and solubility enhancement. 17beta-Estradiol, estriol, 17alpha-ethynylestradiol, p-nonylphenol, p-tert-octylphenol, and dibutylphthalate were selected as endocrine disruptors. Aldrich humic acid, Suwannee River humic and fulvic acids, Nordic fulvic acid, alginic acid, dextran, and tannic acid were selected as DOM surrogates.

Method for predicting photocatalytic oxidation rates of organic compounds.

In designing a photocatalytic oxidation (PCO) system for a given air pollution source, destruction rates for volatile organic compounds (VOCs) are required. The objective of this research was to develop a systematic method of predicting PCO rate constants by correlating rate constants with physical-chemical characteristics of compounds. Accordingly, reaction rate constants were determined for destruction of volatile organics over a titanium dioxide (TiO2) catalyst in a continuous mixed-batch reactor.

Effect of water content on transient nonequilibrium NAPL-gas mass transfer during soil vapor extraction.

The effect of water content on the volatilization of nonaqueous phase liquid (NAPL) in unsaturated soils was characterized by one-dimensional venting experiments conducted to evaluate the lumped mass transfer coefficient. An empirical correlation based upon the modified Sherwood number, Peclet number, and normalized mean grain size was used to estimate initial lumped mass transfer coefficients over a range of water content. The effects of water content on the soil vapor extraction SVE process have been investigated through experimentation and mathematical modeling.