Positive and negative impacts of flue gas desulfurization (FGD) gypsum on water quality.

Flue gas desulfurization (FGD) gypsum, a by-product of carbon-based energy sources, has typically been incorporated as a component of concrete mixes and wallboard and beneficially used as an agricultural amendment to enhance terrestrial crop production and improve the quality of runoff. These various uses for the by-product aid in reducing the amount that is ultimately landfilled. Limited studies have investigated its benefits when used directly in aquatic settings, such as ponds and lakes, to increase hardness and potentially mitigate eutrophication. A 36-day field mesocosm experiment tested a larger range of FGD gypsum concentrations (500-2000 mg/L) than those previously tested in the literature to investigate its desired and potentially undesired impacts on water quality, including the algal community. High FGD gypsum concentrations, 1000 and 2000 mg/L, were found to have more undesired impacts than the 500 mg/L treatment, including an initial spike in cyanobacteria, a decrease in total zooplankton abundance, and an increase in certain trace metals in the highest treatment. Ultimately, the 500 mg/L FGD gypsum treatment was found to have fewer undesired impacts while still resulting in significant desired effects, including those on hardness and pH, as well as moderate reductions in algal abundance. This experiment provides a better understanding of the effects of FGD gypsum when directly used in an aquatic setting, determines an optimal dose for future field experiments, and helps provide the groundwork for developing an upper threshold on FGD gypsum so as to not have the negative effects outweigh the positive.

Efficient Transport Networks in a Dual Electron/Lithium-Conducting Polymeric Composite for Electrochemical Applications.

In this work, an all-functional polymer material composed of the electrically conductive poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonic acid) (PEDOT:PSS) and lithium-conducting poly(ethylene oxide) (PEO) was developed to form a dual conductor for three-dimensional electrodes in electrochemical applications. The composite exhibits enhanced ionic conductivity (∼10-4 S cm-1) and, counterintuitively, electronic conductivity (∼45 S cm-1) with increasing PEO proportion, optimal at a monomer ratio of 20:1 PEO:PEDOT. Microscopy reveals a unique morphology, where PSS interacts favorably with PEO, destabilizing PEDOT to associate into highly branched, interconnected networks that allow for more efficient electronic transport despite relatively low concentrations. Thermal and X-ray techniques affirm that the PSS-PEO domain suppresses crystallinity, explaining the high ionic conductivity. Electrochemical experiments in lithium cell environments indicate stability as a function of cycling and improved overpotential due to dual transport characteristics despite known issues with both individual components.

Catalytic, Conductive Bipolar Membrane Interfaces through Layer-by-Layer Deposition for the Design of Membrane-Integrated Artificial Photosynthesis Systems.

In the presence of an electric field, bipolar membranes (BPMs) are capable of initiating water disassociation (WD) within the interfacial region, which can make water splitting for renewable energy in the presence of a pH gradient possible. In addition to WD catalytic efficiency, there is also the need for electronic conductivity in this region for membrane-integrated artificial photosynthesis (AP) systems. Graphene oxide (GO) was shown to catalyze WD and to be controllably reduced, which resulted in electronic conductivity. Layer-by-layer (LbL) film deposition was employed to improve GO film uniformity in the interfacial region to enhance WD catalysis and, through the addition of a conducting polymer in the process, add electronic conductivity in a hybrid film. Three different deposition methods were tested to optimize conducting polymer synthesis with the oxidant in a metastable solution and to yield the best film properties. It was found that an approach that included substrate dipping in a solution containing the expected final monomer/oxidant ratio provided the most predictable film growth and smoothest films (by UV/Vis spectroscopy and atomic force microscopy/scanning electron microscopy, respectively), whereas dipping in excess oxidant or co-spraying the oxidant and monomer produced heterogeneous films. Optimized films were found to be electronically conductive and produced a membrane ohmic drop that was acceptable for AP applications. Films were integrated into the interfacial region of BPMs and revealed superior WD efficiency (≥1.4 V at 10 mA cm-2 ) for thinner films (<10 bilayers≈100 nm) than for either the pure GO catalyst or conducting polymer individually, which indicated that there was a synergistic effect between these materials in the structure configured by the LbL method.

Reduced Graphene Oxide Bipolar Membranes for Integrated Solar Water Splitting in Optimal pH.

The integration of light absorbers and catalysts for the water splitting process requires a membrane capable of both ion and electron management and product separation to realize efficient solar fuels systems. Bipolar membranes can maintain a pH gradient for optimal reaction conditions by the dissociation of water. Such membranes that contain graphene in the interfacial layer are fabricated by the chemical reduction of a uniformly deposited graphene oxide layer to convert sp(3) catalyst regions to sp(2) conductive regions. The resulting electrical and water dissociation properties are optimized by adjusting the exposure conditions, and treatments of less than 5 min render an interface that exceeds the conductivity requirements for integrated solar water splitting and increases the overpotential by <0.3 V. Integration with photoelectrodes is examined by characterizing the electrical interface formed between graphene and Si microwires, and we found that efficient Ohmic junctions are possible.

Use of bipolar membranes for maintaining steady-state pH gradients in membrane-supported, solar-driven water splitting.

A bipolar membrane can maintain a steady-state pH difference between the sites of oxidation and reduction in membrane-supported, solar-driven water-splitting systems without changing the overall thermodynamics required to split water. A commercially available bipolar membrane that can serve this purpose has been identified, its performance has been evaluated quantitatively, and is demonstrated to meet the requirements for this application. For effective utilization in integrated solar-driven water-splitting systems, such bipolar membranes must, however, be modified to simultaneously optimize their physical properties such as optical transparency, electronic conductivity and kinetics of water dissociation.

Graphene oxide as a water dissociation catalyst in the bipolar membrane interfacial layer.

Bipolar membranes are formed by the lamination of an anion- and cation-exchange layer. Upon a sufficient applied reverse bias, water molecules at the layer junction dissociate, generating OH(-) and H(+), which can be useful in electrodialysis and electrosynthesis applications. Graphene oxide has been introduced into bipolar membrane junctions (illustrated in the adjacent graphic) and is shown to be an efficient new water dissociation catalyst, lowering the overpotential by 75% compared to a control membrane. It was found that adjusting deposition conditions changes the nature of the graphene oxide films, leading to tunable membrane performance. Additionally, it is shown that their low overpotentials are stable, making for industrially viable, high-performance bipolar membranes.

Novel conducting polymer-heteropoly acid hybrid material for artificial photosynthetic membranes.

Artificial photosynthetic (AP) approaches to convert and store solar energy will require membranes capable of conducting both ions and electrons while remaining relatively transparent and chemically stable. A new approach is applied herein involving previously described in situ chemical polymerization of electronically conducting poly(3,4-ethylenedioxythiophene) (PEDOT) in the presence of proton conducting heteropoly acid (HPA) phosphomolybdic acid (PMA). The electrochemical behaviour of the PEDOT/PMA hybrid material was investigated and it was found that the conducting polymer (CP) is susceptible to irreversible oxidative processes at potentials where water is oxidized. This will be problematic in AP devices should the process occur in very close proximity to a conducting polymer-based membrane. It was found that PEDOT grants the system good electrical performance in terms of conductivity and stability over a large pH window; however, the presence of PMA was not found to provide sufficient proton conductivity. This was addressed in an additional study by tuning the ionic (and in turn, electronic) conductivity in creating composites with the proton-permselective polymer Nafion. It was found that a material of this nature with near-equal conductivity for optimal chemical conversion efficiency will consist of roughly three parts Nafion and one part PEDOT/PMA.

Predicting blood usage in cardiac surgery--the transfusion predictor product.

Blood cross-matched for patients undergoing cardiac surgery is used infrequently and represents a significant cost. We investigated the ability to predict the need for intraoperative transfusion. We hypothesized that red blood cell volume is a predictor because dilution is the primary cause for transfusion requirement intraoperatively. A total of 401 consecutive patients having cardiothoracic surgery requiring the use of cardiopulmonary bypass were retrospectively analyzed by revision of their perfusion record. This sample included 82% elective, 17% urgent, and 1% emergency procedures. The product of body surface area and preoperative hemoglobin gave us gHb/l/m2, which are the units of the Transfusion Predictor Product (TPPU). Mean patient age was 66.9 +/- 10.7 years, and 112 (28%) were women. Mean TPP was 257.2 +/- 45.5u. 52 patients (13%) received red blood cells intraoperatively. At less than TPP 211.7u, one standard deviation below the mean value, 32 patients of 69 (46%) received blood transfusion intraoperatively (p < 0.001). At a TPP greater than 211.7u, 20 patients of 322 (6%) had blood transfusion intraoperatively. Patients with a TPP > 211.7u do not require routine cross-matching of blood. Cross-matching for these patients should be individualized on the basis of predicted duration of CPB and/or other types of patient comorbidity.