Au/Pd octopods and concave core@shell Au@Pd nanocrystals have been prepared by coupling for the first time a seed-mediated synthetic method with co-reduction. The integration of these two methods is central to the formation of these binary Au/Pd nanocrystals wherein the kinetics of seeded growth are manipulated via the co-reduction technique to control the final morphology of the nanocrystals. Significantly, the synthesis of these structures under similar reaction conditions illustrates that they are structurally related kinetic products. Detailed characterization by STEM-EDX analysis highlights the unique structural features of these nanocrystals and indicates that Pd localizes on the higher-energy features of the nanocrystals. Optical and electrocatalytic characterization also demonstrates their promise as a new class of multifunctional nanostructures.
The Chicago Sanitary and Ship Canal (CSSC) links the Great Lakes to the Mississippi River starting in downtown Chicago. In addition to storm water, the CSSC receives water from Chicago's wastewater treatment plants (WWTP). Such effluents are known to be sources of organic pollutants to water and sediment. Therefore in 2013, we collected 10 sediment samples from the CSSC and measured the concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), brominated flame retardants, and organophosphate esters (OPEs). Geometric mean concentrations of the summed concentrations of 16 PAHs ranged from 11,000 to 420,000 ng/g dw, with the highest concentrations located at each end of the canal. Total PCB concentrations had a geometric mean of 1,400 ± 500 ng/g dw. Brominated flame retardants were separated into two groups: polybrominated diphenyl ethers (PBDEs) and non-PBDEs. Concentrations of PBDEs and those of the non-PBDE flame retardants had a geometric average of 83 ± 19 and 7.0 ± 5.8 ng/g dw, respectively. The summed concentrations of 8 OPEs ranged from 470 to 2,800 ng/g dw, with the highest concentration detected at a site located downstream of the Stickney water reclamation plant. Using ANOVA results, some hypotheses on sources to the CSSC could be formulated: downtown Chicago is probably a source of PAHs, the Cal-Sag Channel may be a source of PCBs, and neither the WWTP nor the Cal-Sag Channel seem to be significant sources of brominated flame retardants or OPEs.
The concentrations of six organophosphate esters (OPEs) in atmospheric particle phase samples collected once every 12 days at five sites in the North American Great Lakes basin over the period of March 2012 to December 2014, inclusive, are reported. These OPEs include tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP), and tris(1,3-dichloroisopropyl) phosphate (TDCIPP), tri-n-butyl phosphate (TNBP), triphenyl phosphate (TPHP), and 2-ethylhexyl diphenyl phosphate (EHDP). Median total OPE concentrations (∑OPE) ranged from 93 pg/m at Sleeping Bear Dunes to 1046 pg/m at Chicago. The ∑OPE levels were significantly (P < 0.05) higher at Chicago and Cleveland, our urban sites, than at our rural and remote sites. The composition profiles were dominated by chlorinated OPEs at the urban and rural sites and by nonchlorinated OPEs at the remote sites. The concentrations of all OPEs were significantly (P < 0.001) correlated to one another, suggesting that these compounds share similar sources. Most atmospheric ∑OPE concentrations were significantly (P < 0.05) decreasing over time, with halving times of about 3.5 years at the urban sites and about 1.5 years at the rural and remote sites. Interestingly, TCEP and EHDP concentrations were increasing over time at the rural and remote sites with doubling times of 2.2 and 3.7 years, respectively.
<p>This review summarizes our own research, published since 2004, dealing with electrochemical reduction of halogenated organic compounds that are environmental pollutants. Included are sections surveying the direct and mediated reduction of the following species: (a) chlorofluorocarbons; (b) pesticides, fungicides, and bactericides; (c) flame retardants; and (d) disinfection by-products arising from the chlorination of water. To provide the reader with a perspective of these topics beyond our own work, a total of 238 literature citations, pertaining to studies conducted in numerous laboratories around the world, appears at the end of this review.</p>
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