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Response to "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.

Environmental Management

Revisiting the cape cod bacteria injection experiment using a stochastic modeling approach

Bromide and resting-cell bacteria tracer tests conducted in a sandy aquifer at the U.S. Geological Survey Cape Cod site in 1987 were reinterpreted using a three-dimensional stochastic approach. Bacteria transport was coupled to colloid filtration theory through functional dependence of local-scale colloid transport parameters upon hydraulic conductivity and seepage velocity in a stochastic advection - dispersion/attachment - detachment model. Geostatistical information on the hydraulic conductivity (K) field that was unavailable at the time of the original test was utilized as input. Using geostatistical parameters, a groundwater flow and particle-tracking model of conservative solute transport was calibrated to the bromide-tracer breakthrough data. An optimization routine was employed over 100 realizations to adjust the mean and variance ofthe natural-logarithm of hydraulic conductivity (InK) field to achieve best fit of a simulated, average bromide breakthrough curve. A stochastic particle-tracking model for the bacteria was run without adjustments to the local-scale colloid transport parameters. Good predictions of mean bacteria breakthrough were achieved using several approaches for modeling components of the system. Simulations incorporating the recent Tufenkji and Elimelech (Environ. Sci. Technol. 2004, 38, 529-536) correlation equation for estimating single collector efficiency were compared to those using the older Rajagopalan and Tien (AIChE J. 1976, 22, 523-533) model. Both appeared to work equally well at predicting mean bacteria breakthrough using a constant mean bacteria diameter for this set of field conditions. Simulations using a distribution of bacterial cell diameters available from original field notes yielded a slight improvement in the model and data agreement compared to simulations using an average bacterial diameter. The stochastic approach based on estimates of local-scale parameters for the bacteria-transport process reasonably captured the mean bacteria transport behavior and calculated an envelope of uncertainty that bracketed the observations in most simulation cases.

Massachusetts

Wave-induced mass transport affects daily Escherichia coli fluctuations in nearshore water

Characterization of diel variability of fecal indicator bacteria concentration in nearshore waters is of particular importance for development of water sampling standards and protection of public health. Significant nighttime increase in Escherichia coli ( E. coli ) concentration in beach water, previously observed at marine sites, has also been identified in summer 2000 from fixed locations in waist- and knee-deep waters at Chicago 63rd Street Beach, an embayed, tideless, freshwater beach with low currents at night (approximately 0.015 m s –1 ). A theoretical model using wave-induced mass transport velocity for advection was developed to assess the contribution of surface waves to the observed nighttime E. coli replenishment in the nearshore water. Using average wave conditions for the summer season of year 2000, the model predicted an amount of E. coli transported from water of intermediate depth, where sediment resuspension occurred intermittently, that would be sufficient to have elevated E. coli concentration in the surf and swash zones as observed. The nighttime replenishment of E. coli in the surf and swash zones revealed here is an important phase in the cycle of diel variations of E. coli concentration in nearshore water. According to previous findings in Ge et al. (Environ. Sci. Technol. 2010, 44, 6731–6737), enhanced current circulation in the embayment during the day tends to displace and deposit material offshore, which partially sets up the system by the early evening for a new period of nighttime onshore movement. This wave-induced mass transport effect, although facilitating a significant base supply of material shoreward, can be perturbed or significantly influenced by high currents (orders of magnitude larger than a typical wave-induced mass transport velocity), current-induced turbulence, and tidal forcing.

Illinois

Partitioning and transport of total and methyl mercury in the Lower Fox River, Wisconsin

To investigate transport and partitioning processes of Hg(T) in the Fox River, we coupled detailed time series data of total mercury (Hg(T)) at the river mouth with transect sampling in the Lower Fox River. Unfiltered Hg(T) concentrations in the Fox River during the study period (April 1994-October 1995) ranged from 1.8 to 182 ng L(-1) with a median of 24.8 ng L-1, predominantly (93.6%) in the particulate phase. These levels were significantly elevated compared with other large tributaries to Lake Michigan (Hurley, J. P.; Shafer, M. M.; Cowell, S. E.; Overdier, J. T.; Hughes, P. E.; Armstrong, D. E. Environ. Sci. Technol. 1996, 30, 20932098). Transect sampling revealed progressively increasing water column Hg(T) concentrations and Hg(T) particulate enrichment downstream, which were consistent with trends in sediment Hg(T) levels in the river. Resuspended sediments are likely the predominant source of Hg from the Fox River into Green Bay. Despite elevated Hg(T) concentrations, methyl mercury (MeHg) concentrations were relatively low, suggesting limited bioavailability of Hg(T) associated with sediments.To investigate transport and partitioning processes of HgT in the Fox River, we coupled detailed time series data of total mercury (HgT) at the river mouth with transect sampling in the Lower Fox River. Unfiltered HgT concentrations in the Fox River during the study period (April 1994-October 1995) ranged from 1.8 to 182 ng L-1 with a median of 24.8 ng L-1, predominantly (93.6%) in the particulate phase. These levels were significantly elevated compared with other large tributaries to Lake Michigan. Transect sampling revealed progressively increasing water column HgT concentrations and HgT particulate enrichment downstream, which were consistent with trends in sediment HgT levels in the river. Resuspended sediments are likely the predominant source of Hg from the Fox River into Green Bay. Despite elevated HgT concentrations, methyl mercury (MeHg) concentrations were relatively low, suggesting limited bioavailability of HgT associated with sediments.

Environmental Science & Technology

Effect of nanoparticle size and natural organic matter composition on the bioavailability of polyvinylpyrrolidone- coated platinum nanoparticles to a model freshwater invertebrate

The bioavailability of dissolved Pt(IV) and polyvinylpyrrolidone-coated platinum nanoparticles (PtNPs) of five different nominal hydrodynamic diameters (20, 30, 50, 75, and 95 nm) was characterized in laboratory experiments using the model freshwater snail Lymnaea stagnalis . Dissolved Pt(IV) and all nanoparticle sizes were bioavailable to L. stagnalis . Platinum bioavailability, inferred from conditional uptake rate constants, was greater for nanoparticulate than dissolved forms and increased with increasing nanoparticle hydrodynamic diameter. The effect of natural organic matter (NOM) composition on PtNP bioavailability was evaluated using six NOM samples at two nanoparticle sizes (20 and 95 nm). NOM suppressed the bioavailability of 95 nm PtNPs in all cases, and DOM reduced sulfur content exhibited a positive correlation with 95 nm PtNP bioavailability. The bioavailability of 20 nm PtNPs was only suppressed by NOM with a low reduced sulfur content. The physiological elimination of Pt accumulated after dissolved Pt(IV) exposure was slow and constant. In contrast, the elimination of Pt accumulated after PtNP exposures exhibited a triphasic pattern likely involving in vivo PtNP dissolution. This work highlights the importance of PtNP size and interfacial interactions with NOM on Pt bioavailability and suggests that in vivo PtNP transformations could yield unexpectedly higher adverse effects to organisms than dissolved exposure alone.

Environ. Sci. Technol.