A novel ammonia—carbon dioxide forward (direct) osmosis desalination process

A novel forward (direct) osmosis (FO) desalination process is presented. The process uses an ammonium bicarbonate draw solution to extract water from a saline feed water across a semi-permeable polymeric membrane. Very large osmotic pressures generated by the highly soluble ammonium bicarbonate draw solution yield high water fluxes and can result in very high feed water recoveries. Upon moderate heating, ammonium bicarbonate decomposes into ammonia and carbon dioxide gases that can be separated and recycled as draw solutes, leaving the fresh product water. Experiments with a laboratory-scale FO unit utilizing a flat sheet cellulose tri-acetate membrane demonstrated high product water flux and relatively high salt rejection. The results further revealed that reverse osmosis (RO) membranes are not suitable for the FO process because of relatively low product water fluxes attributed to severe internal concentration polarization in the porous support and fabric layers of the RO membrane.     

The Privilege of Looking at the Molecular Details of Biochemical Reactions

The introducing the Laser-Induced-Proton-Pulse (1979) allowed to monitor, at real time, the response of multi equilibria systems to pulse protonation. The reaction was initiated by the excitation of “photo acid” that releases a proton in the sub-ns time-scale, offsetting all acid base equilibria. This method was used to study the interaction of the protons with water, dyes, membranes, and proteins. The complexity of the systems increased from the most basic properties of dynamics up to mapping the structure of proton collecting antenna on protein surfaces, monitoring the chemical activity of water inside proteins, studying the electro-neutral mechanism of proton ion exchange across bio-membranes and charting the trajectories of ions inside ionic channels. The analysis of these systems led to deeper understanding of the physical chemical properties of micro-environments like active sites and ionic channels, as well as a tool for advanced kinetic analysis of multi-equilibria systems.     

The Translocation of Na+ Ion Inside Human Thrombin Accounts for the Activation of the Enzyme

Thrombin is a member of the chymotrypsin family that splits the peptide bond next to arginine. The catalytic activity of thrombin is accelerated by Na⁺. Inspection of the crystal structure reveals an ion binding site 17 Å from the active-site, leading to ambiguous definition of its mode of rate-enhancement. During unbiased Molecular Dynamics simulations in the presence of Na⁺ ions, the Na⁺ ion was noticed to alternate between two locations: the crystal-structure site (adjacent to R221a and K224) and another site next to D189, very close to the binding and the active sites. There is a free passage between the two locations, and both sites can exchange ions with the bulk. When the ion is close to D189 it can assume position between the guanidino moiety of the product and the carboxylate of D189, thus weakening the protein-product interaction. This transient structure either ejects the Na⁺ ion out of the protein or releases the product from the enzyme. We propose that the enhancement of the catalysis by the ion is a reflection of its ability to destabilize the product-enzyme complex.     

Spatial distributions of Cryptosporidium oocysts in porous media: evidence for dual mode deposition

Spatial distributions of Cryptosporidium parvum oocysts in columns packed with uniform glass-bead collectors were measured over a broad range of physicochemical conditions. Oocyst deposition behavior is shown to deviate from predictions based on classical colloid filtration theory (CFT) in the presence of repulsive (unfavorable) colloidal interactions. Specifically, CFT tends to predict greater removal of oocysts (less transport) than that observed in controlled laboratory experiments. Comparison of oocyst retention with results obtained using polystyrene latex particles of similar size suggests that mechanisms controlling particle deposition are the same in both systems. At a given ionic strength, the deposition of Cryptosporidium oocysts is generally greater than that of the microspheres; however, this discrepancy is partly attributable to large differences in oocyst and microsphere zeta potentials. A dual deposition mode (DDM) model is applied which considers the combined influence of "fast" and "slow" oocyst deposition due to the concurrent existence of favorable and unfavorable oocyst-collector interactions. Model simulations of retained oocyst profiles and suspended oocyst concentration at the column effluent are consistent with experimental data. Because classic CFT does not account for the effect of dual mode deposition (i.e., simultaneous "fast" and "slow" oocyst deposition), these observations have important implications for predictions of oocyst transport in subsurface environments, where repulsive electrostatic interactions predominate. Supporting elution experiments further suggest that specific surface interactions between oocyst wall macromolecules and the glass bead collectors could retard or even completely inhibit oocyst release upon perturbation in solution chemistry.     

New perspectives on nanomaterial aquatic ecotoxicity: production impacts exceed direct exposure impacts for carbon nanotoubes

Environmental impacts due to engineered nanomaterials arise both from releases of the nanomaterials themselves as well as from their synthesis. In this work, we employ the USEtox model to quantify and compare aquatic ecotoxicity impacts over the life cycle of carbon nanotubes (CNTs). USEtox is an integrated multimedia fate, transport, and toxicity model covering large classes of organic and inorganic substances. This work evaluates the impacts of non-CNT emissions from three methods of synthesis (arc ablation, CVD, and HiPco), and compares these to the modeled ecotoxicity of CNTs released to the environment. Parameters for evaluating CNT ecotoxicity are bounded by a highly conservative "worst case" scenario and a "realistic" scenario that draws from existing literature on CNT fate, transport, and ecotoxicity. The results indicate that the ecotoxicity impacts of nanomaterial production processes are roughly equivalent to the ecotoxicity of CNT releases under the unrealistic worst case scenario, while exceeding the results of the realistic scenario by 3 orders of magnitude. Ecotoxicity from production processes is dominated by emissions of metals from electricity generation. Uncertainty exists for both production and release stages, and is modeled using a combination of Monte Carlo simulation and scenario analysis. The results of this analysis underscore the contributions of existing work on CNT fate and transport, as well as the importance of life cycle considerations in allocating time and resources toward research on mitigating the impacts of novel materials.     

Field and laboratory investigations of inactivation of viruses (PRD1 and MS2) attached to iron oxide-coated quartz sand

Field and laboratory experiments were conducted to investigate inactivation of viruses attached to mineral surfaces. In a natural gradient transport field experiment, bacteriophage PRD1, radiolabeled with 32P, was injected into a ferric oxyhydroxide-coated sand aquifer with bromide and linear alkylbenzene sulfonates. In a zone of the aquifer contaminated by secondary sewage infiltration, small fractions of infective and 32P-labeled PRD1 broke through with the bromide tracer,followed bythe slow release of 84% of the 32P activity and only 0.011% of the infective PRD1. In the laboratory experiments, the inactivation of PRD1, labeled with 35S (protein capsid), and MS2, dual radiolabeled with 35S (protein capsid) and 32P (nucleic acid), was monitored in the presence of groundwater and sediment from the contaminated zone of the field site. Release of infective viruses decreased at a much faster rate than release of the radiolabels, indicating that attached viruses were undergoing surface inactivation. Disparities between 32P and 35S release suggest that the inactivated viruses were released in a disintegrated state. Comparison of estimated solution and surface inactivation rates indicates solution inactivation is approximately 3 times as fast as surface inactivation. The actual rate of surface inactivation may be substantially underestimated owing to slow release of inactivated viruses.     

Tuning structure and properties of graded triblock terpolymer-based mesoporous and hybrid films

Despite considerable efforts toward fabricating ordered, water-permeable, mesoporous films from block copolymers, fine control over pore dimensions, structural characteristics, and mechanical behavior of graded structures remains a major challenge. To this end, we describe the fabrication and performance characteristics of graded mesoporous and hybrid films derived from the newly synthesized triblock terpolymer, poly(isoprene-b-styrene-b-4-vinylpyridine). A unique morphology, unachievable in diblock copolymer systems, with enhanced mechanical integrity is evidenced. The film structure comprises a thin selective layer containing vertically aligned and nearly monodisperse mesopores at a density of more than 10(14) per m(2) above a graded macroporous layer. Hybridization via homopolymer blending enables tuning of pore size within the range of 16 to 30 nm. Solvent flow and solute separation experiments demonstrate that the terpolymer films have permeabilities comparable to commercial membranes, are stimuli-responsive, and contain pores with a nearly monodisperse diameter. These results suggest that moving to multiblock polymers and their hybrids may open new paths to produce high-performance graded membranes for filtration, separations, nanofluidics, catalysis, and drug delivery.     

Comparison Study of Microstructure and Phase Evolution in Mg-Nd- and Mg-Gd-Based Alloys

Microstructure and phase evolution in Mg-Nd-, Mg-Gd-, and Mg-Gd-Nd-based alloys with additions of Zn, Zr, and Y were analyzed in the as-cast, solution-treated and aged conditions. Close similarity between the as-cast microstructures and precipitation sequence during aging was revealed. Along with this, distinct features of eutectic compounds and of crystal structure, composition, and orientation relationships of β″, β′, and β ₁ phases were established. Formation of Zn₂Zr₃ rods in Mg-Nd-based alloy and cuboid-shaped particles in Mg-Gd- and Mg-Gd-Nd-based alloys is discussed. The features of the age hardening curves were connected with differences between β″ → β′ transformation and different diffusivities of Gd and Nd in Mg-matrix.