Source strength functions from long-term monitoring data and spatially distributed mass discharge measurements.

Source strength functions (SSF), defined as contaminant mass discharge or flux-averaged concentration from dense nonaqueous phase liquid (DNAPL) source zones as a function of time, provide a quantitative model of DNAPL source-zone behavior. Such information is useful for calibration of screening-level models to assist with site management decisions. We investigate the use of historic data collected during long-term monitoring (LTM) activities at a site in Rhode Island to predict the SSF based on temporal mass discharge measurements at a fixed location, as well as SSF estimation using mass discharge measurements at a fixed time from three spatially distributed control planes.

Screening-level estimates of mass discharge uncertainty from point measurement methods.

The uncertainty of mass discharge measurements associated with point-scale measurement techniques was investigated by deriving analytical solutions for the mass discharge coefficient of variation for two simplified, conceptual models. In the first case, a depth-averaged domain was assumed, consisting of one-dimensional groundwater flow perpendicular to a one-dimensional control plane of uniformly spaced sampling points. The contaminant flux along the control plane was assumed to be normally distributed.

Cell wall stress activates expression of a novel stress response facilitator (SrfA) under σ22 (AlgT/U) control in Pseudomonas aeruginosa.

The ECF (extracytoplasmic function) alternative sigma factor, σ(22) (AlgT/U), is required for expression of the algD promoter of the operon for alginate biosynthesis in Pseudomonas aeruginosa. Alginate production promotes chronic pulmonary infections by this opportunistic pathogen in patients with cystic fibrosis and chronic obstructive pulmonary disease. σ(22) is normally sequestered, but its deregulation and activation occur either by mutation in mucA (encoding an anti-sigma factor) or in response to envelope stress, such as inhibition of peptidoglycan synthesis.

High antimicrobial effectiveness with low hemolytic and cytotoxic activity for PEG/quaternary copolyoxetanes.

The alkyl chain length of quaternary ammonium/PEG copolyoxetanes has been varied to discern effects on solution antimicrobial efficacy, hemolytic activity and cytotoxicity. Monomers 3-((4-bromobutoxy)methyl)-3-methyloxetane (BBOx) and 3-((2-(2-methoxyethoxy)ethoxy)methyl)-3-methyloxetane (ME2Ox) were used to prepare precursor P[(BBOx)(ME2Ox)-50:50-4 kDa] copolyoxetane via cationic ring opening polymerization. The 1:1 copolymer composition and Mn (4 kDa) were confirmed by (1)H NMR spectroscopy.

The uncertainty of mass discharge measurements using pumping methods under simplified conditions.

Mass discharge measurements at contaminated sites have been used to assist with site management decisions, and can be divided into two broad categories: point-scale measurement techniques and pumping methods. Pumping methods can be sub-divided based on the pumping procedures used into sequential, concurrent, and tandem circulating well categories. Recent work has investigated the uncertainty of point measurement methods, and to a lesser extent, pumping methods.

Identification of genes in the σ²² regulon of Pseudomonas aeruginosa required for cell envelope homeostasis in either the planktonic or the sessile mode of growth.

Unlabelled: The Pseudomonas aeruginosa extracytoplasmic functioning (ECF) sigma factor σ(22) is encoded by algT/algU and is inhibited by anti-sigma factor MucA. σ(22) was originally discovered for its essential role in the expression of the exopolysaccharide alginate by mucoid strains associated with chronic pulmonary infection. However, σ(22) is now known to also have a large regulon associated with the response to cell wall stress.

Structural basis for alginate secretion across the bacterial outer membrane.

Pseudomonas aeruginosa is the predominant pathogen associated with chronic lung infection among cystic fibrosis patients. During colonization of the lung, P. aeruginosa converts to a mucoid phenotype characterized by the overproduction of the exopolysaccharide alginate.

Use of electrophoresis for transporting nano-iron in porous media.

Research has been conducted to evaluate if electrophoresis could transport surface stabilized nanoscale zero-valent iron (nZVI) through fine grained sand with the intent of remediating a contaminant in situ. The experimental procedure involved determining the transport rates of polymer modified nZVI and hematite in fine grained sands under an applied electrical gradient under different physical and chemical conditions. Results indicated transport of polymer modified nZVI and hematite can be accomplished by electrophoresis, with rates found to be much higher than diffusion alone and comparable to those predicted by electrokinetic theory.

Remediation of NAPL source zones: lessons learned from field studies at Hill and Dover AFB.

Innovative remediation studies were conducted between 1994 and 2004 at sites contaminated by nonaqueous phase liquids (NAPLs) at Hill and Dover AFB, and included technologies that mobilize, solubilize, and volatilize NAPL: air sparging (AS), surfactant flushing, cosolvent flooding, and flushing with a complexing-sugar solution. The experiments proved that aggressive remedial efforts tailored to the contaminant can remove more than 90% of the NAPL-phase contaminant mass. Site-characterization methods were tested as part of these field efforts, including partitioning tracer tests, biotracer tests, and mass-flux measurements.

Highly effective, water-soluble, hemocompatible 1,3-propylene oxide-based antimicrobials: poly[(3,3-quaternary/PEG)-copolyoxetanes].

This study focuses on the solution antimicrobial effectiveness of a novel class of copolyoxetanes with quaternary ammonium and PEG-like side chains. A precursor P[(BBOx-m)(ME2Ox)] copolyoxetane was prepared by cationic ring-opening copolymerization of 3-((4-bromobutoxy)methyl)-3-methyloxetane (BBOx) and 3-((2-(2-methoxyethoxy)ethoxy)methyl)-3-methyloxetane (ME2Ox) to give random copolymers with 14-100 (m) mol % BBOx. Reaction of P[(BBOx-m)(ME2Ox)] with dodecyl dimethylamine gave the corresponding quaternary P[(C12-m)(ME2Ox)] polycation salts, designated C12-m, as viscous liquids in 100% yield.

Bio-inspired chemical reactors for growing aligned gold nanoparticle-like wires.

Bioinspired masks, created by merging sol-gel chemistry with biotemplating, were used as local chemical reactors to grow aligned arrays of gold nanoparticle-like wires.

Use of cell wall stress to characterize sigma 22 (AlgT/U) activation by regulated proteolysis and its regulon in Pseudomonas aeruginosa.

MucA sequesters extracytoplasmic function (ECF) sigma(22) (algT/U encoded) from target promoters including PalgD for alginate biosynthesis. We have shown that cell wall stress (e.g.

Changes in contaminant mass discharge from DNAPL source mass depletion: evaluation at two field sites.

Changes in contaminant fluxes resulting from aggressive remediation of dense nonaqueous phase liquid (DNAPL) source zone were investigated at two sites, one at Hill Air Force Base (AFB), Utah, and the other at Ft. Lewis Military Reservation, Washington. Passive Flux Meters (PFM) and a variation of the Integral Pumping Test (IPT) were used to measure fluxes in ten wells installed along a transect down-gradient of the trichloroethylene (TCE) source zone, and perpendicular to the mean groundwater flow direction.

Continuous determination of high-vapor-phase concentrations of tetrachloroethylene using on-line mass spectrometry.

A method was developed to determine the vapor concentration of tetrachloroethylene (PCE) at and below its equilibrium vapor-phase concentration, 168 000 microg/L (25 degrees C). Vapor samples were drawn by vacuum into a six-port sampling valve and injected through a jet separator into an ion trap mass spectrometer (MS). This on-line MS can continuously sample a vapor stream and provide vapor concentrations every 30 s.

The NtrC family regulator AlgB, which controls alginate biosynthesis in mucoid Pseudomonas aeruginosa, binds directly to the algD promoter.

Alginate production in mucoid (MucA-defective) Pseudomonas aeruginosa is dependent upon several transcriptional regulators, including AlgB, a two-component response regulator belonging to the NtrC family. This role of AlgB was apparently independent of its sensor kinase, KinB, and even the N-terminal phosphorylation domain of AlgB was dispensable for alginate biosynthetic gene (i.e.

Highly effective contact antimicrobial surfaces via polymer surface modifiers.

Contact antimicrobial coatings with poly(alkylammonium) compositions have been a subject of increasing interest in part because of the contribution of biocide release coatings to antibiotic resistance. Herein, a concept for antimicrobial coatings is developed on the basis of the thermodynamically driven surface concentration of soft block side chains. The concept incorporates structural and compositional guidance from naturally occurring antimicrobial proteins and achieves compositional economy via a polymer-surface modifier (PSM).

Cell wall-inhibitory antibiotics activate the alginate biosynthesis operon in Pseudomonas aeruginosa: Roles of sigma (AlgT) and the AlgW and Prc proteases.

A bioassay was developed to identify stimuli that promote the transcriptional induction of the algD operon for alginate biosynthesis in Pseudomonas aeruginosa. Strain PAO1 carried the algD promoter fused to a chloramphenicol acetyl-transferase cartridge (PalgD-cat), and > 50 compounds were tested for promoting chloramphenicol resistance. Most compounds showing PalgD-cat induction were cell wall-active antibiotics that blocked peptidoglycan synthesis.

Independent regulation of MucD, an HtrA-like protease in Pseudomonas aeruginosa, and the role of its proteolytic motif in alginate gene regulation.

Expression of mucD, encoding a homologue of the HtrA(DegP) family of endoserine proteases, was investigated in Pseudomonas aeruginosa. Expressed from the algT-mucABCD operon, MucD was detected in mucoid (FRD1) and nonmucoid (PAO1) parental strains and also when polar insertions were placed upstream in algT or mucB. A transcriptional start site for a mucD promoter (PmucD) was mapped within mucC.

Field demonstration of surfactant-enhanced solubilization of DNAPL at Dover Air Force Base, Delaware.

This study reports on a surfactant-based flood for tetrachloroethylene (PCE) removal from a control test cell at the Dover National Test Site. The surfactant formulation (sodium dihexyl sulfosuccinate (Aerosol-MA or AMA), isopropanol and calcium chloride) was able to achieve a high concentration of PCE in swollen micelles (supersolubilization) without vertical PCE migration. The hydraulic system included eight screened wells that were operated in both vertical circulation and line drive configurations.

Design of aquifer remediation systems: (1) describing hydraulic structure and NAPL architecture using tracers.

Aquifer heterogeneity (structure) and NAPL distribution (architecture) are described based on tracer data. An inverse modelling approach that estimates the hydraulic structure and NAPL architecture based on a Lagrangian stochastic model where the hydraulic structure is described by one or more populations of lognormally distributed travel times and the NAPL architecture is selected from eight possible assumed distributions. Optimization of the model parameters for each tested realization is based on the minimization of the sum of the square residuals between the log of measured tracer data and model predictions for the same temporal observation.

Design of aquifer remediation systems: (2) estimating site-specific performance and benefits of partial source removal.

A Lagrangian stochastic model is proposed as a tool that can be utilized in forecasting remedial performance and estimating the benefits (in terms of flux and mass reduction) derived from a source zone remedial effort. The stochastic functional relationships that describe the hydraulic "structure" and non-aqueous phase liquid (NAPL) "architecture" have been described in a companion paper (Enfield, C.G.

Polyurethane biocidal polymeric surface modifiers.

Polyurethanes (PUs) with soft blocks containing semifluorinated (-CH2OCH2CF3) and 5,5-dimethylhydantoin pendant groups were prepared and employed (2 wt%) as biocidal polymeric surface modifiers (PSMs) for a conventional PU coating comprised of an isophorone diisocyanate/1,4-butanediol-derived hard block (50%) and poly(tetramethylene oxide) soft block. Surface enrichment of the PSM was verified by dynamic contact angle measurements. The PSM modified PU was activated by converting near-surface amide groups to chloramide with 3wt% hypochlorite.

E-ring modified steroids as novel potent inhibitors of 17beta-hydroxysteroid dehydrogenase type 1.

17beta-Hydroxysteroid dehydrogenases (17beta-HSDs) are an important class of steroidogenic enzymes that regulate the bioavailability of active estrogens and androgens and are as yet a relatively unexploited therapeutic target. Based on our investigations and those of others, E-ring modified steroids were identified as a useful template for the design of inhibitors of 17beta-HSD type 1, an enzyme involved in the conversion of estrone into estradiol. The synthesis and biological evaluation of a new series of N- and C-substituted 1,3,5(10)-estratrien-[17,16-c]-pyrazoles and the corresponding SAR are discussed.

Controlled release, blind test of DNAPL remediation by ethanol flushing.

A dense nonaqueous phase liquid (DNAPL) source zone was established within a sheet-pile isolated cell through a controlled release of perchloroethylene (PCE) to evaluate DNAPL remediation by in-situ cosolvent flushing. Ethanol was used as the cosolvent, and the main remedial mechanism was enhanced dissolution based on the phase behavior of the water-ethanol-PCE system. Based on the knowledge of the actual PCE volume introduced into the cell, it was estimated that 83 L of PCE were present at the start of the test.