Characterization of manganese oxide amendments for in situ remediation of mercury-contaminated sediments.

Addition of Mn(iv)-oxide phases pyrolusite or birnessite was investigated as a remedial amendment for Hg-contaminated sediments. Because inorganic Hg methylation is a byproduct of bacterial sulfate reduction, reaction of Mn(iv) oxide with pore water should poise sediment oxidation potential at a level higher than favorable for Hg methylation. Changes in Mn(iv)-oxide mineralogy and oxidation state over time were investigated in sediment tank mesocosm experiments in which Mn(iv)-oxide amendment was either mixed into Hg-contaminated sediment or applied as a thin-layer sand cap on top of sediment. Mesocosms were sampled between 4 and 15 months of operation and solid phases were characterized by X-ray absorption spectroscopy (XAS). For pyrolusite-amended sediments, Mn(iv) oxide was altered to a mixture of Mn(iii)-oxyhydroxide and Mn, Fe(iii, ii)-oxide phases, with a progressive increase in the Mn(ii)-carbonate fraction over time as mesocosm sediments became more reduced. For birnessite-amended sediments, both Mn(iii) oxyhydroxide and Mn(ii) carbonate were identified at 4 months, indicating a faster rate of Mn reduction compared to pyrolusite. After 15 months of reaction, birnessite was converted completely to Mn(ii) carbonate, whereas residual Mn, Fe(iii, ii)-oxide phases were still present in addition to Mn(ii) carbonate in the pyrolusite mesocosm. In the thin-layer sand cap mesocosms, no changes in either pyrolusite or birnessite XAS spectra were observed after 10 months of reaction. Equilibrium phase relationships support the interpretation of mineral redox buffering by mixed-valent (Mn, Fe)(iii, ii)-oxide phases. Results suggest that amendment longevity for redox buffering can be controlled by adjusting the mass and type of Mn(iv) oxide applied, mineral crystallinity, surface area, and particle size. For a given site, amendment capping versus mixing with sediment should be evaluated to determine the optimum treatment approach, which may vary depending on application constraints, rate of Mn(iv) oxide transformation, and frequency of reapplication to maintain desired oxidation state and pH.

Manganese(iv) oxide amendments reduce methylmercury concentrations in sediment porewater.

Manganese(iv) oxide (pyrolusite, birnessite) mineral amendments can reduce dissolved MeHg concentrations in sediment theoretically by inhibiting microbial sulfate reduction, which is a major methylation pathway in sediments. Anaerobic sediment slurry microcosms in which Hg methylation was stimulated by addition of labile organic carbon (acetate) and HgCl2 showed that manganese(iv) oxide reduced the percent MeHg in slurry porewater (filtered), by 1-2 orders of magnitude relative to controls. Sediment-water mesocosms with pyrolusite or birnessite either directly mixed into the top 5 cm or applied in a thin (5 cm) sand layer over sediment showed reductions in percent MeHg in porewater of 66-69% for pyrolusite and 81-89% for birnessite amendment. A thin sand layer alone resulted in 65% reduction. CO2 respirometry experiments showed that the amendments stimulated microbial activity. Microbial community census by PCR and DNA sequencing indicated that the addition of Mn(iv) oxides did not significantly alter the indigenous sediment microbial community structure, although a small increase in abundance of iron and manganese reducers was observed after a 2 week incubation period. The mechanism of decreasing MeHg relative to Hg concentrations in porewater likely involved an increase in the importance of Mn(iv) reduction (relative to sulfate reduction) in heterotrophic microbial metabolism in the sediments amended with Mn(iv) oxides. Manganese reduction was confirmed as the predominant biogeochemical redox process by microelectrode voltammetry profiling of the sediment microcosms, although adsorption to Mn oxide surfaces, enhanced MeHg demethylation, and abiotic reduction of Mn(iv) also may have been involved in reducing percent MeHg and suppressing net MeHg production. These results represent a novel approach for mitigating MeHg impacts from sediments with potential applicability to a range of aquatic settings including intertidal zones, tidal marshes, seasonal wetlands, reservoirs, and lakes.

Silicate Binding and Precipitation on Iron Oxyhydroxides.

Silica-bearing waters in nature often alter the reactivity of mineral surfaces via deposition of Si complexes and solids. In this work, Fourier transform infrared (FTIR) spectroscopy was used to identify hydroxo groups at goethite (α-FeOOH) and lepidocrocite (γ-FeOOH) surfaces that are targeted by ligand exchange reactions with monomeric silicate species. Measurements of samples first reacted in aqueous solutions then dried under N2(g) enabled resolution of the signature O-H stretching bands of singly (-OH), doubly (µ-OH), and triply coordinated (µ3-OH) groups. Samples reacted with Si for 3 and 30 d at pH 4 and 7 revealed that -OH groups were preferentially exchanged by silicate and that µ-OH and µ3-OH groups were not exchanged. Based on knowledge of the disposition of -OH groups on the major crystallographic faces of goethite and lepidocrocite, and the response of these groups to ligand exchange prior oligomerization, our work points to the predominance of rows of mononuclear monodentate silicate species, each separated by at least one -OH group. These species are the attachment sites from which oligomerization and polymerization reactions occur, starting at loadings exceeding ∼1 Si/nm2 and corresponding to soluble Si concentrations that can be as low as ∼0.7 mM after 30 d reaction time. Only above such loadings can reaction products grow away from rows of -OH groups and form hydrogen bonds with nonexchangeable µ-OH and µ3-OH groups. These findings have important repercussions for our understanding of the fate of waterborne silicate ions exposed to minerals.

Influence of phosphate and silica on U(VI) precipitation from acidic and neutralized wastewaters.

Uranium speciation and physical-chemical characteristics were studied in solids precipitated from synthetic acidic to circumneutral wastewaters in the presence and absence of dissolved silica and phosphate to examine thermodynamic and kinetic controls on phase formation. Composition of synthetic wastewater was based on disposal sites 216-U-8 and 216-U-12 Cribs at the Hanford site (WA, USA). In the absence of dissolved silica or phosphate, crystalline or amorphous uranyl oxide hydrates, either compreignacite or meta-schoepite, precipitated at pH 5 or 7 after 30 d of reaction, in agreement with thermodynamic calculations. In the presence of 1 mM dissolved silica representative of groundwater concentrations, amorphous phases dominated by compreignacite precipitated rapidly at pH 5 or 7 as a metastable phase and formation of poorly crystalline boltwoodite, the thermodynamically stable uranyl silicate phase, was slow. In the presence of phosphate (3 mM), meta-ankoleite initially precipitated as the primary phase at pH 3, 5, or 7 regardless of the presence of 1 mM dissolved silica. Analysis of precipitates by U LIII-edge extended X-ray absorption fine structure (EXAFS) indicated that "autunite-type" sheets of meta-ankoleite transformed to "phosphuranylite-type" sheets after 30 d of reaction, probably due to Ca substitution in the structure. Low solubility of uranyl phosphate phases limits dissolved U(VI) concentrations but differences in particle size, crystallinity, and precipitate composition vary with pH and base cation concentration, which will influence the thermodynamic and kinetic stability of these phases.

Arsenic removal from water using flame-synthesized iron oxide nanoparticles with variable oxidation states.

We utilized gas-phase diffusion flame synthesis, which has potential for large-scale production of metal oxide nanoparticles, to produce iron oxide nanoparticles (IONPs) with variable oxidation states. The efficacy of these materials in removal of arsenate (As(V) ) from water was assessed. Two different flame configurations, a diffusion flame (DF) and an inverse diffusion flame (IDF), were employed to synthesize six different IONPs by controlling flame conditions. The IONPs produced in the IDF configuration (IDF-IONPs) had smaller particle diameters (4.8 - 8.2 nm) and larger surface areas (141-213 m2/g) than the IONPs produced in the DF configuration (29 nm, 36 m2/g), which resulted in their higher adsorption capacities. As(V) adsorption capacities of the IDF-IONPs increased when the IONPs were synthesized in more oxidizing conditions. The fully oxidized IDF-IONPs, maghemite (γ-Fe2O3), showed the highest As(V) adsorption capacity, comparable to that of magnetite nanocrystals synthesized by thermal decomposition of iron pentacarbonyl and equivalent to three to four times higher capacity than that of a commonly used goethite-based adsorbent. All IONPs were magnetically responsive, which is of great importance for solid-liquid separation. This study demonstrates that the IONPs synthesized in gas-phase flame, particularly IDF-IONPs, are excellent adsorbents because of their high As(V) sorption capacity, potential for large-scale production, and useful magnetic property.

Individual and combined effects of water quality and empty bed contact time on As(V) removal by a fixed-bed iron oxide adsorber: implication for silicate precoating.

The individual and combined effects of changes in water quality (i.e. pH, initial concentrations of arsenate (As(V)) and competing ions) and empty bed contact time (EBCT) on As(V) removal performance of a fixed-bed adsorber (FBA) packed with a nanostructured goethite-based granular porous adsorbent were systematically studied under environmentally relevant conditions. Rapid small scale column tests (RSSCTs) were extensively conducted at different EBCTs with synthetic waters in which pH and the concentrations of competing ions (phosphate, silicate, and vanadate) were controlled. In the absence of the competing ions, the effects of initial As(V) concentration, pH, and EBCT on As(V) breakthrough curves were successfully predicted by the homogeneous surface diffusion model (HSDM) with adsorption isotherms predicted by the extended triple layer model (ETLM). The interference effects of silicate and phosphate on As(V) removal were strongly influenced by pH, their concentrations, and EBCT. In the presence of silicate (≤21 mg/L as Si), a longer EBCT surprisingly resulted in worse As(V) removal performance. We suggest this is because silicate, which normally exists at much higher concentration and moves more quickly through the bed than As(V), occupies or blocks adsorption sites on the media and interferes with later As(V) adsorption. Here, an alternative operating scheme of a FBA for As(V) removal is proposed to mitigate the silicate preloading. Silicate showed a strong competing effect to As(V) under the tested conditions. However, as the phosphate concentration increased, its interference effect dominated that of silicate. High phosphate concentration (>100 µg/L as P), as experienced in some regions, resulted in immediate As(V) breakthrough. In contrast to the observation in the presence of silicate, longer EBCT resulted in improved As(V) removal performance in the presence of phosphate. Vanadate was found to compete with As(V) as strongly as phosphate. This study reveals the competitive interactions of As(V) with the competing ions in actual adsorptive treatment systems and the dependence of optimal operation scheme and EBCT on water quality in seeking improved As(V) removal in a FBA.

Quantification of the effects of organic and carbonate buffers on arsenate and phosphate adsorption on a goethite-based granular porous adsorbent.

Interest in the development of oxide-based materials for arsenate removal has led to a variety of experimental methods and conditions for determining arsenate adsorption isotherms, which hinders comparative evaluation of their adsorptive capacities. Here, we systematically investigate the effects of buffer (HEPES or carbonate), adsorbent dose, and solution pH on arsenate and phosphate adsorption isotherms for a previously well characterized goethite-based adsorbent (Bayoxide E33 (E33)). All adsorption isotherms obtained at different adsorbate/adsorbent concentrations were identical when 1 mM of HEPES (96 mg C/L) was used as a buffer. At low aqueous arsenate and phosphate concentration (∼1.3 µM), however, adsorption isotherms obtained using 10 mM of NaHCO(3) buffer, which is a reasonable carbonate concentration in groundwater, are significantly different from those obtained without buffer or with HEPES. The carbonate competitive effects were analyzed using the extended triple layer model (ETLM) with the adsorption equilibrium constant of carbonate calibrated using independent published carbonate adsorption data for pure goethite taking into consideration the different surface properties. The successful ETLM calculations of arsenate adsorption isotherms for E33 under various conditions allowed quantitative comparison of the arsenate adsorption capacity between E33 and other major adsorbents initially tested under varied experimental conditions in the literature.

Extended triple layer modeling of arsenate and phosphate adsorption on a goethite-based granular porous adsorbent.

The extended triple layer model (ETLM), which is consistent with spectroscopic and theoretical molecular evidence, is first systematically tested for its capability to model adsorption of arsenate and phosphate, a strong competitor, on a common goethite-based granular porous adsorptive media (Bayoxide E33 (E33)) in water treatment systems under a wide range of solution conditions. Deprotonated bidentate-binuclear, protonated bidentate-binuclear, and deprotonated monodentate complexes are chosen as surface species for both arsenate and phosphate. The estimated values of the ETLM parameters of arsenate for the adsorbent are close to those for pure goethite minerals previously determined by others. The ETLM predictions for arsenate and phosphate adsorption basically agree with experimental results over a wide range of pH, surface coverage, and solid concentrations. High background electrolyte concentration (i.e., I = 0.1 M), however, was found to strongly impact arsenate and phosphate adsorption on E33 probably because of the porous structure of the adsorbent, which cannot be observed for pure goethite minerals and could not be completely modeled by the ETLM. Prediction of phosphate adsorption isotherms at higher pH were relatively poor, and this may suggest searching for alternative surface species for phosphate. Since adsorption equilibrium constants of major coexisting ions encountered in water treatment systems for goethite minerals have been estimated by others, the application of ETLM theory to this common goethite-based adsorptive media will enable us to understand how those coexisting ions macroscopically and thermodynamically interact with arsenate and phosphate in the environment of adsorptive water treatment system in a way consistent with molecular and spectroscopic evidence.

Origins and transport of aquatic dioxins in the Japanese watershed: soil contamination, land use, and soil runoff events.

Significant dioxins accumulations in Japanese forests and paddy fields have been observed, and surface soil runoff caused by rainfall and irrigation (i.e., soil puddling in paddy fields) results in dioxins input into the aquatic environment. An extensive investigation into the origins and transport of aquatic dioxins in the Yasu watershed, Japan was conducted considering surface soil contamination level, land use, and type of soil runoff event (i.e., irrigation runoff [IR], rainfall runoff [RR], and base flow [BF]). Combined use of the chemically activated luciferase expression (CALUX) assay together with high-resolution gas chromatography and high-resolution mass spectrometry (HRGC/HRMS) efficiently enabled this study, so that origins, transport, and dynamic movement of aquatic dioxins in the watershed were revealed. The particulate organic carbon normalized particulate-dioxins WHO-toxic equivalent (TEQ) concentration predicted by the CALUX assay (Spar) was found to be a convenient molecular marker to indicate origins of aquatic dioxins and clearly reflect surface soil contamination level, land use, and soil runoff events. Using experimental results and theoretical modeling, the annual loading amount of dioxins at the middle reach of the river was estimated to be 0.458 mg WHO-TEQ in 2004. More than 96.6% of the annual loading amount was attributed to RR and derived almost evenly from forest and paddy fields at the study location. Because the annual loading amount at the middle reach is less than 0.5% of the total dioxins accumulated in the upper basin, dioxins runoff from the Japanese watershed will continue. This study shows that the combined use of the bioassay with HRGC/HRMS can provide new insights into dioxins transport and fate in the environment.

Characterization and potential environmental risks of leachate from shredded rubber mulches.

In order to determine whether shredded rubber mulches (RM) pose water quality risks when used in stormwater best management practices (BMPs) such as bioretention basins, batch leaching tests were conducted to identify and quantify constituents in leachates from RM such as metal ions, nutrients, total organic carbon (TOC), and aryl hydrocarbon receptor (AhR) activity (determined by the chemically activated luciferase gene expression (CALUX) bioassay) at varied temperature and initial pH values. The results indicate that aqueous extracts of RM contain high concentrations of zinc (Zn) compared with wood mulches (WM), and its concentration increased at lower pH and higher temperature. Although methanol extracts of RM displayed high AhR activity, none of the aqueous extracts of RM had significant activity. Hence, while unknown constituents that have significant AhR activity are present in RM, they appear to be not measurably extracted by water under environmental conditions relevant for stormwater (5

Mass loading and partitioning of dioxins in irrigation runoff from Japanese paddy fields: combination usage of the CALUX assay with HRGC/HRMS.

Lack of understanding of dioxins mass loading into the aquatic environment motivated the quantitative investigation of dioxins runoff from paddy fields during one entire irrigation period in the Minakuchi region, Japan. Combination use of the chemically activated luciferase gene expression (CALUX) bioassay together with high resolution gas chromatography and high resolution mass spectrometry (HRGC/HRMS) enabled efficient investigation of dioxins contamination. The result shows that the congener profile in irrigation runoff is quite similar to those in paddy soil samples and that 1,3,6,8-/1,3,7,9-TeCDD and OCDD derived from pesticides (i.e., pentachlorophenol (PCP) and chloronitrophen (CNP)) are predominant congeners in irrigation runoff. Although it is not surprising that dioxins concentration was strongly dependent on the suspended solids (SS) and the particulate organic carbon (POC) concentration, the dioxins toxic equivalency (TEQ) concentration was extremely high in irrigation runoff (max: 16,380 pg/L, corresponding to 12 pg WHO-TEQ/L) due to runoff of highly contaminated paddy soils. The results imply that dioxins concentration in a river must be monitored considering soil contamination level, land use, and soil runoff events. Using experimental data and a theoretical model, the mass loading of dioxins from the paddy fields by irrigation runoff was estimated to be 1.50 x 10(-2)% of total amount of dioxins accumulated in the paddy fields. Given the results of other researches, it is implied the following: 1) large portion of paddy soils released into the river appear to be settled on the riverbed due to small water flux, and, then, washed out and transported by rainfall runoff after irrigation period, 2) rainfall runoff itself also wash out paddy soils directly from paddy fields. Combination use of the CALUX bioassay with HRGC/HRMS is demonstrated as an alternative strategy to assess dioxins contamination in the environment.