Subfossil Chironomid Assemblages as Indicators of Remedial Efficacy in the Historically Contaminated St. Lawrence River at Cornwall, Ontario.

Long-term data are required to quantify the impacts of historic industrial pollution and subsequent remedial action on the nearshore benthic community in the St. Lawrence River Area of Concern at Cornwall, Ontario. Specifically, high-quality temporal records are needed to understand changes in benthic invertebrate assemblages in response to multiple possible drivers including industrial pollution, environmental heterogeneity, and climate warming. We compare long-term records of subfossil chironomid assemblages and geochemical variables among sediment cores from two Cornwall sites with differing pollution histories and a minimally disturbed downstream reference site. Chironomids were functionally absent from the Cornwall sediment cores when mercury and zinc concentrations were elevated. As metal concentrations decreased in more recent sediment intervals, chironomid abundance and the relative abundance of pollution-sensitive taxa increased. Recently deposited sediment in all three sediment cores display increased relative abundance of warm-water, macrophyte-associated taxa. We conclude that these temporal changes in chironomid assemblages provide evidence for ecological recovery for both of the impacted sites, consistent with the objectives of the current management strategy. These findings advance our understanding of industrial impacts on fluvial chironomid ecology, directly inform local management strategies, and further develop the application of chironomids as bioindicators for contaminated sediments.

Nearshore Sedimentary Mercury Concentrations Reflect Legacy Point Sources and Variable Sedimentation Patterns Under a Natural Recovery Strategy.

The St. Lawrence River at Cornwall, Ontario, Canada, received substantial inputs of mercury from local, shoreline-based industries through much of the 20th century. Although emission controls were implemented in the late 20th century to reduce the influx of mercury and other metals entering the river, legacy contamination of riverine sediments continues to be a concern. Monitored natural recovery was prescribed in 2005 to remediate contaminated sediments; however, few surveys have been undertaken to examine its effectiveness on shallow, nearshore sediments in contaminated areas. Surface sediments were collected at shallow, nearshore sites in contaminated zones and upstream reference areas to evaluate the current state of sedimentary contamination of mercury and other metals. A Getis-Ord Gi* "hot spot" analysis was employed to assess the spatial distribution of contaminants. In addition, 3 sediment cores were collected from contaminated zones and dated using radioisotopes (210 Pb) to assess sedimentation patterns over time. Results indicated that surface sediments from contaminated zones remained elevated in mercury relative to reference sites but spatial distribution of contaminants was highly heterogeneous. Dated sediment cores suggested that sedimentation was not occurring consistently across all areas; variable sedimentation and resuspension patterns over small spatial scales were likely factors driving heterogeneous sedimentary contamination. Such patterns complicate remediation strategies because unburied sediments may serve as continuing sources of contaminants to the ecosystem. Environ Toxicol Chem 2021;40:1788-1799. © 2021 SETAC.

Mercury Concentrations in Sentinel Fish Exposed to Contaminated Sediments Under a Natural Recovery Strategy Within the St. Lawrence River Area of Concern at Cornwall, Ontario, Canada.

Legacy mercury (Hg) sediment deposits are a long-term issue within the St. Lawrence River (Cornwall) area of concern with three depositional areas along the Cornwall, ON waterfront containing sediments that exceed the Ontario Sediment Quality Guidelines for Hg. Assessing the bioavailability of these Hg-contaminated sediments plays a crucial role in evaluating the effectiveness of the Cornwall Sediment Strategy based on a natural recovery approach. We collected specimens of fallfish (Semotilus corporalis), round goby (Neogobius melanostomus), and yellow perch (Perca flavescens) to assess spatial and temporal trends of Hg concentrations in various areas along the Cornwall waterfront, including zones of contaminated sediments and non-contaminated reference sites. This study revealed that (1) Hg concentrations in fish collected from the contaminated zones remain greater than those of fish from non-impacted locations, indicating that natural recovery is not yet achieved, (2) total Hg concentrations in yellow perch collected in 2016 were greater than those obtained during a previous assessment, indicating a reversal of the previously observed long-term declines, and (3) total Hg concentrations in yellow perch collected at the outlet of Gray's Creek compared with yellow perch from contaminated zones, suggesting other important inputs of Hg to the ecosystem than the legacy contaminated sediments.

Dynamic mass balance model for mercury in the St. Lawrence River near Cornwall, Ontario, Canada.

A dynamic mass balance model was developed for the St. Lawrence River near Cornwall, Ontario that predicts and hindcasts mercury concentrations and fluxes in three forms, elemental Hg (Hg(0)), divalent mercury (Hg(2+)), and methyl mercury (MeHg), in a six compartment environment (air, water, porewater, sediment, periphyton, and benthic invertebrates). Our objective was to construct a dynamic mass balance model for mercury in the St. Lawrence River near Cornwall, Ontario based on the framework and results of a steady-state mass balance model developed previously for this site. The second objective was to estimate industrial mercury emissions based on mercury residues deposited in sediments prior to 1970, the year when regulations were implemented to reduce mercury pollution in the environment. We compiled mercury concentrations, fluxes, and transformation rates from previous studies completed in this section of the river (area of approximately 100km(2)) to develop the model. Estimated mercury concentrations in all media were similar to measured data (R(2)=0.99), with only minor exceptions, providing a satisfactory overall description of the mercury loadings and transformation rates of the different mercury species. The estimated historical emissions prior to 1970 from local industries along the Cornwall waterfront were approximately 400kgyear(-1). A storm sewer discharge of 5000m(3)/day resulted in a significant increase in mercury concentrations, particularly in sediment (617ngg(-1) to 624ngg(-1); p=0.004). Model results suggest that discharges of mercury from sources such as local industries and storm sewers have an impact on mercury in media such as sediment and water. This model should provide a basis for predicting and hindcasting mercury concentrations in other river environments as well, because it considers three distinct forms of mercury, and contains environmental media common to all rivers, including some (e.g. periphyton) not typically included in previous mercury models.

Mercury concentrations in amphipods and fish of the Saint Lawrence River (Canada) are unrelated to concentrations of legacy mercury in sediments.

Past industrial activity at Cornwall, Ontario, Canada has contaminated Lake Saint Francis, a fluvial lake on the Saint Lawrence River, with mercury (Hg). A spatial survey of Hg concentrations in sediments, amphipods, and yellow perch (Perca flavescens) in 2008 inferred current sources of Hg to the lake and spatial variations in risks to human consumers. Patterns of total and methyl Hg concentrations in sediment reflected upstream inputs, declining concentrations downstream, and highest concentrations at north shore sites near industrial sources; concentrations were lowest on the south shore because river currents limit north-south advective exchange. Surprisingly, concentrations of total or methyl Hg in sediments and pore water were unrelated to concentrations in amphipods and yellow perch. Concentrations in biota, and risks to consumers of fish, were highest at north shore sites near tributaries, and not at the most contaminated industrial sites. These results suggest that 'legacy' Hg in surficial sediments is not bioavailable to aquatic biota; tributaries and atmospheric deposition are possible sources of bioavailable Hg; and that sediment remediation would not resolve issues of Hg in fish. Fish consumption advisories for the entire lake based on single samples of fish could over- or under-protect consumers, depending on sampling location. To understand the actual risk to fish consumers for a large and complex lake system with multiple sources of Hg, more intensive sampling is needed to assess the spatial distribution of risk.

Steady-state mass balance model for mercury in the St. Lawrence River near Cornwall, Ontario, Canada.

We have developed a local mass balance model for the St. Lawrence River near Cornwall, Ontario that describes the fate and transport of mercury in three forms, elemental, divalent, and methylated, in a five compartment environment (air, water, sediments, periphyton, and benthos). Our objective was to construct a steady-state mass balance model to determine the dominant sources and sinks of mercury in this environment. We compiled mercury concentrations, fluxes, and transformation rates from previous studies completed in this section of the river to develop the model. The inflow of mercury was the major source to this system, accounting for 0.42 mol month(-1), or 95.5% of all mercury inputs, whereas outflow was 0.28 mol month(-1), or 63.6% of all losses, and sediment deposition was 0.12 mol month(-1), or 27.3% of all losses. Uncertainty estimates were greatest for advective fluxes in surface water, porewater, periphyton, and benthic invertebrates.

Ebullition rates and mercury concentrations in St. Lawrence river sediments and a benthic invertebrate.

Ebullition, the release of gas from anaerobic decomposition in sediments, was recorded in a mercury-contaminated depositional zone (Zone 1) of the St. Lawrence River Area of Concern in Cornwall, Ontario, Canada. The aim of the present study was to test if this disturbance affected the bioavailability of total mercury (THg) and methylmercury (MeHg) in surficial sediments to a benthic invertebrate (Echinogammarus ischnus). Ebullition rates ranged from <1 to 2,800 ml/m(2) daily, with methane gas comprising 29 to 84% of the total. No direct effects of ebullition were found on either abiotic (sediment or pore water THg or MeHg concentrations) or biotic (amphipod THg or MeHg concentrations) variables measured. Instead, amphipod MeHg concentrations were best predicted by pore water THg and MeHg concentrations, organic matter of surficial sediments, and water depth and location. Trend surface analyses demonstrated that a shallow, southwestern part of Zone 1 was most contaminated with pore water mercury, which decreased in a gradient toward the northeast. Further study is needed to determine if the amount of sediment resuspended by ebullition affects the spatial distribution of mercury.

Mercury transport between sediments and the overlying water of the St. Lawrence River area of concern near Cornwall, Ontario.

Contaminated sediments in the St. Lawrence River remain a difficult problem despite decreases in emissions. Here, sediment and pore water phases were analyzed for total mercury (THg) and methyl mercury (MeHg) and diffusion from the sediment to the overlying water was 17.5 + or - 10.6 SE ng cm(-2) yr(-1) for THg and 3.8 + or - 1.7 SE ng cm(-2) yr(-1) for MeHg. These fluxes were very small when compared to the particle-bound mercury flux accumulating in the sediment (183 + or - 30 SE ng cm(-2) yr(-1)). Studies have reported that fish from the westernmost site have higher Hg concentrations than fish collected from the other two sites of the Cornwall Area of Concern, which could not be explained by differences in the Hg flux or THg concentrations in sediments, but the highest concentrations of sediment MeHg, and the greatest proportions of MeHg to THg in both sediment and pore water were observed where fish had highest MeHg concentrations.

Sediment mercury dynamics and historical trends of mercury deposition in the St. Lawrence River area of concern near Cornwall, Ontario, Canada.

The St. Lawrence River near Cornwall, Ontario was designated an Area of Concern by the International Joint Commission in 1985. Sediments from this area have historically been contaminated with mercury (Hg), and although concentrations have decreased since the 1970s, they still remain high. Nine sediment cores were collected from three sites within the Area of Concern in 2004/05 to determine the variability in historical profiles of Hg deposition to the river. Sediment and pore water phases were analyzed for total mercury (THg) and methyl mercury (MeHg) and cores were analyzed for 210Pb to determine chronologies of sedimentation at these sites. Mercury diffusion rates in pore waters within the sediment column were determined to be very low (between 0 and 2.15 ng cm(-2) year(-1), n = 3) compared to the recent Hg sedimentation rates at these sites (183+/- 30 ng cm(-2) year(-1) SE, n = 9) determined by multiplying surface Hg concentrations with 210Pb-derived sedimentation rates. These results indicate that Hg profiles in these cores accurately depict historical releases of Hg to the river bed. The influence of federal regulations in the early 1970s to restrict Hg emissions to the river was apparent in these dated sediment cores, as were the closures of several local industries in the mid 1990s. Mercury accumulation rates prior to 1970 were 60 times higher than those occurring after 1995. Methyl mercury showed surface enrichment in most of these sediment cores providing evidence that mercury methylation occurred most rapidly near the sediment surface.