The Effect of Drying/Re-Flooding on Trace Metal, As and Se Fluxes in a Treatment Wetland: Addressing Growing Environmental Concerns.

The retention of heavy metals in water treatment wetlands is well documented, but little understood. Fluxes to and from sediments for moderate concentrations of dissolved metals are particularly unknown. Treatment wetlands are dried out seasonally or occasionally for maintenance. The extent to which heavy metals may be released by drying/re-flooding is of particular concern because of the potential for toxic levels of metals to be mobilized. A 36 ha treatment wetland receiving treated oil refinery effluent in California was dried for 6 months, then re-flooded to an average depth of >10 cm. The concentrations of 11 metals, As and Se in inflow, outflow, and porewaters were measured weekly for 4 months. Mass flux rates showed that the wetland acted as a sink for As and Se, six metals (Co, Cr, Mg, Mn, Ni, and Sr) and S were overall sources and five showed zero net flux (Ba, Cu, Fe, Mo, and Zn). Porewater results indicate that oxidation of the sediments caused the source metals to be released. Removal for As > Cu, Fe, Mo, Zn > Co, Mn, Ni was consistent with the thermodynamically-predicted 'sulfide ladder', suggesting that available sulfide was insufficient to re-sequester the entire pool of mobile chalcophile elements. Our results suggest that less-soluble sulfide metals may be immobilized prior to more-soluble metals following drying/re-flooding in coastal systems with multiple metal contaminants. Ponding for up to several weeks, depending on the metals of concern, will facilitate metal re-immobilization within sediments before waters are released and minimize impacts downstream. Research on how to speed-up the conversion of soluble metals to their insoluble sulfides or other immobilized forms is urgently needed.

Unit Process Wetlands for Removal of Trace Organic Contaminants and Pathogens from Municipal Wastewater Effluents.

Treatment wetlands have become an attractive option for the removal of nutrients from municipal wastewater effluents due to their low energy requirements and operational costs, as well as the ancillary benefits they provide, including creating aesthetically appealing spaces and wildlife habitats. Treatment wetlands also hold promise as a means of removing other wastewater-derived contaminants, such as trace organic contaminants and pathogens. However, concerns about variations in treatment efficacy of these pollutants, coupled with an incomplete mechanistic understanding of their removal in wetlands, hinder the widespread adoption of constructed wetlands for these two classes of contaminants. A better understanding is needed so that wetlands as a unit process can be designed for their removal, with individual wetland cells optimized for the removal of specific contaminants, and connected in series or integrated with other engineered or natural treatment processes. In this article, removal mechanisms of trace organic contaminants and pathogens are reviewed, including sorption and sedimentation, biotransformation and predation, photolysis and photoinactivation, and remaining knowledge gaps are identified. In addition, suggestions are provided for how these treatment mechanisms can be enhanced in commonly employed unit process wetland cells or how they might be harnessed in novel unit process cells. It is hoped that application of the unit process concept to a wider range of contaminants will lead to more widespread application of wetland treatment trains as components of urban water infrastructure in the United States and around the globe.

Reduction in labile copper in the 7-day Ceriodaphnia dubia toxicity test due to the interaction with zooplankton food.

Due to the increased popularity of zooplankton toxicity tests, it is important to investigate potential confounding factors. Though zooplankton food has been studied extensively to meet the nutritional needs of the zooplankton, less research has been done on whether food addition reduces the toxicity of metals in the tested sample. This investigation combines toxicity tests and metal speciation analysis to determine whether the EPA recommended food of YCT (yeast, cerophyll, and trout chow) and Pseudokirchneriella subcapitata (formerly Selenastrum capricornutum) reduces copper toxicity by decreasing the concentration of labile copper. Toxicity tests were performed with Ceriodaphnia dubia on culture water spiked with 0, 787, and 1574 nM copper with five different food levels. A Chelex-100 cation exchange resin and a graphite furnace-atomic absorption spectrophotometer were used in conjunction with the toxicity tests to measure the amount of labile copper in the culture water. At the EPA recommended food dosage, the C. dubia food has a chelating capacity of approximately 500 nM Cu. For both concentrations of spiked culture water, the toxicity to C. dubia was reduced with increasing food level, which seemed to be both from a decrease in labile copper concentration and an increase in the nutritional condition of the zooplankton.

Reduction of net mercury methylation by iron in Desulfobulbus propionicus (1pr3) cultures: implications for engineered wetlands.

Although one potential drawback of wetland construction and restoration is the formation of monomethylmercury, it may be possible to decrease net mercury methylation with the use of an appropriate sediment amendment. Using pure cultures of the sulfate-reducing bacterium Desulfobulbus propionicus (1pr3), we tested the hypothesis that adding ferrous iron to sulfidic wetland sediments decreases mercury solubility and bioavailability and, therefore, net methylation. In sediment-free cultures, net mercury methylation decreased with increasing [Fe(II)]. After 72 h of incubation, more than four times as much net methylmercury formed in the lowest ([Fe(II)] = 10(-6) M) treatment (180 +/- 33 pM) as compared with the highest ([Fe(II)] = 10(-2) M) treatment (42 +/- 14 pM). In cultures containing a model wetland sediment, more than three times as much methylmercury was observed in 10(-6) M Fe(II) treatments (1,010 +/- 95 pM) as compared with treatments amended with 10(-2) M Fe(II) (300 +/- 46 pM). Initial filterable mercury measurements and chemical equilibrium speciation predictions suggest that the lower net methylmercury production in the high-iron treatments was due to a decrease in sulfide activity and a concomitant decrease in the concentration of dissolved mercury. Although iron amendments could potentially minimize net mercury methylation in engineered wetland sediments, further research under field conditions is required to assess the efficacy of this approach.