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Leonard W Lion

Publications and source records attributed to Leonard W Lion.

10 recordsLinked to original sources

Engineered polymeric nanoparticles for bioremediation of hydrophobic contaminants.

Sorption of hydrophobic organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs), to soil has been shown to limit their solubilization rate and mobility. In addition, sequestration of contaminants by sorption to soil and by partitioning in nonaqueous phase liquids (NAPLs) reduces their bioavailability. Polymeric nano-network particles have been demonstrated to increase the "effective" solubility of a representative hydrophobic organic contaminant, phenanthrene (PHEN) and to enhance the release of PHEN from contaminated aquifer material. In this study, we investigate the usefulness of nanoparticles made from a poly(ethylene) glycol modified urethane acrylate (PMUA) precursor chain, in enhancing the bioavailability of PHEN. PMUA nanoparticles are shown to increase the mineralization rate of PHEN crystal in water, PHEN sorbed on aquifer material, and PHEN dissolved in a model NAPL (hexadecane) in the presence of aquifer media. These results show that PMUA particles not only enhance the release of sorbed and NAPL-sequestered PHEN but also increase its mineralization rate. The accessibility of contaminants in PMUA particles to bacteria also suggests that particle application may be an effective means to enhance the in-situ biodegradation rate in remediation through natural attenuation of contaminants. In pump-and-treat or soil washing remediation schemes, bioreactors could be used to recycle extracted nanoparticles. The properties of PMUA nanoparticles are shown to be stable in the presence of a heterogeneous active bacterial population, enabling them to be reused after PHEN bound to the particles has been degraded by bacteria.

Adsorption↗

Determination of spatial distributions of zinc and active biomass in microbial biofilms by two-photon laser scanning microscopy.

The spatial distributions of zinc, a representative transition metal, and active biomass in bacterial biofilms were determined using two-photon laser scanning microscopy (2P-LSM). Application of 2P-LSM permits analysis of thicker biofilms than are amenable to observation with confocal laser scanning microscopy and also provides selective excitation of a smaller focal volume with greater depth localization. Thin Escherichia coli PHL628 biofilms were grown in a minimal mineral salts medium using pyruvate as the carbon and energy source under batch conditions, and thick biofilms were grown in Luria-Bertani medium using a continuous-flow drip system. The biofilms were visualized by 2P-LSM and shown to have heterogeneous structures with dispersed dense cell clusters, rough surfaces, and void spaces. Contrary to homogeneous biofilm model predictions that active biomass would be located predominantly in the outer regions of the biofilm and inactive or dead biomass (biomass debris) in the inner regions, significant active biomass fractions were observed at all depths in biofilms (up to 350 microm) using live/dead fluorescent stains. The active fractions were dependent on biofilm thickness and are attributed to the heterogeneous characteristics of biofilm structures. A zinc-binding fluorochrome (8-hydroxy-5-dimethylsulfoamidoquinoline) was synthesized and used to visualize the spatial location of added Zn within biofilms. Zn was distributed evenly in a thin (12 microm) biofilm but was located only at the surface of thick biofilms, penetrating less than 20 microm after 1 h of exposure. The relatively slow movement of Zn into deeper biofilm layers provides direct evidence in support of the concept that thick biofilms may confer resistance to toxic metal species by binding metals at the biofilm-bulk liquid interface, thereby retarding metal diffusion into the biofilm (G. M. Teitzel and M. R. Park, Appl. Environ. Microbiol. 69:2313-2320, 2003).

Biofilms↗

Behavior of lead in a model microbial predator-prey system.

Predation at the microbial level can affect the fate of toxic trace metals. Metals associated with bacterial prey can be released into the dissolved phase following digestion by a predator, and/or metals can remain in the predator and be transferred potentially to the next level of the food chain. Toxic metal ions in the aqueous phase also are expected to modify the growth and predation rate of a microbial predator. A model predator-prey system was developed to test the effects of Pb on cells and to help elucidate the fate of Pb in this type of interaction. Established methods that have been shown to be suitable for distinguishing dissolved, prey-bound, predator-bound, and ingested Pb were used to establish the pathway of Pb over time. Growth parameters were measured using batch reactors for the protozoan predator Tetrahymena thermophila and the bacterial prey Pseudomonas putida without Pb and at several concentrations of Pb. The effect of prey density on predation and Pb phase distribution also was investigated. Results demonstrate that some kinetic parameters related to prey consumption and growth of T. thermophila are altered by Pb. Upon addition of predator to prey cells in equilibrium with dissolved Pb, dissolved and prey-bound Pb become associated with the predator through ingestion and adsorption. Ingested Pb is excreted later as a bound metal associated with T. thermophila waste matter. A preliminary mathematical model was developed to describe predator-prey dynamics and their influence on the behavior and fate of Pb. Growth data were used to obtain model parameters, and model simulations for Pb fractionation are compared to experimental observations.

Animals↗

Engineered polymeric nanoparticles for soil remediation.

Hydrophobic organic groundwater contaminants, such as polynuclear aromatic hydrocarbons (PAHs), sorb strongly to soils and are difficult to remove. We report here on the synthesis of amphiphilic polyurethane (APU) nanoparticles for use in remediation of soil contaminated with PAHs. The particles are made of polyurethane acrylate anionomer (UAA) or poly(ethylene glycol)-modified urethane acrylate (PMUA) precursor chains that can be emulsified and cross-linked in water. The resulting particles are of colloidal size (17-97 nm as measured by dynamic light scattering). APU particles have the ability to enhance PAH desorption and transport in a manner comparable to that of surfactant micelles, but unlike the surface-active components of micelles, the individual cross-linked precursor chains in APU particles are not free to sorb to the soil surface. Thus, the APU particles are stable independent of their concentration in the aqueous phase. In this paper we show that APU particles can be engineered to achieve desired properties. Our experimental results show that the APU particles can be designed to have hydrophobic interior regions that confer a high affinity for phenanthrene (PHEN) and hydrophilic surfaces that promote particle mobility in soil. The affinity of APU particles for contaminants such as PHEN can be controlled by changing the size of the hydrophobic segment used in the chain synthesis. The mobility of colloidal APU suspensions in soil is controlled by the charge density or the size of the pendent water-soluble chains that reside on the particle surface. Exemplary results are provided illustrating the influence of alternative APU particle formulations with respect to their efficacy for contaminant removal. The ability to control particle properties offers the potential to produce different nanoparticles optimized for varying contaminant types and soil conditions.

Engineering↗

Mobilization of adsorbed copper and lead from naturally aged soil by bacterial extracellular polymers.

Sorption of pollutants is a dominant phase transfer process affecting the fate and transport of metals through the subsurface. The movement of contaminants is retarded by sorption to the stationary subsurface porous media and can seriously hinder remediation efforts. Research has shown that the binding of adsorbed metals becomes more pronounced the longer the contaminant is in the subsurface and the release rates of aged metal contaminants have not received the research attention given to freshly added metals in laboratory studies. Metal release rates are also influenced by the presence of dissolved ligands that compete with mineral soil surfaces by providing binding sites. Dissolved organic matter such as bacterial extracellular polymers are common in natural soil solutions and the metal binding properties of bacterial polymers are well established. Therefore, binding of metals to dissolved biopolymers may result in mobilization of an adsorbed metal. This is important for cases where the metals are assumed to be relatively immobile such as in the case of land applied biosolids. In addition, naturally occurring adherent bacteria commonly produce extracellular polymers and thus may modify the bioavailability of meal contaminants at the point of their attachment. In this study samples from three sites, one a land applied sludge test site, were used to investigate the ability of bacterial extracellular polymers to release metals from soils with long-term exposures. The presence of ?200mg/L bacterial extracellular polymer was found to increase the short-term (less than 350h) release of Cu and Pb by a factor of 2-4-fold.

Adsorption↗

Predicting the rate and extent of cadmium and copper desorption from soils in the presence of bacterial extracellular polymer.

The movement of cationic transition metals through the subsurface is strongly retarded by sorption to the porous media. However, dissolved organic ligands can compete with soil surfaces by providing binding sites for metals in solution. An extracellular polymer produced by a bacterium isolated from soil was used in this study to observe and model the influence of a naturally occurring ligand on the release of adsorbed metals from two test soils. Experimental results show that the presence of dissolved extracellular polymer enhanced the rate and extent of desorptive release of soil-bound cadmium and copper. A kinetic model that uses a gamma distribution of rate constants to account for the physical and chemical heterogeneity of the soil matrix was employed to describe the release of cadmium and copper in batch experiments. Model parameters describing soil, metal and extracellular polymer interactions were obtained through separate experiments. With these parameters the model successfully predicted the influence of dissolved polymer on the rate and extent of release of cadmium and copper from soil in independent batch experiments. These results suggest that the presence of natural metal-binding ligands such as bacterial extracellular polymers can act to increase the driving force for desorption by lowering the aqueous concentration of free unbound metals in solution.

Adsorption↗

Development of a model microbial predator-prey system suitable for studies of the behavior of toxic trace metals.

Interactions between microbial predators and their prey can significantly influence the behavior of toxic trace metals. Ingested bacterial prey-bound metals can either accumulate within a predator or be excreted and potentially reintroduced into the dissolved phase. A defined predator-prey system suitable for developing a more fundamental understanding of metal behavior in simple microbial food chains was designed and tested by using lead (Pb) as a representative cationic transition metal. Desired features of this system were the ability to define the chemical speciation of dissolved metals as well as to distinguish between prey- and predator-bound metals. Pseudomonas putida and the ciliate protozoan Tetrahymena thermophila were selected as representative bacterial prey and predator species, respectively. In addition, the use of fluorescent microspheres was evaluated as an experimental surrogate for bacterial prey. Filtration techniques for size-selective separation were developed so that the distribution of Pb between cells of T. thermophila, cells of P. putida or microspheres, and the dissolved phase could be assessed. Filtration units were selected based on their ability to perform separations with minimal metal loss at circumneutral pH. Five-micron polycarbonate filter membranes successfully separated T. thermophila from P. putida with good cell retention and low metal loss. Centrifuge filters successfully separated dissolved and particle-bound metal (<5,000 nominal molecular wt limit). Exemplary experimental results are presented and show that predation on Pb-exposed cells of P. putida or microspheres increases uptake of Pb by T. thermophila.

Animals↗

Pb scavenging from a freshwater lake by Mn oxides in heterogeneous surface coating materials.

Selective extraction techniques were used to assay the importance of specific solid phases in Pb binding by heterogeneous surface coating materials (biofilms) in Cayuga Lake, NY. Hydroxylamine hydrochloride (NH(2)OH.HC1) was used to extract easily reducible Mn oxides, and sodium dithionite (Na(2)S(2)O(4)) was used to extract Mn and Fe oxides in two sets of biofilm samples retrieved from the lake. Pb remaining after extraction was removed by extraction with 10% HNO(3), determined by analysis of Pb(208) using a sector field mass spectrometer with an inductively coupled plasma ion source (ICP-MS), and compared to the total extractable Pb. The results indicate that the greatest contribution to total Pb binding to the heterogeneous surface coating materials was from Mn oxides. Pb adsorption capacity of Mn oxides exceeded that of Fe oxides on a molar basis by approximately an order of magnitude. The high reactivity observed for natural Mn oxides indicates that they are biogenic in origin, consistent with expectations based on the relative biotic and abiotic rates of Mn(II) oxidation under circumneutral conditions. Collectively, these results confirm expectations based on prior observations of adsorption of added Pb by Cayuga Lake biofilms before and after selective extraction, and also confirm predictions for Pb phase association in the lake based on the behavior of laboratory surrogates for adsorptive surfaces.

Adsorption↗

Reduced Cd accumulation in Zea mays: a protective role for phytosiderophores?

Cadmium is a nonessential trace metal and a frequent soil contaminant. Because plants vary in their accumulation of Cd, an understanding of the specific processes that control uptake could reveal methods for reducing Cd levels in edible plant tissues and conversely increasing Cd accumulation in plants used for phytoremediation. Phytosiderophores are iron chelators excreted by graminaceous plants under conditions of iron limitation, but they also complex other metals including cadmium. Here we examine the influence of Cd exposure on phytosiderophore production by hydroponically grown maize. Cd increased the rate of the phytosiderophore 2'-deoxymugineic acid (DMA) release under both Fe-sufficient and Fe-limiting conditions (+/-Fe). In addition, the -Fe plants released more DMA while taking up less Cd than the +Fe plants. In other short-term Cd uptake experiments, plants exposed to Cd in the presence of root exudates in which the DMA-Cd complex was likely the dominant Cd species displayed reduced Cd accumulation in root tissue, and plants similarly exposed to strongly chelated Cd in the presence of EDTA (employed as a positive control) contained the least Cd. Collectively, these results indicate that Cd stress causes Fe deficiency symptoms that result in greater DMA production by maize roots, and then the DMA appears to reduce Cd accumulation.

Azetidinecarboxylic Acid↗

Effect of oxide formation mechanisms on lead adsorption by biogenic manganese (hydr)oxides, iron (hydr)oxides, and their mixtures.

The effects of iron and manganese (hydr)oxide formation processes on the trace metal adsorption properties of these metal (hydr)oxides and their mixtures was investigated by measuring lead adsorption by iron and manganese (hydr)oxides prepared by a variety of methods. Amorphous iron (hydr)oxide formed by fast precipitation at pH 7.5 exhibited greater Pb adsorption (gamma(max) = 50 mmol of Pb/mol of Fe at pH 6.0) than iron (hydr)oxide formed by slow, diffusion-controlled oxidation of Fe(II) at pH 4.5-7.0 or goethite. Biogenic manganese(III/IV) (hydr)oxide prepared by enzymatic oxidation of Mn(II) by the bacterium Leptothrix discophora SS-1 adsorbed five times more Pb (per mole of Mn) than an abiotic manganese (hydr)oxide prepared by oxidation of Mn(II) with permanganate, and 500-5000 times more Pb than pyrolusite oxides (betaMnO2). X-ray crystallography indicated that biogenic manganese (hydr)oxide and iron (hydr)oxide were predominantly amorphous or poorly crystalline and their X-ray diffraction patterns were not significantly affected by the presence of the other (hydr)oxide during formation. When iron and manganese (hydr)oxides were mixed after formation, or for Mn biologically oxidized with iron(III) (hydr)oxide present, observed Pb adsorption was similar to that expected for the mixture based on Langmuir parameters for the individual (hydr)oxides. These results indicate that interactions in iron/manganese (hydr)oxide mixtures related to the formation process and sequence of formation such as site masking, alterations in specific surface area, or changes in crystalline structure either did not occur or had a negligible effect on Pb adsorption by the mixtures.

Adsorption↗