Mercury concentrations in the Laurentian Great Lakes waters are among the lowest reported in the literature, while game fish concentrations approach consumption advisory limits, particularly in Lakes Superior, Huron, and Michigan, indicating efficient methylmercury transfer from water to game fish. To determine if increased transfer efficiency is evident within the lower food web, we measured (2010–2018) mercury and dissolved organic carbon (DOC) in water, and in size-sieved seston, dietary tracers (carbon and nitrogen isotope ratios), phytoplankton methylmercury bioaccumulation, and methylmercury biomagnification between increasing seston size fractions. We observed consistently low filter-passing methylmercury (<0.010 ng L^–1) and comparatively variable DOC (1.1 to 3.4 mg L^–1) concentrations. Methylmercury biomagnification factors between size-sieved seston were similar between lakes. Bioaccumulation factors in phytoplankton were among the highest in the literature (log 5.5 to 6.1), exceeding those in oceans, smaller lakes, and streams, and was influenced by DOC. Higher bioaccumulation rates increase the susceptibility of methylmercury accumulation into the food web. Because mercury is dominantly delivered to the Great Lakes through the atmosphere and the biota therein is highly susceptible to methylmercury uptake, we propose that the Laurentian Great Lakes are excellent sentinels to trace the success of efforts to decrease global mercury emissions (e.g., Minamata Treaty) in the future.

Mercury monitoring results from about 300 Morone saxatilis (striped bass) muscle tissue samples collected by the State of Utah from Lake Powell resulted in a Utah/Arizona fish consumption advisory issued in 2012 for approximately the lower 100 kilometers of the reservoir. Chemical, physical, and biological data were collected during two synoptic sampling cruises on Lake Powell during May/June 2014 and August 2015 to test three hypotheses associated with a conceptual model developed to explain the observed geographic concentration gradient of Hg in fish tissue samples. This model proposes that in the transition from a primarily riverine system to a reservoir, there is a change in the concentration and composition of water-column particulate material, increasing in the proportion of organic content moving downstream, as the larger size fractions of the inorganic particulate load are deposited in the upper reservoir. This change alleviates light limitation of phytoplankton production and leads to a higher proportion of autochthonous primary production in the downstream direction. This, in turn, drives increased microbial methylmercury (MeHg) production in the benthos and potentially the water column, in the downstream direction, and results in the observed elevated fish Hg levels in the lower part of the reservoir. The model also proposes that there are differences between the main stem of Lake Powell and side canyons, embayments, or secondary rivers entering the reservoir, in terms of Hg cycling dynamics and bioaccumulations, driven mainly by differences in hydrology. Finally, seasonal differences in Hg dynamics within the reservoir are proposed, based on seasonal dynamics associated with primary production and the physical process of seasonal stratification.A total of three statistically testable hypotheses were proposed and postulated that measurable differences in key Hg and non-Hg metrics exist between: (1) the upper and lower reservoir; (2) main stem and river arm/side canyon/embayment sites; and (3) early-season (May/June 2014, less stratified) and late-season (August 2015, stratified) conditions. Statistically modeled least square means in combination with the graphical analysis of Hg and non-Hg parameters were used to examine the data collected during the study and test these hypotheses. Data collected during the study are included in a U.S. Geological Survey data release and are available online at https://doi.org/10.5066/F74X560J.In general, water-column, plankton, and surface sediment samples collected during the synoptic sampling cruises are supportive of the three hypotheses associated with the conceptual model. In support of hypothesis 1 (comparing upper and lower reservoir sites), the least square mean for turbidity was higher in the upper reservoir. In contrast, surface water particulate organic carbon (as a percentage of total particulate mass), particulate MeHg (by mass [in nanograms per gram] and as a percentage of total mercury [THg]), and particulate-dissolved partitioning coefficients for THg and MeHg were higher in the lower reservoir. Plankton THg concentrations also were significantly (probability [p] less than (<) 0.05) higher in the lower reservoir. Surface sediment metrics in support of hypothesis 1 include higher MeHg production potential rates in the lower reservoir. In contrast, there were no statistically significant differences between the upper and lower reservoir for surface sediment percent of MeHg and MeHg concentration, percent MeHg, or methylation rate constants. These spatial trends associated with hypothesis 1 indicate a pathway for enhanced Hg bioavailability in the lower reservoir.Hypothesis 2, which tested for differences between main stem and river arm/side canyon/embayment sites, was supported by a number of water-column parameters, including particulate THg and MeHg concentrations by mass (in nanograms per gram) and percent particulate MeHg being significantly (p<0.05) higher in the river arms, side canyons, and embayments relative to the main stem channel. Plankton MeHg concentrations (by mass [in nanograms per gram] and volume [in nanograms per liter] and as a percentage of THg) were elevated in river arm/side canyon/embayment sites compared to main stem sites, indicating an enhanced potential for MeHg bioaccumulation at the base of the pelagic food web in river arms, side canyons, and embayments. In contrast, few of the sediment metrics differed between main stem and river arm/side canyon/embayment sampling sites; however, the potential for MeHg degradation in surface sediment was significantly higher in the main stem. The data indicate that river arm/side canyon/embayment sites may experience enhanced Hg bioaccumulation, compared to the main stem, because of higher MeHg levels at the base of the pelagic food web. This conclusion is supported by the elevated Hg detected in striped bass muscle tissue samples collected in the San Juan Arm during this study (2014). Fish collected from the lower reservoir exhibited a distinct Hg isotopic signature that was enriched in delta (δ)202Hg and capital delta (Δ)199Hg relative to fish samples collected from either Good Hope Bay or the San Juan Arm.Hypothesis 3 tested for differences between early (May/June) high-flow and late (August) low-flow seasons. This test was supported by a range of non-Hg metrics (nitrate, phosphate, chlorophyll a, dissolved oxygen, fluorescent dissolved organic matter, temperature, and pH) that reflect the increase in chlorophyll a, decrease in nutrients, and buildup of stratified conditions in the transition from early- to late-season sampling periods. Significant seasonal differences also were noted for multiple Hg metrics, including (a) water-column filtered and particulate (by mass) MeHg and THg concentrations; (b) plankton MeHg and THg concentration (by mass); and (c) sediment percent MeHg, Hg(II)-methylation rate constant, and microbial ribosomal...

An LC/MS method was developed and validated for the quantitative determination and confirmation of antimycin-A (ANT-A) in water from lakes or streams. Three different water sample volumes (25, 50, and 250 mL) were evaluated. ANT-A was stabilized in the field by immediately extracting it from water into anhydrous acetone using SPE. The stabilized concentrated samples were then transported to a laboratory and analyzed by LC/MS using negative electrospray ionization. The method was determined to have adequate accuracy (78 to 113% recovery), precision (0.77 to 7.5% RSD with samples ≥500 ng/L and 4.8 to 17% RSD with samples ≤100 ng/L), linearity, and robustness over an LOQ range from 8 to 51 600 ng/L.

The whole-fish total mercury (Hg) concentrations were determined in 25 mature female and 26 mature male white suckers (Catostomus commersonii) caught during their spawning run in the Kewaunee River, a tributary to Lake Michigan. The age of each fish was estimated using thin-sectioned otoliths, and total length (TL) and weight were determined for each fish. When adjusted for the effect of age, males were found to be 7% higher in Hg concentration than females. Nearly all (about 98%) of the Hg found in the white suckers was determined to be methylmercury. In an earlier study on the same 51 white suckers from the Kewaunee River spawning run, males were found to be 18% higher than females in polychlorinated biphenyl (PCB) concentration. We determined that the ratio of Hg concentration to PCB concentration in females was significantly higher than that in males. Thus, sex significantly interacted with contaminant type (Hg or PCBs) in determining contaminant concentrations. The most plausible explanation for this interaction was that males eliminated Hg at a faster rate than females, most likely due to the boosting of the Hg-elimination rate by certain androgens such as testosterone and 11-ketotestosterone. Hg concentrations in the white suckers were well below federal guidelines for fish consumption.

Mercury is a global contaminant that can be detrimental to wildlife and human health. Anthropogenic emissions and point sources are primarily responsible for elevated mercury concentrations in sediments and waters. Mercury can physically move and chemically transform in the environment, resulting in biomagnification of mercury, in the form of methylmercury, in the food web and causing elevated mercury concentrations in upper trophic levels. The ability to measure total mercury concentrations in the environment has existed for several decades and makes it possible to detect hotspots that might exist because of ongoing or previous anthropogenic activity. However, recent (within the past 15 years) developments in mass spectrometry have made it possible to complete low level stable isotope analysis allowing for the determination of mercury sources—natural and anthropogenic—in the environment through “fingerprinting.” Grubers Grove Bay in Lake Wisconsin, the focus area of this study, was determined to have elevated mercury levels even after multiple remediation efforts, resulting in its listing on the Federal list of impaired waters pursuant to the Clean Water Act. Adjacent to the bay is the former Badger Army Ammunition Plant, which manufactured ammunition for the U.S. Army during the early and middle 20th century, after which it was put on standby before being fully decommissioned. This study assesses mercury concentrations in the sediments and suspended particulate matter of Grubers Grove Bay, Wiegands Bay, and upstream sites, and in adjacent soils on the former Badger Army Ammunition Plant site. This study confirmed that mercury contamination exists in the sediments of Grubers Grove Bay even after dredging attempts by the U.S. Army. Additionally, using isotope ratios and a two-endmember mixing model, it was determined that soil from within Badger Army Ammunition Plant’s former site contributed a substantial amount of mercury to the bay. This result was supported by an observed gradient of high to low mercury concentrations from the innermost (nearest Badger Army Ammunition Plant) to the outermost (farthest from Badger Army Ammunition Plant) part of the bay.