Impact of chloride on denitrification potential in roadside wetlands.

Developed landscapes are exposed to changes in hydrology and water chemistry that limit their ability to mitigate detrimental impacts to coastal water bodies, particularly those that result from stormwater runoff. The elevated level of impervious cover increases not only runoff but also contaminant loading of nutrients, metals, and road salt used for deicing to water bodies. Here we investigate the impact that road salt has on denitrification in roadside environments. Sediments were collected from a series of forested and roadside wetlands and acclimated with a range of Cl(-) concentrations from 0 to 5000 mg L(-1) for 96 h. Denitrification rates were measured by the isotope pairing technique using (15)N-NO3(-), while denitrifying community structures were compared using terminal restriction fragment length polymorphism (T-RFLP) of nitrous oxide reductase genes (nosZ). Chloride significantly (p < 0.05) inhibited denitrification in forested wetlands at a Cl(-) dosage of 2500 or 5000 mg L(-1), but the decrease in denitrification rates was less and not significant for the roadside wetlands historically exposed to elevated concentrations of Cl(-). The difference could not be attributed to other significant changes in conditions, such as DOC concentrations, N species concentrations, or pH levels. Denitrifying communities, as measured by T-RFs of the nosZ gene, in the roadside wetlands with elevated concentration of Cl(-) were distinctly different and more diverse compared to forested wetlands, and also different in roadside wetlands after 96 h exposures to Cl(-). The shifts in denitrifying communities seem to minimize the decrease in denitrification rates in the wetlands previously exposed to Cl. As development results in more Cl(-) use and exposure to a broad range of natural or manmade wetland structures, an understanding of the seasonal effect of Cl on denitrification processes in these systems would aid in design or mitigation of the effects on N removal rates.

Wetland influence on mercury fate and transport in a temperate forested watershed.

The transport and fate of mercury (Hg) was studied in two forest wetlands; a riparian peatland and an abandoned beaver meadow. The proportion of total mercury (THg) that was methyl mercury (% MeHg) increased from 2% to 6% from the upland inlets to the outlet of the wetlands. During the growing season, MeHg concentrations were approximately three times higher (0.27ng/L) than values during the non-growing season (0.10ng/L). Transport of Hg species was facilitated by DOC production as indicated by significant positive relations with THg and MeHg. Elevated concentrations of MeHg and % MeHg (as high as 70%) were found in pore waters of the riparian and beaver meadow wetlands. Groundwater interaction with the stream was limited at the riparian peatland due to the low hydraulic conductivity of the peat. The annual fluxes of THg and MeHg at the outlet of the watershed were 2.3 and 0.092microg/m2-year respectively.

Development of a plant uptake model for cyanide.

A model for cyanide species uptake by willow (Salix eriocephala L. var. Michaux) was developed to interpret data from hydroponic experiments quantitatively. While the potential for cyanide phytoremediation has been demonstrated modeling will aid in determining plant processes that contribute to cyanide transport and metabolism in willow and will target specific physiological parameters for field-scale phytoremediation design and optimization. The objective of the model development was to gain insight into the relative role of different processes with respect to dissolved free and iron-complexed cyanide transport and assimilation in plants and to determine rates at which these processes occur within the willow plant under the experimental conditions. A physiologically-based model describing plant uptake, transport, and metabolism of cyanide species was developed to reflect the processes that influence the movement of cyanide into and throughout the plant. Plant compartmentalization (root, stem, and leaf) corresponded to the level of detail in the data collected via hydroponic experiments. Inclusion of more detailed intra- and intercellular processes would create a model inconsistent with the macroscale nature of the data. Mass balances around each compartment were developed via kinetic representations for the mass transfer processes and were combined to form a model describing the fate of cyanide species within plant-water systems.

Parameter estimation of a plant uptake model for cyanide: application to hydroponic data.

A plant uptake model is applied to describe free cyanide and ferrocyanide transport and fate in willow (Salix eriocephala var. Michaux) grown in hydroponics. The model is applied to experimental data to determine best-fit parameter values, their associated uncertainty, and their relative importance to field-scale phytoremediation applications. The fitted model results, using least-squares optimization of the observed log concentrations, indicate that free cyanide volatilization from leaf tissue and free cyanide cell wall adsorption were negligible. The free cyanide maximum uptake rate and assimilate (noncyanide 15N) first-order leaf loss rate were the only coefficients that significantly affected the model goodness of fit and were concurrently sensitive to data uncertainty in the parameter optimization. Saturation kinetics may be applicable for free cyanide uptake into plants, but not for ferrocyanide uptake, which may occur via preferential protein-mediated or inefficient transpiration stream uptake. Within the free cyanide system, the relative magnitudes of the saturation uptake parameters and the demonstration of an active role for plants in uptake relative to transpiration suggest the potential importance of preferential diffusion through the cell membranes as reported in the literature, rather than protein-mediated uptake. The fitted 13-parameter model matched the observed data well except for the predicted stem and leaf tissue assimilate concentrations, which were significantly underestimated, particularly in the free cyanide system. These low predicted values, combined with the slightly underestimated solution free cyanide removal, suggest that noncyanide 15N redistribution in phloem should be considered.

Ferrocyanide adsorption on aluminum oxides.

Ferrocyanide (Fe(CN)6(4-)) adsorption onto gamma-alumina ( gamma-Al2O3(s) ) and gibbsite (Al(OH)3(s)) was investigated over a wide pH range and at various solid loadings. Batch experiments were performed using 100-ml solutions (I = 0.01 M NaCl) dosed with 1.0 mgl(-1) Fe(CN)6(4-) as CN. Equilibrium adsorption-pH edges were developed for 0.3, 0.6, 1.2, and 2.0 gl(-1) gamma-Al(2)O3(s) and 25 gl(-1) Al(OH)3(s). Ferrocyanide adsorption increased as pH decreased, consistent with the general pH dependence for adsorption of anions onto oxide minerals. Ferrocyanide adsorption onto Al(OH)3(s) was approximately 300 times lower than onto gamma-Al(2)O3(s) on a unit weight basis due to the higher surface reactivity of the gamma-Al(2)O3(s). Ferrocyanide adsorption onto gamma-Al(2)O3(s) was significantly greater than has been reported for goethite (FeOOH(s)), and both gamma-Al(2)O3(s) and FeOOH(s) adsorbed ferrocyanide to a greater extent than Al(OH)3(s) . The investigation showed that ferrocyanide can adsorb significantly onto aluminum oxides spanning a range of crystallinity and properties, with the extent of adsorption highly dependent on pH, the solid crystalline structure, and associated surface reactivity.