Joseph T. Bushey

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.

Inputs, storage, and transport of total and methyl mercury in two temperate forest wetlands

connectivity to stream water. The volatilization rate of elemental mercury (Hg o )i n the beaver meadow wetland is of similar magnitude compared to total atmospheric Hg deposition and constitutes an important component of the overall annual Hg budget. In contrast, annual Hg o fluxes exhibited net transfer from the atmosphere to soil at the riparian wetland possibly because volatilization rates were retarded by slower diffusion of Hg o through soil to the air-water interface in water-saturated soil. The storage of THg and MeHg in wetland soil is a large pool which appears coupled with carbon and sulfur accumulation. In the current scenario of decreasing Hg emissions and atmospheric deposition, the large ‘‘active’’ soil pool in wetlands is a potential short-term and long-term source of Hg and MeHg to downstream aquatic ecosystems.

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.

PLANT TISSUE EXTRACTION METHOD FOR COMPLEXED AND FREE CYANIDE

A method for free cyanide and strongly-complexed cyanide measurement within plant tissue was developed to study uptake and movement of cyanide species separately from cyanide metabolism and metabolite movement by a willow plant (Salix eriocephala var. Michaux). Spike recoveries from solutions with and without plant tissue, using various solvent combinations, and background control tissue contributions were investigated to obtain an accurate and precise extraction method for measurement of complexed and free cyanide concentrations within plant tissue. The optimum extraction technique involved the freezing of plant tissue with liquid nitrogen to facilitate homogenization prior to extraction. Homogenized willow tissue samples, 1 to 1.5 g-fresh weight, were ground a second time under liquid nitrogen followed by grinding in slurry with 2.5 M NaOH. The slurry was brought to 100 mL volume, sonicated for 5 min, extracted in the dark for 16 h, and analyzed without filtration for total and free cyanide by acid distillation and microdiffusion respectively. Sample tissue extraction controls found recoveries of 89% and 100% for 100 μg L−1 CNT as KCN and K4Fe(CN)6 spiked in willow tissue slurries. Methanol, hexane, and 2-octanol inclusion in the solvent matrix with 2.5 M NaOH interfered with the cyanide analytical technique while chloroform reacted with NaOH and free cyanide in solution. Filtration was not included due to increased cyanide loss, and analysis of control tissue showed minimal release of cyanide or interference of plant tissue with the cyanide analytical method. Tissue cyanide concentrations from hydroponically-exposed tissue using the optimal extraction method agreed with tissue cyanide stable isotope (15N) results.

Phytoremediation of Iron Cyanide Complexes in Soil-Water Systems

Stephen D. Ebbs—Department of Plant Biology, 420 Life Science II, MC 6509, Southern Illinois University-Carbondale, Carbondale, IL, 62901, USA, sebbs@plant.siu.edu, Telephone: (618) 4533220, Fax: (618) 453-3441; Joseph T. Bushey—Department of Civil and Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA, 15213, USA, jbushey@andrew.cmu.edu, Telephone: (412) 268-5811; Fax: 412-268-7813; David A. Dzombak—Department of Civil and Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA, 15213, USA, dzombak@cmu.edu, Telephone: (412) 268-2946; Fax: 412-268-7813