Many current treatments for the reclamation of contaminated water sources are chemical-intensive, energy-intensive, and/or require posttreatment due to unwanted by-product formation. We demonstrate that through the integration of nanostructured materials, enzymatic catalysis, and iron-catalyzed free radical reactions within pore-functionalized synthetic membrane platforms, we are able to conduct environmentally important oxidative reactions for toxic organic degradation and detoxification from water without the addition of expensive or harmful chemicals. In contrast to conventional, passive membrane technologies, our approach utilizes two independently controlled, nanostructured membranes in a stacked configuration for the generation of the necessary oxidants. These include biocatalytic and organic/inorganic (polymer/ iron) nanocomposite membranes. The bioactive (top) membrane contains an electrostatically immobilized enzyme for the catalytic production of one of the main reactants, hydrogen peroxide (H 2 O 2 ), from glucose. The bottom membrane contains either immobilized iron ions or ferrihydrite/iron oxide nanoparticles for the decomposition of hydrogen peroxide to form powerful free radical oxidants. By permeating (at low pressure) a solution containing a model organic contaminant, such as trichlorophenol, with glucose in oxygen-saturated water through the membrane stack, significant contaminant degradation was realized. To illustrate the effectiveness of this membrane platform in real-world applications, membrane-immobilized ferrihydrite/iron oxide nanoparticles were reacted with hydrogen peroxide to form free radicals for the degradation of a chlorinated organic contaminant in actual groundwater. Although we establish the development of these nanostructured materials for environmental applications, the practical and methodological advances demonstrated here permit the extension of their use to applications including disinfection and/or virus inactivation.enzyme catalysis | functionalized membranes | pollutant | microfiltration | responsive materials

The primary objective of this research was to model and understand the chelate-modified Fenton reaction for the destruction of trichloroethylene (TCE) present in both the aqueous and organic (in the form of droplets) phases. The addition of a nontoxic chelate (L), such as citrate or gluconic acid, allows for operation at near-neutral pH and controlled release of Fe(II)/Fe(III). For the standard Fenton reaction at low pH in two-phase systems, an optimum H2O2:Fe(II) molar ratio was found to be between 1:1 and 2:1. Experimentation proved the chelate-modified Fenton reaction effectively dechlorinated TCE in both the aqueous and organic phases at pH 6–7 using low H2O2:Fe(II) molar ratios (4:1 to 8:1). Increasing the L:Fe ratio was found to decrease the rate of H2O2 degradation in both Fe(II) and Fe(III) systems at near-neutral pH. Generalized models were developed to predict the concentration of TCE in the aqueous phase and TCE droplet radius as a function of time using literature-reported hydroxyl radical reaction kinetics and mass transfer relationships. Additional aspects of this work include the reusability of the Fe–citrate complex under repeated H2O2 injections in real water systems as well as packed column studies for simulated groundwater injection.

Medical examiners frequently rely on the finding of free morphine present in postmortem specimens to assist in certifying deaths associated with narcotics. In vitro hydrolysis of morphine-3-D glucuronide (M3DG) to free morphine was studied using variable specimen pH, initial degree of specimen putrefaction, storage temperature and time, and the effectiveness of sodium fluoride (NaF) preservation. Reagent M3DG was added to opiate-free fresh blood and urine and to autopsy-derived blood specimens. Reagent bovine glucuronidase was also added to certain specimens. Freshly collected and refrigerated NaF-preserved blood produced minimal free morphine, whereas four of five autopsy blood specimens produced free morphine from M3DG. Increased storage time, temperature, and initial degree of putrefaction resulted in greater free morphine generation despite the absence of viable bacteria. Hydrolysis occurring during specimen storage can generate free morphine from M3DG and may result in erroneous conclusions in certifying narcotic deaths.

Membrane-based separation processes have been used extensively for drinking water purification, wastewater treatment, and numerous other applications. More recent developments in membrane functionalization have made the use of membrane science important in diverse fields, from tunable separations to catalysis. The focus of this work is to create a common membrane platform for the incorporation of technologies capable of degrading target pollutants. Functionalized membranes capable of metal capture were created using water-based and solvent-based acrylic acid polymerization to synthesize poly (acrylic acid) (PAA) within poly(vinylidene fluoride) (PVDF) membrane pores. The COO − groups of PAA were used to capture Fe(II), which was then either reduced and doped with Pd to form Fe/Pd nanoparticles or used as-is for free radical generation with hydrogen peroxide. Fe/Pd nanoparticles were synthesized within the pores of a PAA/PVDF membrane functionalized via aqueous (green) chemistry and used to dechlorinate trichloroethylene (TCE) and 2,2′-dichlorobiphenyl (DiCB). A PAA/PVDF membrane containing immobilized Fe(III) was used to obtain controlled free radical generation and target organic (pentachlorophenol) degradation within the membrane pore under convective flow conditions.