Fluorinated anionic surfactants have drawn considerable attention due to recent work showing significant concentrations in surface waters and biota from around the globe. A detailed understanding of the transport and fate of fluorinated surfactants through soil and like media must include an elucidation of mineral surface chemistry. Five materials were equilibrated with solutions of perfluorooctane sulfonate (PFOS) to characterize adsorption: kaolinite, Ottawa sand standard, synthetic goethite, Lake Michigan sediment, and iron-coated sand from Mappsville, VA. Aqueous and adsorbed PFOS was quantified with LC/MS (mass balance average: 101 ( 12 %, n ) 37). The materials showed a near linear increase in adsorption as the equilibrium concentrations increased. Isotherms and calculated solid/solution distribution ratio experiments indicated that PFOS adsorption is significant but smaller than hydrocarbon analogues or organic compounds of similar molecular weight. Surface area normalized adsorption increased for the materials in the following order: goethite < kaolinite < high iron sand < Ottawa sand standard. Experimental results and comparisons to published data suggest that organic carbon may play an important role in sorption whereas electrostatic attraction may play a role when organic carbon is not present.
Iron oxides and oxyhydroxides are common and important materials in the environment, and they strongly impact the biogeochemical cycle of iron and other species at the Earth's surface. These materials commonly occur as nanoparticles in the 3 -10 nm size range. This paper presents quantitative results demonstrating that iron oxide reactivity is particle size dependent. The rate and extent of the reductive dissolution of iron oxyhydroxide nanoparticles by hydroquinone in batch experiments were measured as a function of particle identity, particle loading, and hydroquinone concentration. Rates were normalized to surface areas determined by both transmission electron microscopy and Braunauer-Emmett-Teller surface. Results show that surface-area-normalized rates of reductive dissolution are fastest ͑by as much as 100 times͒ in experiments using six-line ferrihydrite versus goethite. Furthermore, the surface-area-normalized rates for 4 nm ferrihydrite nanoparticles are up to 20 times faster than the rates for 6 nm ferrihydrite nanoparticles, and the surface-area-normalized rates for 5 ϫ 64 nm goethite nanoparticles are up to two times faster than the rates for 22ϫ 367 nm goethite nanoparticles.
Iron oxides and oxyhydroxides are common and important materials in the environment, and they strongly impact the biogeochemical cycle of iron and other species at the Earth's surface. These materials commonly occur as nanoparticles in the 3 -10 nm size range. This paper presents quantitative results demonstrating that iron oxide reactivity is particle size dependent. The rate and extent of the reductive dissolution of iron oxyhydroxide nanoparticles by hydroquinone in batch experiments were measured as a function of particle identity, particle loading, and hydroquinone concentration. Rates were normalized to surface areas determined by both transmission electron microscopy and Braunauer-Emmett-Teller surface. Results show that surface-area-normalized rates of reductive dissolution are fastest ͑by as much as 100 times͒ in experiments using six-line ferrihydrite versus goethite. Furthermore, the surface-area-normalized rates for 4 nm ferrihydrite nanoparticles are up to 20 times faster than the rates for 6 nm ferrihydrite nanoparticles, and the surface-area-normalized rates for 5 ϫ 64 nm goethite nanoparticles are up to two times faster than the rates for 22ϫ 367 nm goethite nanoparticles.
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