R. A. Bodaly

Whole-ecosystem study shows rapid fish-mercury response to changes in mercury deposition

Methylmercury contamination of fisheries from centuries of industrial atmospheric emissions negatively impacts humans and wildlife worldwide. The response of fish methylmercury concentrations to changes in mercury deposition has been difficult to establish because sediments/soils contain large pools of historical contamination, and many factors in addition to deposition affect fish mercury. To test directly the response of fish contamination to changing mercury deposition, we conducted a whole-ecosystem experiment, increasing the mercury load to a lake and its watershed by the addition of enriched stable mercury isotopes. The isotopes allowed us to distinguish between experimentally applied mercury and mercury already present in the ecosystem and to examine bioaccumulation of mercury deposited to different parts of the watershed. Fish methylmercury concentrations responded rapidly to changes in mercury deposition over the first 3 years of study. Essentially all of the increase in fish methylmercury concentrations came from mercury deposited directly to the lake surface. In contrast, <1% of the mercury isotope deposited to the watershed was exported to the lake. Steady state was not reached within 3 years. Lake mercury isotope concentrations were still rising in lake biota, and watershed mercury isotope exports to the lake were increasing slowly. Therefore, we predict that mercury emissions reductions will yield rapid (years) reductions in fish methylmercury concentrations and will yield concomitant reductions in risk. However, a full response will be delayed by the gradual export of mercury stored in watersheds. The rate of response will vary among lakes depending on the relative surface areas of water and watershed.

Recovery of Mercury-Contaminated Fisheries

Abstract In this paper, we synthesize available information on the links between changes in ecosystem loading of inorganic mercury (Hg) and levels of methylmercury (MeHg) in fish. Although it is widely hypothesized that increased Hg load to aquatic ecosystems leads to increases in MeHg in fish, there is limited quantitative data to test this hypothesis. Here we examine the available evidence from a range of sources: studies of ecosystems contaminated by industrial discharges, observations of fish MeHg responses to changes in atmospheric load, studies over space and environmental gradients, and experimental manipulations. A summary of the current understanding of the main processes involved in the transport and transformation from Hg load to MeHg in fish is provided. The role of Hg loading is discussed in context with other factors affecting Hg cycling and bioaccumulation in relation to timing and magnitude of response in fish MeHg. The main conclusion drawn is that changes in Hg loading (increase or decrease) will yield a response in fish MeHg but that the timing and magnitude of the response will vary depending of ecosystem-specific variables and the form of the Hg loaded.

Temperature, growth and dietary effects on fish mercury dynamics in two Ontario lakes

A bioenergetics-based model was used to investigate the effects of temperature, growth and dietary exposure on methylmercury dynamics in walleye (Stizostedion vitreum) and yellow perch (Perca flavescens) from two lakes sampled in northwestern Ontario. Orange Lake was smaller, warmer, had slower fish growth and higher mercury concentrations in yearling yellow perch and walleye (three fold difference in 40 cm walleye) than Trout Lake. The model was applied to test the hypothesis that higher water temperatures in Orange Lake increased metabolic needs, food consumption and mercury uptake in fish. The effects of different growths rates in the lakes were also considered. Temperature/metabolic effects and growth effects on internal methylmercury dynamics in walleye and perch were predicted to occur but be of secondary importance. Different dietary exposure to methylmercury was likely the dominant source of variation in fish mercury concentrations between the two lakes.

Impacts of Reservoir Creation on the Biogeochemical Cycling of Methyl Mercury and Total Mercury in Boreal Upland Forests

The FLooded Upland Dynamics Experiment (FLUDEX) at the Experimental Lakes Area (ELA) in northwest Ontario was designed to test the hypothesis that methylmercury (MeHg) production in reservoirs is related to the amount, and subsequent decomposition, of flooded organic matter. Three upland forest sites that varied in the amounts of organic carbon stored in vegetation and soils (Low C, 30,870 kg C ha−1; Medium C, 34,930 kg C ha−1; and High C, 45,860 kg C ha−1) were flooded annually from May to September with low-organic carbon, low-MeHg water pumped from a nearby lake. Within five weeks of flooding, MeHg concentrations in the reservoir outflows exceeded those in reservoir inflows and remained elevated for the duration of the experiment, peaking at 1.60 ng L−1 in the Medium C reservoir. We estimated the net production of MeHg in each reservoir by calculating annual changes in pools of MeHg stored in flooded soils, periphyton, zooplankton, and fish. Overall, there was an initial pulse of MeHg production (range = 120–1590 ng m−2 day−1) in all FLUDEX reservoirs that lasted for 2 years, after which time net demethylation (range = 360–1230 ng MeHg degraded m−2 day−1) began to reduce the pools of MeHg in the reservoirs, but not back to levels found prior to flooding. Rates of MeHg production were generally related to the total amount of organic carbon flooded to create the reservoirs. Large increases in MeHg stores in soils compared to those in water and biota indicate that flooded soils were the main sites of MeHg production. This study should assist hydroelectric utilities and government agencies in making informed decisions about selecting sites for future reservoir development to reduce MeHg contamination of the reservoir fisheries.

Carbon Dioxide and Methane Production in Small Reservoirs Flooding Upland Boreal Forest

The FLooded Uplands Dynamics EXperiment (FLUDEX) was designed to assess the impact of reservoir creation on carbon cycling in boreal forests by (a) determining whether production of the greenhouse gases (GHG) carbon dioxide (CO2) and methane (CH4) in reservoirs is related to the amount of organic carbon (OC) stored in the flooded landscape, (b) examining temporal trends in GHG production during initial stages of flooding, and (c) considering the net difference between GHG fluxes before and after flooding to estimate the true effect of reservoir creation on atmospheric GHG levels. Three forested sites that varied in the amount of OC stored in soils and vegetation (30,870–45,860 kg C ha–1) were experimentally flooded from June to September in 1999–2001. Throughout the study, net CO2 and CH4 production in all three reservoirs was not related to overall site OC storage. During the 1st flooding season, net CO2 production in the three reservoirs was 703–797 kg C ha–1, but it decreased during the 2nd and 3rd flooding seasons to between 408 and 479 kg C ha–1. However, CH4 production increased in all reservoirs with each flooding season, from about 3.2–4.6 kg C ha–1 in 1999 to 12.8–24.9 kg C ha–1 in 2000 and 29.7–35.2 kg C ha–1 in 2001. Over the long term, effects of boreal reservoir creation on atmospheric GHG levels may be largely due to net changes in CH4 cycling between the undisturbed and flooded ecosystems.

Temporal changes in the distribution, methylation, and bioaccumulation of newly deposited mercury in an aquatic ecosystem.

Our objective was to examine how the behavior of atmospheric mercury (Hg) deposited to boreal lake mesocosms changed over time. We added inorganic Hg enriched in a different stable isotope in each of two years, which allowed us to differentiate between Hg added in the first and second year. Although inorganic Hg and methylmercury (MeHg) continued to accumulate in sediments throughout the experiment, the availability of MeHg to the food web declined within one year. This decrease was detected in periphyton, zooplankton, and water mites, but not in gomphid larvae, amphipods, or fish. We suggest that reductions in atmospheric Hg deposition should lead to decreases in MeHg concentrations in biota, but that changes will be more easily detected in short-lived pelagic species than long-lived species associated with benthic food webs.

Distribution and biogeochemical controls on net methylmercury production in Penobscot River marshes and sediment

The distribution of mercury and methylmercury (MeHg) in sediment, mudflats, and marsh soils of the Hg-contaminated tidal Penobscot River was investigated, along with biogeochemical controls on production. Average total Hg in surface samples (0-3 cm) ranged from 100 to 1200 ng/g; average MeHg ranged from 5 to 50 ng/g. MeHg was usually highest at or near the surface except in highly mobile mudflats. Although total Hg concentrations in the Penobscot are elevated, it is the accumulation of MeHg that stands out in comparison to other ecosystems. Surface soils in the large Mendall Marsh, about 17 km downstream from the contamination source, contained particularly high %MeHg (averaging 8%). In Mendall marsh soil porewaters, MeHg often accounted for more than half of total Hg. Salt marshes are areas of particular concern in the Penobscot River, for they are depositional environments for a Hg-contaminated mobile pool of river sediment, hot spots for net MeHg production, and sources of risk to marsh animals. We hypothesized that exceptionally low mercury partitioning between the solid and aqueous phases (with log Kd averaging ~4.5) drives high MeHg in Penobscot marshes. The co-occurrence of iron and sulfide in filtered soil porewaters, sometimes both above 100 μM, suggests the presence of nanoparticulate and/or colloidal metal sulfides. These colloids may be stabilized by high concentrations of aromatic and potentially sulfurized dissolved organic matter (DOM) in marsh soils. Thus, Hg in Penobscot marsh soils appears to be in a highly available for microbial methylation through the formation of DOM-associated HgS complexes. Additionally, low partitioning of MeHg to marsh soils suggests high MeHg bioavailability to animals. Overall, drivers of high MeHg in Penobscot marshes include elevated Hg in soils, low partitioning of Hg to solids, high Hg bioavailability for methylation, rapidly shifting redox conditions in surface marsh soils, and high rates of microbial activity.

Elevated mercury in blood and feathers of breeding marsh birds along the contaminated lower Penobscot River, Maine, USA

Mercury (Hg) concentrations in the blood and feathers of five species of migratory marsh birds, Nelsons sparrow (Ammodramus nelson subvirgatus), song sparrow (Melospiiza melodia), swamp sparrow (Melospiza geogiana), red-winged blackbird (Agelaius phoeniceus), and Virginia rail (Rallus limicola), breeding in marshes along the lower Penobscot River, Maine, far exceeded reference concentrations, exceeded concentrations associated with reproductive health, and are the highest Hg concentrations reported to date for several species. Blood Hg concentrations in adult Nelsons sparrows were greatest in 2007, at 6.6μg/gww (geometric mean) and in 2012, at 6.5μg/gww and greatest in red-winged blackbirds in 2012, 8.0μg/gww. Mercury in blood increased with residence time on the contaminated marshes at an estimated rate of 0.04 to 0.07μg/gww per day. Feather mercury concentrations in specific primary, secondary and tail feathers (P1, S2, R6) were strongly associated with exposure location at the time of feather formation. Geometric mean Hg concentrations in primary feathers (P1) reached 39.6μg/gfw in 2010 in Nelsons sparrows. The paper documents the dynamic nature of Hg concentrations in avian blood and feathers, an important consideration in contaminant study design, and the increased risk to marsh birds posed by Hg deposition from upstream sources.

Fifty years after its discharge, methylation of legacy mercury trapped in the Penobscot Estuary sustains high mercury in biota

Fifty years ago, the Penobscot Estuary was contaminated by mercury discharged from the chlor-alkali plant located in Orrington, Maine, USA. Almost all of the mercury was discharged from the plant during the late 1960s and early 1970s. Despite the much lower mercury discharges in recent decades, present-day concentrations in surface sediment remain high (averaging 350-1100 ng/g dw) and are still high in blood of marsh birds (up to 10.5 μg/g), black duck muscle (0.8 μg/g), and lobster muscle (0.4 μg/g). Methyl mercury (MeHg) concentrations in marsh birds exceed levels that impair reproduction. There are health advisories for duck hunters and closures of shellfish fisheries. These continuing high mercury concentrations are caused by the trapping of legacy mercury in a mobile pool of sediment that is retained in the upper estuary above a tidally forced salinity front, which travels up and down the estuary each tidal cycle - slowing the transport of particulate mercury to Penobscot Bay. The trapped legacy mercury continues to be available for methylation 50 years after it first entered the estuary. This is demonstrated by the fact that rates of MeHg production are positively related to the inorganic mercury concentration in parts of the estuary with elevated concentrations of legacy mercury. Thus, remediation measures that would lower the THg concentration in surface sediment would lower the MeHg in birds, fish and shellfish. All of this new information leads us to recommend two remediation options. Addition of mercury binding agents may lower mercury concentrations in birds in some wetland areas. System-wide, we also recommend Enhanced Natural Recovery (ENR), a novel approach that involves the partial removal of the contaminated mobile sediment pool followed by replacement with clean-clay particulates to dilute inorganic mercury concentrations, which would lower methylation rates and mercury concentrations in biota.

Spatial and temporal trends of mercury in the aquatic food web of the lower Penobscot River, Maine, USA, affected by a chlor-alkali plant

Mercury (Hg) concentrations in aquatic biota, including fish and shellfish, were measured over the period 2006-2012 in the lower Penobscot River and upper estuary (Maine, USA). The Penobscot is a system contaminated with Hg by a chlor-alkali plant that operated from 1967 to 2000, discharging 6-12 tons of mercury into the river. Mercury levels in aquatic biota were highest at sites downstream of the chlor-alkali plant and spatial trends were similar to those of sediments. Mean total Hg concentrations in fish muscle (adjusted for size or age) in the most affected areas were 521 (480, 566; 95% CI) ng/g ww in American eels, 321 (261,395) in mummichog, 121 (104, 140) in rainbow smelt, 155 (142,169) in tomcod, 55.2 (42.7,71.4) in winter flounder, and 328 (259,413) in American lobster tail and 522 (488,557) ng/g dw in blue mussel. Levels exceeded the 50 ng/g ww considered protective for piscivorous predators and were of concern for human health, with American eels and American lobster exceeding Maines mercury action level of 200 ng/g ww. Calculations of trophic position (using nitrogen isotopes) suggested that the spatial patterns observed in total Hg concentrations were not due to changes in feeding habits of the species. Fish feeding in benthic food webs, as defined by stomach content and stable carbon isotope analyses, showed no change in Hg concentrations over time. In contrast, declining trends in Hg were found in two species dependent on pelagic food webs. The absence of declines in Hg concentrations in the benthically-based food webs, despite the fact that most Hg was discharged into the system >40 years ago, is consistent with the long recovery predicted from dated sediment cores and from similar studies elsewhere.