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Binary (M1− M2− O) and ternary (M1− M2− M3− O) metal-oxide nanoparticles (NPs) have been prepared by thermal decomposition in benzyl ether of the appropriate M(acac)n(M = Fe, Mn, Pd, Cu, Al, Gd) compounds in the presence of a mixture of oleic acid and oleylamine templating (surface capping) ligands, and 1,2-hexadecanediol as an accelerating agent. The metal percentage and the particle size were investigated as a function of the starting composition. The NP composition is controlled by the relative reaction rates of the particular precursors, such that prediction of NP composition from reagent ratios is not straightforward. However, understanding reaction rate limitations allows for alternative synthesis to be developed. In some cases, ligand exchange reaction and subsequent decomposition are possibly more important than thermal decomposition. [ABSTRACT FROM AUTHOR]

A new method of modifying TiO2 photocatalysts with SiO2 is developed in which SiO2 nanoparticles are simply mixed with TiO2 in water under ambient conditions. This method does not require the use of toxic solvents or significant energy input. Although the SiO2 modification slightly reduces hydroxyl free radical production, the composite SiO2-TiO2 nanomaterials have markedly higher photocatalytic inactivation rates for a common surrogate virus, bacteriophage MS2 (up to 270% compared to the unmodified TiO2), due to the greatly improved adsorptive density and dark inactivation of MS2. The Langmuir isotherm describes the adsorption data well and shows that the TiO2 modified with 5% SiO2 has a maximum adsorption density qmax 37 times that of the unmodified TiO2. The Langmuir-Hinshelwood model fits the photocatalytic inactivation kinetic data well. The SiO2-TiO2 material produces a greater maximum initial inactivation rate yet a lower intrinsic surface reaction rate constant, consistent with the reduced hydroxyl radical production and enhanced adsorption. These results suggest that modifying photocatalyst surface to increase contaminant adsorption is an important strategy to improve photocatalytic reaction efficiency. Simple and cheap synthesis methods such as that used in this study bring photocatalysis closer to being a viable water treatment option. [ABSTRACT FROM AUTHOR]

A detailed analysis is reported of the organic composition of produced water samples from typical shale gas wells in the Marcellus (PA), Eagle Ford (TX), and Barnett (NM) formations. The quality of shale gas produced (and frac flowback) waters is a current environmental concern and disposal problem for producers. Re-use of produced water for hydraulic fracturing is being encouraged; however, knowledge of the organic impurities is important in determining the method of treatment. The metal content was determined by inductively coupled plasma optical emission spectrometry (ICP-OES). Mineral elements are expected depending on the reservoir geology and salts used in hydraulic fracturing; however, significant levels of other transition metals and heavier main group elements are observed. The presence of scaling elements (Ca and Ba) is related to the pH of the water rather than total dissolved solids (TDS). Using gas chromatography mass spectrometry (GC/MS) analysis of the chloroform extracts of the produced water samples, a plethora of organic compounds were identified. In each water sample, the majority of organics are saturated (aliphatic), and only a small fraction comes under aromatic, resin, and asphaltene categories. Unlike coalbed methane produced water it appears that shale oil/gas produced water does not contain significant quantities of polyaromatic hydrocarbons reducing the potential health hazard. Marcellus and Barnett produced waters contain predominantly C6-C16 hydrocarbons, while the Eagle Ford produced water shows the highest concentration in the C17-C30 range. The structures of the saturated hydrocarbons identified generally follows the trend of linear > branched > cyclic. Heterocyclic compounds are identified with the largest fraction being fatty alcohols, esters, and ethers. However, the presence of various fatty acid phthalate esters in the Barnett and Marcellus produced waters can be related to their use in drilling fluids and breaker additives rather than their presence in connate fluids. Halogen containing compounds are found in each of the water samples, and although the fluorocarbon compounds identified are used as tracers, the presence of chlorocarbons and organobromides formed as a consequence of using chlorine containing oxidants (to remove bacteria from source water), suggests that industry should concentrate on non-chemical treatments of frac and produced waters.