Response to Julian et al. (2015) "comment on and reinterpretation of Gabriel et al. (2014) 'fish mercury and surface water sulfate relationships in the everglades protection area'".

The purpose of this forum is to respond to a rebuttal submitted by Julian et al., Environ Manag 55:1-5, 2015 where they outlined their overall disagreement with the data preparation, methods, and interpretation of results presented in Gabriel et al. (Environ Manag 53:583-593, 2014). Here, we provide background information on the research premise presented in Gabriel et al. (Environ Manag 53:583-593, 2014) and provide a defense for this work using five themes. In spite of what Julian et al. perceive as limitations in the sampling methods and analytical tools used for this work, the relationships found between fish total mercury and surface water sulfate concentrations in Gabriel et al. (Environ Manag 53:583-593, 2014) are comparable to relationships between pore water methylmercury (MeHg) and pore water sulfate found in past studies indicating that sulfate is important to MeHg production and bioaccumulation in the Everglades. Julian et al. state "…there is no way to justify any ecosystem-wide sulfur strategy as a management approach to reduce mercury risk in the (Everglades) as suggested by Gabriel et al. (Environ Manag 53:583-593, 2014), Corrales et al. (Sci Tot Environ 409:2156-2162, 2011) and Orem et al. (Rev Environ Sci Technol 41 (S1):249-288, 2011)." We disagree, and having stated why sulfate input reduction to the Everglades may be the most effective means of reducing mercury in Everglades fish, it is important that research on sulfur and mercury biogeochemistry continues. If further studies support the relationship between sulfate loading reduction and MeHg reduction, sulfur mass balance studies should commence to (1) better quantify agricultural and connate seawater sulfate inputs and (2) define opportunities to reduce sulfate inputs to the Everglades ecosystem.

Fish mercury and surface water sulfate relationships in the Everglades Protection Area.

Few published studies present data on relationships between fish mercury and surface or pore water sulfate concentrations, particularly on an ecosystem-wide basis. Resource managers can use these relationships to identify the sulfate conditions that contain fish with health-concerning total mercury (THg) levels and to evaluate the role of sulfate in methyl-mercury (MeHg) production. In this study, we derived relationships between THg in three fish trophic levels (mosquitofish, sunfish, and age-1 largemouth bass) and surface water sulfate from 1998 to 2009 for multiple stations across the Everglades Protection Area (EPA). Results show the relationship between sulfate and fish THg in each fish type is nonlinear and largely skewed, similar to the relationship between MeHg production and sulfate concentration in peatland sediment pore water identified by other researchers. Peak fish THg levels occurred in ~1 to 12 mg/L sulfate conditions. There was significant variability in the fish THg data, and there were several instances of high-fish THg levels in high-sulfate conditions (>30 mg/L). Health-concerning fish THg levels were present in all surface water sulfate conditions; however, most of these levels occurred in 1-20 mg/L sulfate. The data in this study, including recent studies, show consistent and identifiable areas of high- and low-fish THg across the spectrum of surface water sulfate concentration, therefore, applying an ecosystem-wide sulfur strategy may be an effective management approach as it would significantly reduce MeHg risk in the EPA.

Temporal and spatial patterns of internal phosphorus recycling in a South Florida (USA) stormwater treatment area.

Large constructed wetlands, known as stormwater treatment areas (STAs), have been deployed to remove phosphorus (P) in drainage waters before discharge into the Everglades in South Florida, USA. Their P removal performance depends on internal P cycling under typically hydrated, but with occasionally desiccated, conditions. We examined the spatial and temporal P removal capacity under different hydrologic conditions along a STA flow path. While inflow soils are P enriched, the outflow region of the wetland contained P-unsaturated soils with minimal net recycling of bound soil P to the water column as plant-available P. The outflow-region soils were characterized by low porewater soluble reactive P (SRP) (≤40 µg L) and high total sulfide (TS) (2-9 mg L) concentrations, and total ammoniacal nitrogen (TAN) and SRP flux rates that averaged 1.51 and 0.002 mg m d, respectively. Pronounced increases in porewater and surface-water concentrations of SRP, dissolved organic P (DOP), and TAN were observed immediately after rehydration of the cell after an extended drought. Elevated total P concentrations persisted at the outfall of the cell for several months thereafter, resulting in an annual outflow total P concentration nearly threefold higher than the long-term mean. Relative to processes that can occur during extended periods of inundation, such as sulfate-enhanced P release from organic matter mineralization or iron sulfide formation, aerobic oxidation of organic matter during prolonged dryout periods is a more significant biogeochemical process in compromising soil P retention in STAs.

Evaluating the spatial variation of total mercury in young-of-year yellow perch (Perca flavescens), surface water and upland soil for watershed-lake systems within the southern Boreal Shield.

The primary objective of this research is to investigate relationships between mercury in upland soil, lake water and fish tissue and explore the cause for the observed spatial variation of THg in age one yellow perch (Perca flavescens) for ten lakes within the Superior National Forest. Spatial relationships between yellow perch THg tissue concentration and a total of 45 watershed and water chemistry parameters were evaluated for two separate years: 2005 and 2006. Results show agreement with other studies where watershed area, lake water pH, nutrient levels (specifically dissolved NO(3)(-)-N) and dissolved iron are important factors controlling and/or predicting fish THg level. Exceeding all was the strong dependence of yellow perch THg level on soil A-horizon THg and, in particular, soil O-horizon THg concentrations (Spearman rho=0.81). Soil B-horizon THg concentration was significantly correlated (Pearson r=0.75) with lake water THg concentration. Lakes surrounded by a greater percentage of shrub wetlands (peatlands) had higher fish tissue THg levels, thus it is highly possible that these wetlands are main locations for mercury methylation. Stepwise regression was used to develop empirical models for the purpose of predicting the spatial variation in yellow perch THg over the studied region. The 2005 regression model demonstrates it is possible to obtain good prediction (up to 60% variance description) of resident yellow perch THg level using upland soil O-horizon THg as the only independent variable. The 2006 model shows even greater prediction (r(2)=0.73, with an overall 10 ng/g [tissue, wet weight] margin of error), using lake water dissolved iron and watershed area as the only model independent variables. The developed regression models in this study can help with interpreting THg concentrations in low trophic level fish species for untested lakes of the greater Superior National Forest and surrounding Boreal ecosystem.

Principal biogeochemical factors affecting the speciation and transport of mercury through the terrestrial environment.

It is increasingly becoming known that mercury transport and speciation in the terrestrial environment play major roles in methyl-mercury bioaccumulation potential in surface water. This review discusses the principal biogeochemical reactions affecting the transport and speciation of mercury in the terrestrial watershed. The issues presented are mercury-ligand formation, mercury adsorption/desorption, and elemental mercury reduction and volatilization. In terrestrial environments, OH-, Cl- and S- ions have the largest influence on ligand formation. Under oxidized surface soil conditions Hg(OH)2, HgCl2, HgOH+, HgS, and Hg0 are the predominant inorganic mercury forms. In reduced environments, common mercury forms are HgSH+, HgOHSH, and HgClSH. Many of these mercury forms are further bound to organic and inorganic ligands. Mercury adsorption to mineral and organic surfaces is mainly dictated by two factors: pH and dissolved ions. An increase in Cl- concentration and a decrease in pH can, together or separately, decrease mercury adsorption. Clay and organic soils have the highest capability of adsorbing mercury. Important parameters that increase abiotic inorganic mercury reduction are availability of electron donors, low redox potential, and sunlight intensity. Primary factors that increase volatilization are soil permeability and temperature. A decrease in mercury adsorption and an increase in soil moisture will also increase volatilization. The effect of climate on biogeochemical reactions in the terrestrial watershed indicates mercury speciation and transport to receiving water will vary on a regional basis.