Bioaccumulation of methylmercury within the marine food web of the outer Bay of Fundy, Gulf of Maine.

Mercury and methylmercury were measured in seawater and biota collected from the outer Bay of Fundy to better document mercury bioaccumulation in a temperate marine food web. The size of an organism, together with δ13 C and δ15 N isotopes, were measured to interpret mercury levels in biota ranging in size from microplankton (25µm) to swordfish, dolphins and whales. Levels of mercury in seawater were no different with depth and not elevated relative to upstream sources. The δ13 C values of primary producers were found to be inadequate to specify the original energy source of various faunas, however, there was no reason to separate the food web into benthic, demersal and pelagic food chains because phytoplankton has been documented to almost exclusively fuel the ecosystem. The apparent abrupt increase in mercury content from "seawater" to phytoplankton, on a wet weight basis, can be explained from an environmental volume basis by the exponential increase in surface area of smaller particles included in "seawater" determinations. This physical sorption process may be important up to the macroplankton size category dominated by copepods according to the calculated biomagnification factors (BMF). The rapid increase in methylmercury concentration, relative to the total mercury, between the predominantly phytoplankton (<125µm) and the zooplankton categories is likely augmented by gut microbe methylation. Further up the food chain, trophic transfer of methylmercury dominates resulting in biomagnification factors greater than 10 in swordfish, Atlantic bluefin tuna, harbour porpoise, Atlantic white-sided dolphin and common thresher shark. The biomagnification power of the northern Gulf of Maine ecosystem is remarkably similar to that measured in tropical, subtropical, other temperate and arctic oceanic ecozones.

Mercury sources and fate in the Gulf of Maine.

Most human exposure to mercury (Hg) in the United States is from consuming marine fish and shellfish. The Gulf of Maine is a complex marine ecosystem comprising twelve physioregions, including the Bay of Fundy, coastal shelf areas and deeper basins that contain highly productive fishing grounds. Here we review available data on spatial and temporal Hg trends to better understand the drivers of human and biological exposures. Atmospheric Hg deposition from U.S. and Canadian sources has declined since the mid-1990s in concert with emissions reductions and deposition from global sources has increased. Oceanographic circulation is the dominant source of total Hg inputs to the entire Gulf of Maine region (59%), followed by atmospheric deposition (28%), wastewater/industrial sources (8%) and rivers (5%). Resuspension of sediments increases MeHg inputs to overlying waters, raising concerns about benthic trawling activities in shelf regions. In the near coastal areas, elevated sediment and mussel Hg levels are co-located in urban embayments and near large historical point sources. Temporal patterns in sentinel species (mussels and birds) have in some cases declined in response to localized point source mercury reductions but overall Hg trends do not show consistent declines. For example, levels of Hg have either declined or remained stable in eggs from four seabird species collected in the Bay of Fundy since 1972. Quantitatively linking Hg exposures from fish harvested from the Gulf of Maine to human health risks is challenging at this time because no data are available on the geographic origin of seafood consumed by coastal residents. In addition, there is virtually no information on Hg levels in commercial species for offshore regions of the Gulf of Maine where some of the most productive fisheries are located. Both of these data gaps should be priorities for future research.

Response of a macrotidal estuary to changes in anthropogenic mercury loading between 1850 and 2000.

Methylmercury (MeHg) bioaccumulation in marine food webs poses risks to fish-consuming populations and wildlife. Here we develop and test an estuarine mercury cycling model for a coastal embayment of the Bay of Fundy, Canada. Mass budget calculations reveal that MeHg fluxes into sediments from settling solids exceed losses from sediment-to-water diffusion and resuspension. Although measured methylation rates in benthic sediments are high, rapid demethylation results in negligible net in situ production of MeHg. These results suggest that inflowing fluvial and tidal waters, rather than coastal sediments, are the dominant MeHg sources for pelagic marine food webs in this region. Model simulations show water column MeHg concentrations peaked in the 1960s and declined by almost 40% by the year 2000. Water column MeHg concentrations respond rapidly to changes in mercury inputs, reaching 95% of steady state in approximately 2 months. Thus, MeHg concentrations in pelagic organisms can be expected to respond rapidly to mercury loading reductions achieved through regulatory controls. In contrast, MeHg concentrations in sediments have steadily increased since the onset of industrialization despite recent decreases in total mercury loading. Benthic food web MeHg concentrations are likely to continue to increase over the next several decades at present-day mercury emissions levels because the deep active sediment layer in this system contains a large amount of legacy mercury and requires hundreds of years to reach steady state with inputs.

Precipitation of heavy metals in produced water: influence on contaminant transport and toxicity.

Produced water undergoes changes in its physical chemistry including precipitation of heavy metals after being discharged and mixed with ambient seawater. Potential impacts of the precipitation of heavy metals on their transport and toxicity were studied using samples from offshore oil production sites on the Scotian Shelf off eastern Canada. Concentrations of aluminum, cadmium, chromium, cobalt, copper, iron, lead, manganese, nickel and zinc were measured in total, particulate and dissolved fractions together with Microtox tests for assessment of toxicity. Heavy metals in produced water were transformed from dissolved to particulate phase in a period of hours under oxygenated conditions, and aggregated to larger particles that settle rapidly (>100 m/day) over a few days. In addition, there was production of buoyant particles comprised of heavy metal precipitates sequestered onto oil droplets that were transported to the surface. The particulate fraction was generally more toxic than the dissolved fraction. This was evident at the mixing interface between produced water and seawater where elevated particulate and toxicity levels were observed. Laboratory studies suggest an increase in the toxicity of discharged produced water over time. Time-series experiments showed a sustained toxic response for more than a week following the oxidation of freshly discharged produced water that initially elicited little or no toxic response in the Microtox test. Chemical processes identified in this study, namely precipitation of heavy metals and consequent settling and rising fluxes of particles, will influence the toxicity, the fate and the transport of potential contaminants in the produced water. Therefore, these processes need to be considered in assessment of the environmental impact associated with offshore oil and gas operations.

Determination of mercury evasion in a contaminated headwater stream.

Evasion from first- and second-order streams in a watershed may be a significant factor in the atmospheric recycling of volatile pollutants such as mercury; however, methods developed for the determination of Hg evasion rates from larger water bodies are not expected to provide satisfactory results in highly turbulent and morphologically complex first- and second-order streams. A new method for determining the Hg evasion rates from these streams, involving laboratory gas-indexing experiments and field tracer tests, was developed in this study to estimate the evasion rate of Hg from Gossan Creek, a first-order stream in the Upsalquitch River watershed in northern New Brunswick, Canada. Gossan Creek receives Hg-contaminated groundwater discharge from a gold mine tailings pile. Laboratory gas-indexing experiments provided the ratio of gas-exchange coefficients for zero-valent Hg to propane (tracer gas) of 0.81+/-0.16, suggesting that the evasion mechanism in highly turbulent systems can be described by the surface renewal model with an additional component of enhanced gas evasion probably related to the formation of bubbles. Deliberate field tracer tests with propane and chloride tracers were found to be a reliable and practical method for the determination of gas-exchange coefficients for small streams. Estimation of Hg evasion from the first 1 km of Gossan Creek indicates that about 6.4 kg of Hg per year is entering the atmosphere, which is a significant fraction of the regional sources of Hg to the atmosphere.