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Park Falls, WI, United States

Yin H.,Huazhong Agricultural University | Li H.,Huazhong Agricultural University | Wang Y.,Huazhong Agricultural University | Ginder-Vogel M.,Environmental Chemistry and Technology Program | And 4 more authors.
Chemical Geology | Year: 2014

Natural hexagonal birnessites are enriched in various transition metals (TMs). Many studies have examined the effects of single metal doping on the structures and properties of birnessites, but none focused on the simultaneous interaction mechanism of coprecipitation of two different TMs with birnessite. In this work Co and Ni co-doped hexagonal birnessites were synthesized and characterized by powder X-ray diffraction (XRD), elemental analysis, field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) spectroscopy to investigate the effects of co-doping on the structure and reactivity of birnessite and the crystal chemistry of Co and Ni. These co-doped birnessites have lower crystallinity, i.e., fewer manganese layers stacking in the c* direction, larger specific surface areas (SSAs) and increased Mn average oxidation states (AOSs) than the undoped birnessite, and Co exists in a valence of +3. Co, Ni and Mn K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) spectra demonstrate an increase in edge-sharing Ni-Me (Me=Ni, Co and Mn) distances in birnessite layers with the increase of the contents of dopants while Mn-Me distances first decrease and then increase while those of Co-Me pairs are nearly constant, coupled with first a decrease and then increase of the in-plane unit-cell parameter b. The effect of co-doping on the amounts of structural Mn and K+, numbers of [MnO6] layers stacked in c* axis, and SSAs, is larger than the effects of doping with Co alone, but less than singly Ni doping. In birnessites doped with both Co and Ni, ~74-79% of the total Co and ~23-39% of the total Ni are present within the manganese layers. Compared with the spatial distribution of TM in singly doped birnessites, the coexistence of Ni hinders the incorporation of Co into the layers during birnessite crystallization; however, coprecipitation with Co has little effects, neither hindrance nor promotion, on the insertion of Ni into the layers. These results provide insight into the interaction mechanism between coexisting Co, Ni within layered Mn oxides. It further helps us to interpret the geochemical characteristics of multi-metal incorporation into natural Mn oxides and their effects on the structures and physicochemical properties of these minerals. © 2014 Elsevier B.V.

Rutter A.P.,Environmental Chemistry and Technology Program | Schauer J.J.,Environmental Chemistry and Technology Program | Schauer J.J.,Wisconsin State Laboratory of Hygiene | Shafer M.M.,Environmental Chemistry and Technology Program | And 7 more authors.
Environmental Science and Technology | Year: 2011

Foliar accumulations of gaseous elemental mercury (GEM) were measured in three plant species between nominal temperatures of 10 and 30 °C and nominal irradiances of 0, 80, and 170 W m-2 (300 nm-700 nm) in a 19 m 3 controlled environment chamber. The plants exposed were as follows: White Ash (Fraxinus americana; WA); White Spruce (Picea glauca; WS); and Kentucky Bluegrass (Poa partensis; KYBG). Foliar enrichments in the mercury stable isotope (198Hg) were used to measure mercury accumulation. Exposures lasted for 1 day after which the leaves were digested in hot acid and the extracted mercury was analyzed with ICPMS. Resistances to accumulative uptake by leaves were observed to be dependent on both light and temperature, reaching minima at optimal growing conditions (20 °C; 170 W m-2 irradiance between 300-700 nm). Resistances typically increased at lower (10 °C) and higher (30 °C) temperatures and decreased with higher intensities of irradiance. Published models were modified and used to interpret the trends in stomatal and leaf interior resistances to GEM observed in WA. The model captured the experimental trends well and revealed that stomatal and internal resistances were both important across much of the temperature range. At high temperatures, however, stomatal resistance dominated due to increased water vapor pressure deficits. The resistances measured in this study were used to model foliar accumulations of GEM at a northern US deciduous forest using atmospheric mercury and climate measurements made over the 2003 growing season. The results were compared to modeled accumulations for GEM, RGM, and PHg using published deposition velocities. Predictions of foliar GEM accumulation were observed to be a factor of 5-10 lower when the temperature and irradiance dependent resistances determined in this study were used in place of previously published data. GEM uptake by leaves over the growing season was shown to be an important deposition pathway (2.3-3.7 μg m-2 of one-sided leaf area; OSLA) when compared to total mercury wet deposition (1.2 μg m -2 OSLA) and estimates of reactive mercury dry deposition (0.1-6 μg m-2 OSLA). Resistance-Temperature-Irradiance relationships are provided for use in models. © 2011 American Chemical Society.

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