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Methylmercury (MeHg) is a toxic and bioaccumulative organo-metallic compound that is naturally produced in many ecosystems. Organisms that occupy the lower trophic positions in food webs may be key factors in the assessment of MeHg biomagnification between ecosystems. Here we present a review of the peer-reviewed literature examining MeHg bioaccumulation in freshwater invertebrates, focused principally on insects. This review aims to characterize the invertebrates that bioaccumulate higher MeHg concentrations and therefore pose a higher risk to upper trophic levels and to clarify which ecosystems are more susceptible to bioaccumulation in lower trophic levels. However, we found that few studies provided robust environmental data (notably water chemistry) as part of their papers, dramatically limiting our ability to test for factors that might contribute to different concentrations of MeHg in invertebrates. We highlight the importance of providing physical and chemical characteristics of study sites in publications examining MeHg bioaccumulation and biomagnification. Adopting the proposed recommendations will improve the available information for future mercury risk assessment analyses.

Pinnipeds are sentinel species for marine pollution, but their role as vectors of trace elements (TEs) or rare earth elements (REEs) to ecosystems has been poorly studied. The present study tested pinniped feces for 61 elements, including REEs. Feces of adult seals (Mirounga leonina, Hydrurga leptonyx) from Fildes Bay, King George Island, Antarctica, were analyzed by ICP-MS. TEs varied by several orders of magnitude across the suite examined herein, with Fe, Al, Zn, Mn, HgII and Sr as the top six in both species. Of the REEs, Ce, Dy, Er, Eu, Gd, Ho, La, Lu, Nd, Pr, Sc, Sm, Tb, Y and Yb were found consistently in all samples and ranged from 0.935 to 0.006 μg g

The biomagnification of toxic methylmercury (MeHg) and selenium (Se) through aquatic food webs using nitrogen stable isotopes (δ

Sympatric communities of organisms may exploit different ecological niches to avoid intra- and interspecific competition. We examined the isotopic niches of American black ducks ( Anas rubripes) and mallards ( A. platyrhynchos) wintering in coastal and urban areas of Atlantic Canada and compared isotopic niche with digestive tract morphologies and blood mercury (Hg) concentrations. Isotopic niche width (for δ13C and δ15N) varied between the three groups of ducks studied, with coastally foraging black ducks exhibiting the widest isotopic niche, followed by coastal mallards, while urban feeding black ducks had a narrow isotopic niche. These niche differences had physical and chemical consequences: coastal black ducks had longer digestive tracts, a larger range in gizzard sizes, and higher and more variable Hg concentrations than urban black ducks and coastal mallards. This plasticity in ecological niche may reduce competition among and within species, and subsequently explain why winter numbers of black ducks and mallards have increased in Atlantic Canada.

Net photoreduction of divalent mercury (Hg(II)) and volatilization of photoreduction products (i.e., elemental mercury (Hg(0))/dissolved gaseous mercury (DGM)) is a mechanism by which mercury burdens in ecosystems are lessened. The effects of salinity on mercury photoreactions were investigated while controlling the concentration of DOM (1 kDa) using natural surface water from the tidal Jijuktu'kwejk (Cornwallis River) and processed with a tangential ultrafiltration-dilution technique. Pseudo first-order rate constants in estuarine water salinity dilutions ranged between 0.22 h

Forest harvesting affects dissolved organic matter (DOM) and aqueous mercury inputs as well as the food web structure in small-headwater streams, but how these upstream changes manifest downstream is unclear. To address this uncertainty, we examined DOM quality, autochthony in the caddisfly Hydropsychidae (using δ

Aquatic invertebrates vary in methylmercury (MeHg) levels among systems which has been attributed, in part, to environmental conditions, but may also be linked to differences in their biochemical composition. As MeHg is known to bind to thiol-containing amino acids such as cysteine in proteins of fish, our objective was to determine if these amino acids explain MeHg variability among aquatic invertebrate taxa. Benthic macroinvertebrates from diverse functional feeding groups and bulk zooplankton were collected from six acidic lakes in Kejimkujik National Park, Nova Scotia, Canada, and analyzed for MeHg, cysteine (as cysteic acid), methionine (as methionine sulfone), and nitrogen (relative trophic level, δ 15 N) and carbon (carbon source, δ 13 C) isotopes. MeHg was significantly and positively related to cysteine or methionine in zooplankton, caddisfly and stonefly tissues (R 2 from 0.24 to 0.57). In addition, methionine or cysteine in combination with δ 15 N and/or δ 13 C were better predictors of MeHg levels in stoneflies, mayflies, caddisflies and zooplankton among these lakes (R 2 adj = 0.25–0.91). Overall, these novel findings suggest that the variability in MeHg of aquatic invertebrates can be explained, in part, by their tissue levels of thiol-containing amino acids.

Methylmercury (MeHg) biomagnifies through aquatic food webs resulting in elevated concentrations in fish globally. Stable carbon and nitrogen isotopes are frequently used to determine dietary sources of MeHg and to model its biomagnification. However, given the strong links between MeHg and sulfur cycling, we investigated whether sulfur isotopes (δ34S) would improve our understanding of MeHg concentrations ([MeHg]) in Arctic lacustrine food webs. Delta34S values and total mercury (THg) or MeHg were measured in water, sediments, and biota from six lakes near Resolute Bay, NU, Canada. In two lakes impacted by historical eutrophication, aqueous sulfate δ34S was ∼8‰ more positive than sedimentary δ34S, suggestive of bacterial sulfate reduction in the sediment. In addition, aqueous δ34S showed a significant positive relationship with aqueous [MeHg] across lakes. Within taxa across lakes, [THg] in Arctic char muscle and [MeHg] in their main prey, chironomids, were positively related to their δ34S values across lakes, but inconsistent relationships were found across entire food webs among lakes. Across lakes, nitrogen isotopes were better predictors of biotic [THg] and [MeHg] than δ34S within this dataset. Our results suggest some linkages between Hg and S biogeochemistry in high Arctic lakes, which is an important consideration given anticipated climate-mediated changes in nutrient cycling.

Methylmercury (MeHg) is a toxic and bioaccumulative organo-metallic compound that is naturally produced in many ecosystems. Organisms that occupy the lower trophic positions in food webs may be key factors in the assessment of MeHg biomagnification between ecosystems. Here we present a review of the peer-reviewed literature examining MeHg bioaccumulation in freshwater invertebrates, focused principally on insects. This review aims to characterize the invertebrates that bioaccumulate higher MeHg concentrations and therefore pose a higher risk to upper trophic levels and to clarify which ecosystems are more susceptible to bioaccumulation in lower trophic levels. However, we found that few studies provided robust environmental data (notably water chemistry) as part of their papers, dramatically limiting our ability to test for factors that might contribute to different concentrations of MeHg in invertebrates. We highlight the importance of providing physical and chemical characteristics of study sites in publications examining MeHg bioaccumulation and biomagnification. Adopting the proposed recommendations will improve the available information for future mercury risk assessment analyses.

The Leach's storm-petrel (Hydrobates leucorhous) is one of the most abundant and widely distributed marine birds in the North Atlantic but is under global population decline, possibly linked to marine pollution. We determined levels of ingested plastic and hepatic total mercury (THg) in recently fledged juveniles that stranded in Newfoundland and Labrador, Canada, and assessed the relationship to body condition, size and diet. Plastic prevalence was high (87.5%) but hepatic THg was relatively low (mean 486.7 ng/g dry weight) compared to other studies. Levels of neither pollutant were significantly related to body metrics of health. Our data confirm that plastic and mercury are pervasive in the western North Atlantic Ocean, prominent even in young birds.

Quantifying methylmercury (MeHg) concentrations and uptake at the base of the food web is useful for assessing mercury exposure risk to higher trophic level organisms. Higher MeHg concentrations near the base of the food web may result in more MeHg exposure and accumulation in higher trophic organisms. Here, we analyze MeHg in caddisflies, mayflies, lake water, and sediment collected from two temperate lakes and one brook in Kejimkujik National Park, Nova Scotia, Canada. Overall, caddisfly larvae MeHg (15.38–276.96 ng/g; n = 29) was not significantly correlated with water chemistry. Whereas mayfly naiads MeHg (14.28–166.82 ng/g; n = 31) was positively correlated with water MeHg (rs = 0.43), negatively correlated with pH (rs = −0.49), and positively correlated with dissolved organic carbon (DOC; rs = 0.48). Of the mercury in insect tissues, the %MeHg ranged from 56 to 75 % in caddisfly larvae and 38–47 % in mayfly naiads. MeHg bioaccumulation factors (BAF) varied greatly (water to tissue BAFs = 0.145 × 106–1.054 × 106; sediment to tissue BAFs = 0.017 × 106–0.541 × 106). This study highlights the importance of quantifying variations in MeHg bioaccumulation and BAFs of common aquatic insect bioindicators at the base of complex food webs.

Mercury (Hg) is a toxic element which has increased in marine environments for more than a century, due largely to anthropogenic activities, and biomagnifies in food chains to harmful levels in some top predators like waterfowl and seabirds. We analysed total mercury (THg) concentrations in blood, brain and muscle tissue from healthy specimens of 13 coastal and pelagic bird species from eastern and northern Canada to provide a baseline on current concentrations, especially for brain concentrations which are highly underrepresented in the literature. We also examined within and among tissues relationships of THg concentrations within individuals. THg concentrations were generally higher in pelagic species and scavenging gulls, when compared to coastal waterfowl. Brain and muscle tissue had similar concentrations of THg in the birds examined, but both of these tissues had lower concentrations that those found in blood. Our results, and that of a previous study, suggest that body condition has a large influence on blood THg concentrations and should be considered when using blood as a sampling medium. Many of the species we examined had tissue THg above levels known to cause deleterious, sublethal effects in some species.

Methylmercury (MeHg) bioaccumulation is a growing concern in ecosystems worldwide. The absorption of solar radiation by dissolved organic matter (DOM) and other photoreactive ligands can convert MeHg into less toxic forms of mercury through photodemethylation. In this study, spectral changes and photoreactivity of DOM were measured to assess the potential to control photoreactions and predict in situ MeHg concentration. Water samples collected from a series of lakes in southwestern Nova Scotia in June, August, and September were exposed to controlled ultraviolet-A (UV-A) radiation for up to 24 hr. Dissolved organic matter photoreactivity, measured as the loss of absorbance at 350 nm at constant UV-A irradiation, was positively dependent on the initial DOM concentration in lake waters (r2 = 0.94). This relationship was consistent over time with both DOM concentration and photoreactivity increasing from summer into fall across lakes. Lake in situ MeHg concentration was positively correlated with DOM concentration and likely catchment transport in June (r = 0.77) but not the other sampling months. Despite a consistent seasonal variation in both DOM and Fe, and their respective correlations with MeHg, no discernable seasonal trend in MeHg was observed. However, a 3-year dataset from the 6 study lakes revealed a positive correlation between DOM concentration and both Fe (r = 0.91) and MeHg concentrations (r = 0.51) suggesting a more dominant landscape mobility control on MeHg. The DOM-MeHg relationships observed in these lakes highlights the need to examine DOM photoreactivity controls on MeHg transport and availability in natural waters particularly given future climate perturbations.

Mercury (Hg) in the Arctic is a significant concern due to its bioaccumulative and neurotoxic properties, and the sensitivity of Arctic environments. Previous research has found high levels of Hg in snowpacks with high chloride (Cl−) concentrations. We hypothesised that Cl− would increase Hg retention by decreasing Hg photoreduction to Hg(0) in melted Arctic snow. To test this, changes in Hg photoreduction kinetics in melted Alert, NU snow were quantified with changing Cl− concentration and UV intensity. Snow was collected and melted in Teflon bottles in May 2014, spiked with 0–10 μg/g Cl−, and irradiated with 3.52–5.78 W·m− 2 UV (280–400 nm) radiation in a LuzChem photoreactor. Photoreduction rate constants (k) (0.14–0.59 hr−1) had positive linear relationships with [Cl−], while photoreduced Hg amounts (Hg(II)red) had negative linear relationships with [Cl−] (1287–64 pg in 200 g melted snow). Varying UV and [Cl−] both altered Hg(II)red amounts, with more efficient Hg stabilisation by Cl− at higher UV intensity, while k can be predicted by Cl− concentration and/or UV intensity, depending on experimental parameters. Overall, with future projections for greater snowpack Cl− loading, our experimental results suggest that more Hg could be delivered to Arctic aquatic ecosystems by melted snow (smaller Hg(II)red expected), but the Hg in the melted snow that is photoreduced may do so more quickly (larger k expected).

Photodemethylation can be one of the primary processes for loss of neurotoxic methylmercury (MeHg) in freshwater lakes. Few studies have quantified seasonal variations in photodemethylation rate constants as a function of dissolved organic matter (DOM). We conducted 1-week irradiation experiments in two seasons to test for spatial and temporal differences in photodemethylation potential in temperate lake waters. Six study lakes in Kejimkujik National Park, Nova Scotia were sampled in summer and fall to include a range of naturally occurring DOM concentrations (4.4-13.4 and 3.9-16.4 mg C L-1, respectively). A negative linear relationship (R2 = 0.76, p = 0.01) was found between DOM concentration and photodemethylation rate constant across seasons, indicating that DOM is a strong predictor of MeHg photodemethylation independent of seasonal effects. The two highest carbon lakes (BDW and PEB) had significantly higher energy-normalized photodemethylation rate constants in summer compared to fall corresponding with lower DOM concentrations in summer relative to fall. Additionally, there were negative linear relationships between MeHg photodemethylation and DOM photomineralization (R2s = 0.58-0.72) and DOM photobleaching (R2s = 0.83-0.90). This key finding suggests that competition for photons within DOM structures may reduce the potential for MeHg photodemethylation in high carbon waters and that this relationship persists across seasons.

We used a paleolimnological approach at Long Lake, Nova Scotia, to construct a 10 500-year record of metal deposition in lakebed sediments and elucidate the influence of both natural and anthropogenic environmental changes. Aquatic sediment concentrations of mercury (Hg), arsenic (As), and chromium (Cr) in Long Lake fluctuated substantially and, during some periods, exceeded guidelines for the protection of aquatic life. Increases in lead (Pb), Hg, Cr, trace metals, and nitrogen stable isotopes (δ15N) were broadly coincident with a period of widespread drying from ca. 8000 to 4000 cal BP and were likely a consequence of regional fires. From ca. 4000 cal BP until 1700 AD, metal levels in general were low due to decreased erosion, increased precipitation, and reduced fire activity. Water level lowering and forced sediment aggradation (tiding) in the 1800s led to increases in minerogenic Pb and Cr, though fossil fuel combustion also likely contributed to total Pb concentrations. Stratigraphic proxies indicated increased inorganic sedimentation rates, and reduced autochthonous productivity were coincident with lower Hg and As concentrations in the Long Lake sediment. Our data indicate that natural phenomena (fire) can result in sediment contaminant exceedances, that most metals have multiple sources, and that both human-induced disturbance and emissions have contributed to Pb contamination in the last 200 years. In addition, wetter and generally cooler climate appeared to favour lower concentrations of contaminants in lake sediments. Although wetland sediments in the Cumberland Basin Marshes are not heavily polluted with metals, the development of constructed wetlands and the disruption of aquatic sediments have the potential to concentrate, mobilize, and increase the bioavailability of metals.

To assess the role of salt-marsh plants on the vegetation-atmospheric Hg0 fluxes, three salt marsh plant species, Halimione portulacoides, Sarcocornia fruticosa and Spartina maritima were selected from a moderately contaminated site in the Tagus estuary during May 2012. Total mercury in stems and leaves for each plant as well as total gaseous mercury and vegetation-air Hg0 fluxes were measured over two continuous days. Mercury fluxes were estimated with a dynamic flux Tedlar® bag coupled to a high-resolution automated mercury analyzer (Tekran 2537A). Other environmental parameters such as air temperature, relative humidity and net solar radiation were also measured aside. H. portulacoides showed the highest total mercury concentrations in stems and leaves and the highest average vegetation-air Hg0 flux (0.48 ± 0.40 ng Hg m−2 h−1). The continuous measurements converged to a daily pattern for all plants, with enhanced fluxes during daylight and lower flux during the night. It is noteworthy that throughout the measurements a negative flux (air-vegetation) was never observed, suggesting the absence of net Hg0 deposition. Based on the above fluxes and the total area occupied by each species we have estimated the total amount of Hg0 emitted from this salt-marsh plants. A daily emission of 1.19 mg Hg d−1 was predicted for the Alcochete marsh and 175 mg Hg d−1 for the entire salt marsh area of the Tagus estuary.

Salt marshes are ecologically sensitive ecosystems where mercury (Hg) methylation and biomagnification can occur. Understanding the mechanisms controlling gaseous Hg flux from salt marshes is important to predict the retention of Hg in coastal wetlands and project the impact of environmental change on the global Hg cycle. We monitored Hg flux from a remote salt marsh over 9 days which included three cloudless days and a 4 mm rainfall event. We observed a cyclical diel relationship between Hg flux and solar radiation. When measurements at the same irradiance intensity are considered, Hg flux was greater in the evening when the sediment was warm than in the morning when the sediment was cool. This is evidence to suggest that both solar radiation and sediment temperature directly influence the rate of Hg(II) photoreduction in salt marshes. Hg flux could be predicted from solar radiation and sediment temperature in sub-datasets collected during cloudless days (R2 = 0.99), and before (R2 = 0.97) and after (R2 = 0.95) the rainfall event, but the combined dataset could not account for the lower Hg flux after the rainfall event that is in contrast to greater Hg flux observed from soils after rainfall events.

Methylmercury (MeHg) exposure and adverse health effects in fishes have been documented, but the molecular mechanisms involved in toxicity have not been fully characterized. The objectives of the current study were to (1) determine whether total Hg (THg) in the muscle was predictive of MeHg concentrations in the brain of wild female yellow perch (Perca flavescens) collected from four lakes in Kejimkujik National Park, a known biological mercury (Hg) hotspot in Nova Scotia, Canada and (2) to determine whether transcripts involved in the oxidative stress response were altered in abundance in fish collected across five lakes representing a MeHg gradient. In female yellow perch, MeHg in whole brain (0.38 to 2.00 μg/g wet weight) was positively associated with THg in muscle (0.18 to 2.13 μg/g wet weight) (R2 = 0.61, p

The present study examined potential effects of seasonal variations in photoreactive dissolved organic matter (DOM) on methylmercury (MeHg) photodemethylation rates in freshwaters. A series of controlled experiments were carried out using natural and photochemically preconditioned DOM in water collected from one lake in June, August, and October. Natural DOM concentrations doubled between June and August (DOC = 10.2–21.2 mg C L−1) and then remained stable into October (DOC = 19.4 mg C L−1). Correspondingly, MeHg concentrations peaked in August (0.42 ng L−1) along with absorbances at 350 nm (A350) and 254 nm (SUVA254). Up to 70% of the MeHg was photodemethylated in the short 48-hour irradiation experiments with June having significantly higher rates than the other sampling months (p 0.10). However, MeHg photodemethylation efficiencies (quantified in mole MeHg lost/mole photon absorbed) were higher in treatments with less photoreactive DOM. Congruently, MeHg photodemethylation efficiencies also decreased over summer by up to 10× across treatments in association with increased photoreactive DOM, and were negatively correlated with DOM concentration. These results suggest that an important driver of MeHg photodemethylation is the interplay between MeHg and DOM with greater potential for photodemethylation in freshwaters with more photobleached DOM and lower DOM content. This article is protected by copyright. All rights reserved

The bioaccumulation of Potentially Toxic Elements (PTEs) by benthic invertebrates in estuarine sediments is poorly understood. We sampled and analysed PTEs in sediments and benthic invertebrates from five sites in the Skeena Estuary (British Columbia, Canada), including sites adjacent to an abandoned cannery and a decommissioned papermill. Our aim was to elucidate baseline levels of PTE concentrations at sites that may be recovering from disturbance associated with prior industrial development and identify organisms that could be used to biomonitor the impact of future industrial developments. There was no indication that sediments of the salmon cannery were polluted, but acidic sediments adjacent to the papermill contained elevated concentrations of Cd, Cr, Hg and Pb. Benthic invertebrate community assemblages confirm that sediments have mostly recovered from prior industrial development associated with discharge of papermill sludge. Overall, we did not observe any relationship between PTE concentrations in the sediment and PTE concentrations in invertebrate tissues. However, we did observe a negative relationship between sediment pH and the Biota-Sediment Accumulation Factor (BSAF) of most PTEs for Oregon pill bugs (Gnorimosphaeroma oregonensis). G. oregonensis, observed at all sites, feeds on the fibers associated with the papermill discharge. Thus, G. oregonensis is a useful biomonitors for quantifying the impact of the decommissioned papermill, and are candidate biomonitors for assessing the impact of similar industrial development projects on intertidal ecosystems.

Methylmercury (MeHg) is a global environmental contaminant that poses significant risks to the health of humans, wildlife, and ecosystems. Assessing MeHg exposure in biota across the landscape and over time is vital for monitoring MeHg pollution and gauging the effectiveness of regulations intended to reduce new mercury (Hg) releases. We used MeHg concentrations measured in museum specimen feathers (collected between 1869 and 2014) and total Hg concentrations (as a proxy for MeHg) of feathers sampled from wild birds (collected between 2008 and 2017) to investigate temporal patterns in exposure over approximately 150 years for North American songbirds. For individual species, we found greater concentrations for samples collected post-2000 compared to those collected during historic times (pre-1900) for six of seven songbird species. Mean feather concentrations measured in samples collected post-2000 ranged between 1.9 and 17 times (mean 6.6) greater than historic specimens. The proportion of individual songbirds with feather concentrations that exceeded modeled toxicity benchmarks increased in samples collected after 1940. Only 2% of individual songbirds collected prior to 1940 had feather concentrations greater than 2.4 μg/g (a toxicity benchmark related to a 10% decrease in nest success) compared to 35% of individuals collected post-1940. Many species included in this study have a vulnerable or near-threatened conservation status, suggesting recovery actions are needed to address mercury pollution.

The use of naturally occurring epiphytic lichens can be an effective tool for regional monitoring of mercury (Hg) and other potentially toxic elements (PTEs). Nova Scotia, Canada is a hotspot for mercury and other trace metal accumulation in ecosystems; partially attributed to long-range transport of air pollution. The relative contribution of local and international sources of Hg to local air in Nova Scotia is unknown. This study assessed the potential of epiphytic lichens (Usnea spp.) as passive samplers for PTE air pollution in Nova Scotia. Lichens (n = 190) collected across mainland Nova Scotia were analyzed for PTEs. Results indicate that there are 3 distinct clusters of PTEs which suggest patterns and sources for each elemental cluster. Hg was correlated with longitude and prevailing wind direction, and Hg was not significantly different in site-specific hotspot sampling nor year of sampling. Our data support the hypothesis that Hg in lichens is from historical and ongoing long-range transport and diffuse emission patterns rather than localized pollution sources. PTE concentrations were shown to have median values that are similar to other remote regions (such as the Antarctic) however the maximum values were observed to be substantially higher for some elements (e.g. lead, cadmium). This research supports the use of lichens as biomonitors and provides a baseline for future monitoring efforts to identify changes in PTE distribution in Nova Scotia with ongoing industrial activity and a changing climate.

Relationships between concentrations of Potentially Toxic Elements (PTEs) in estuarine sediments and their impact benthic invertebrate communities are poorly understood. We sampled and analysed PTEs in sediments and benthic invertebrates from five sites surrounding the Skeena Estuary, including sites adjacent to an abandoned cannery and a decommissioned papermill. There was no indication that sediments of the salmon cannery are polluted, but acidic sediments adjacent to the papermill contained elevated concentrations of Cd, Cr, Hg and Pb. Benthic invertebrate community assemblages confirm that sediments have recovered from prior disturbances associated with discharge of papermill sludge. Oregon pill bugs (Gnorimosphaeroma oregonensis), observed at all five sites, feed on the fibers associated with the papermill discharge. Thus, G. oregonensis are useful biomonitors for quantifying the impact of the decommissioned papermill, and similar industrial development projects, on intertidal ecosystems along the north coast of British Columbia, Canada.

Dissolved gaseous mercury (DGM) production was examined in relation to ultraviolet radiation within a marine aquaculture site in the contaminated Marano and Grado Lagoon (Italy). The measured rates of DGM production relative to time elapsed (17.06 and 20.68 pg h−1, respectively) were substantially (6–20 times) higher than what has been observed in other marine Hg studies. We measured similar levels of DGM relative to dissolved total mercury (THgD) (0.84%–8.91%) at these sites in comparison to uncontaminated marine sites, however relative to other moderately-contaminated marine sites in Portugal the % DGM/THgD was high. These results suggest a substantial capacity for Hg volatilization from these highly contaminated lagoons to the atmosphere due to photoreduction mechanisms.

In situ air concentrations of gaseous elemental mercury (Hg(0)) and vegetation–atmosphere fluxes were quantified in both high (Cala Norte, CN) and low-to-moderate (Alcochete, ALC) Hg-contaminated saltmarsh areas of the Tagus estuary colonized by plant species Halimione portulacoides (Hp) and Sarcocornia fruticosa (Sf). Atmospheric Hg(0) ranged between 1.08–18.15 ng m−3 in CN and 1.18–3.53 ng m−3 in ALC. In CN, most of the high Hg(0) levels occurred during nighttime, while the opposite was observed at ALC, suggesting that photoreduction was not driving the air Hg(0) concentrations at the contaminated site. Vegetation–air Hg(0) fluxes were low in ALC and ranged from −0.76 to 1.52 ng m−2 (leaf area) h−1 for Hp and from −0.40 to 1.28 ng m−2 (leaf area) h−1 for Sf. In CN, higher Hg fluxes were observed for both plants, ranging from −9.90 to 15.45 ng m−2 (leaf area) h−1 for Hp and from −8.93 to 12.58 ng m−2 (leaf area) h−1 for Sf. Mercury flux results at CN were considered less reliable due to large and fast variations in the ambient air concentrations of Hg(0), which may have been influenced by emissions from the nearby chlor-alkali plant, or historical contamination. Improved experimental setup, the influence of high local Hg concentrations and the seasonal activity of the plants must be considered when assessing vegetation–air Hg(0) fluxes in Hg-contaminated areas.

Mercury (Hg) is a global pollutant of concern because its organic and more toxic form, methylHg (MeHg), bioaccumulates and biomagnifies through aquatic food webs to levels that affect the health of fish and fish consumers, including humans. Although much is known about trophic transfer of MeHg in aquatic food webs at temperate latitudes in the northern hemisphere, it is unclear whether its fate is similar in biota from coastal zones of the southeastern Pacific. To assess this gap, MeHg, total Hg and food web structure (using δ13C and δ15N) were measured in marine macroinvertebrates, fishes, birds, and mammals from Patagonian fjords and the Antarctic Peninsula. Trophic magnification slopes (TMS; log MeHg versus δ15N) for coastal food webs of Patagonia were high when compared with studies in the northern hemisphere, and significantly higher near freshwater inputs as compared to offshore sites (0.244 vs 0.192). Similarly, in Antarctica, the site closer to glacial inputs had a significantly higher TMS than the one in the Southern Shetland Islands (0.132 vs 0.073). Composition of the food web also had an influence, as the TMS increased when mammals and seabirds were excluded (0.132-0.221) at a coastal site. This study found that both the composition of the food web and the proximity to freshwater outflows are key factors influencing the TMS for MeHg in Patagonian and Antarctic food webs.

Seasonal and spatial variations of dissolved and particulate methylmercury were evaluated for the first time in sediment cores from the Tagus Estuary. Results showed the highest MeHg concentrations in summer months indicating that the "seasonally" methylation process occurs not only at the topmost layers of the sediments but also in the deeper layers of the sediment column. The proportion of MeHg (up to 92%) in some of our pore water samples was higher than values reported in the literature for other estuaries suggesting that the sedimentary environment in the Tagus tends to favour Hg methylation. This work points to the importance of seasonal variation of the MeHg production in sediment cores. In physically dominated estuaries this enhances seasonal MeHg production in deeper sediments that can have serious ecological impacts due to resuspension or advection processes under extreme events by the increase of MeHg transported to the water column.

We investigated the impact of managed retreat on mercury (Hg) biogeochemistry at a site subject to diffuse contamination with Hg. We collected sediment cores from an area of land behind a dyke one year before and one year after it was intentionally breached. These sediments were compared to those of an adjacent mudflat and a salt marsh. The concentration of total mercury (THg) in the sediment doubled after the dyke was breached due to the deposition of fresh sediment that had a smaller particle size, and higher pH. The concentration of methylmercury (MeHg) was 27% lower in the sediments after the dyke was breached. We conclude that coastal flooding during managed retreat of coastal flood defences at this site has not increased the risk of Hg methylation or bioavailability during the first year. As the sediment becomes vegetated, increased activity of Hg-methylating bacteria may accelerate Hg-methylation rate.

Methylmercury (MeHg) is a neurotoxin and endocrine disruptor that bioaccumulates and biomagnifies through trophic levels, resulting in potentially hazardous concentrations. Although wetlands are known hotspots for mercury (Hg) methylation, the effects of avian biovectors on these processes are poorly understood. We examined Hg speciation and distribution in shallow groundwater and surface water from a raised-bog with over 30 years of avian biovector (herring gulls Larus argentatus and great black-backed gulls Larus marinus ) colonization and guano input. Compared to the reference site, the avian-impacted bog had elevated concentrations of total dissolved organic carbon (TOC), total Hg, MeHg, phosphate (PO 4 3− ), and other trace metals, notably Pb, As, Cd and Ni. Spatial interpolation showed that the densest area of gull nesting was co-located with areas that had the highest concentrations of PO 4 3− , MeHg, As and Cd, but not total mercury (THg), and models suggested that Mn, PO 4 3− , and dissolved TOC were strong predictors of MeHg. Our findings suggest that while these gulls may not be a significant source of Hg, the excess of PO 4 3− (a well recognised component of guano) and the subsequent changes in water chemistry due to avian biovector subsidies may increase net Hg methylation.

Mercury (Hg) concentrations are a concern in the Canadian Arctic, because they are relatively high compared to background levels and to similar species farther south, and are increasing in many wildlife species. Among marine birds breeding in the Canadian Arctic, Hg concentrations have been monitored regularly in eggs and intermittently in livers, but feathers have generally not been used as an indicator of Hg exposure or burden. We examined Hg concentrations in six marine bird species in the Canadian Arctic. Ivory gull Pagophila eburnea, feather Hg was exceptionally high, while glaucous gull Larus hyperboreus feather Hg was unexpectedly low, and ratios of feather THg to egg THg varied across species. The proportion of total Hg that was comprised of methyl Hg in ivory gull feathers was lower than in other species, and may be related to photo-demethylation or keratin breakdown in semi-opaque feather tissue.

Controlled experiments were performed with frozen and melted Arctic snow to quantify relationships between mercury photoreaction kinetics, ultra violet (UV) radiation intensity, and snow ion concentrations. Frozen (-10°C) and melted (4°C) snow samples from three Arctic sites were exposed to UV (280-400 nm) radiation (1.26-5.78 W · m(-2)), and a parabolic relationship was found between reduction rate constants in frozen and melted snow with increasing UV intensity. Total photoreduced mercury in frozen and melted snow increased linearly with greater UV intensity. Snow with the highest concentrations of chloride and iron had larger photoreduction and photooxidation rate constants, while also having the lowest Hg(0) production. Our results indicate that the amount of mercury photoreduction (loss from snow) is the highest at high UV radiation intensities, while the fastest rates of mercury photoreduction occurred at both low and high intensities. This suggests that, assuming all else is equal, earlier Arctic snow melt periods (when UV intensities are less intense) may result in less mercury loss to the atmosphere by photoreduction and flux, since less Hg(0) is photoproduced at lower UV intensities, thereby resulting in potentially greater mercury transport to aquatic systems with snowmelt.

In temperate regions of Canada, mercury (Hg) concentrations in biota and the magnitude of Hg biomagnification through food webs vary between neighboring lakes and are related to water chemistry variables and physical lake features. However, few studies have examined factors affecting the variable Hg concentrations in landlocked Arctic char (Salvelinus alpinus) or the biomagnification of Hg through their food webs. We estimated the food web structure of six high Arctic lakes near Resolute Bay, Nunavut, Canada, using stable carbon (δ(13)C) and nitrogen (δ(15)N) isotopes and measured Hg (total Hg (THg) in char, the only fish species, and methylmercury (MeHg) in chironomids and zooplankton) concentrations in biota collected in 2010 and 2011. Across lakes, δ(13)C showed that benthic carbon (chironomids) was the dominant food source for char. Regression models of log Hg versus δ(15)N (of char and benthic invertebrates) showed positive and significant slopes, indicting Hg biomagnification in all lakes, and higher slopes in some lakes than others. However, no principal components (PC) generated using all water chemistry data and physical characteristics of the lakes predicted the different slopes. The PC dominated by aqueous ions was a negative predictor of MeHg concentrations in chironomids, suggesting that water chemistry affects Hg bioavailability and MeHg concentrations in these lower-trophic-level organisms. Furthermore, regression intercepts were predicted by the PCs dominated by catchment area, aqueous ions, and MeHg. Weaker relationships were also found between THg in small char or MeHg in pelagic invertebrates and the PCs dominated by catchment area, and aqueous nitrate and MeHg. Results from these high Arctic lakes suggest that Hg biomagnification differs between systems and that their physical and chemical characteristics affect Hg concentrations in lower-trophic-level biota.

Mercury is a toxic and bioaccumulative environmental contaminant, which may be transported to remote regions around the world, such as the Arctic. Snowmelt is a major source of mercury to many surface water environments, but the amount of mercury in snow varies considerably. This variation is due to the balance of mercury retention and losses from snow, which is largely controlled by photochemical mechanisms controlling speciation. As such, quantifying these photochemical reaction rates and the factors affecting them will allow for the prediction of mercury speciation and movement into receiving water bodies. This will consequently improve our ability to predict exposure of aquatic organisms to mercury. This review highlights knowledge gaps in the quantification of mercury photochemical kinetics and the specific research required to advance the science of mercury photochemistry in snow, while examining the physical and chemical snowpack variables that influence snowpack mercury reactions. At present, our lack of mechanistic and kinetic knowledge of mercury reactions in snow is one of the greatest gaps preventing accurate predictions of mercury fate in regions containing seasonal snowpacks.

Mercury contamination is a growing concern for freshwater food webs in ecosystems without point sources of mercury. Methylmercury (MeHg) is of particular concern, as this is the form of mercury that crosses the blood-brain barrier and is neurotoxic to organisms. Wetlands and benthic sediments have high organic content and low oxygen availability. Anaerobic bacteria drive the metabolic function in these ecosystems and subsequently can methylate mercury. The bioavailability of MeHg is controlled by physicochemical characteristics such as pH, binding affinities, and dissolved organic matter (DOM). Similarly, photodemethylation is influenced by similar characteristics and thereby the two processes should be studied in tandem. The degradation of MeHg through photochemistry is an effective destruction mechanism in freshwater lakes. This review will highlight the uncertainties and known effects of DOM on subsequent photoreactions that lead to the occurrence of mercury photodemethylation and reduction in mercury bioavailability in freshwater ecosystems.

Although estuaries are critical habitats for many aquatic species, the spatial trends of toxic methylmercury (MeHg) in biota from fresh to marine waters are poorly understood. Our objective was to determine if MeHg concentrations in biota changed along a salinity gradient in an estuary. Fourspine Stickleback (Apeltes quadracus), invertebrates (snails, amphipods, and chironomids), sediments, and water were collected from ten sites along the Saint John River estuary, New Brunswick, Canada in 2015 and 2016, with salinities ranging from 0.06 to 6.96. Total mercury (proxy for MeHg) was measured in whole fish and MeHg was measured in a subset of fish, pooled invertebrates, sediments, and water. Stable sulfur (δ34S), carbon (δ13C), and nitrogen (δ15N) isotope values were measured to assess energy sources (S, C) and relative trophic level (N). There were increases in biotic δ13C and δ34S from fresh to more saline sites and these measures were correlated with salinity. Though aqueous MeHg was higher at the freshwater than more saline sites, only chironomid MeHg increased significantly with salinity. In the Saint John River estuary, there was little evidence that MeHg and its associated risks increased along a salinity gradient.

Mercury is a globally distributed, environmental contaminant. Quantifying the retention and loss of mercury is integral for predicting mercury-sensitive ecosystems. There is little information on how dissolved organic carbon (DOC) concentrations and particulates affect mercury photoreaction kinetics in freshwater lakes. To address this knowledge gap, samples were collected from ten lakes in Kejimkujik National Park, Nova Scotia (DOC: 2.6–15.4 mg/L). Filtered (0.2 μm) and unfiltered samples were analysed for gross photoreduction, gross photooxidation, and net reduction rates of mercury using pseudo first-order curves. Unfiltered samples had higher concentrations (p = 0.04) of photoreducible divalent mercury (Hg(II)RED) (mean of 754 ± 253 pg/L) than filtered samples (mean of 482 ± 206 pg/L); however, gross photoreduction and photooxidation rate constants were not significantly different in filtered or unfiltered samples in early summer. DOC was not significantly related to gross photoreduction rate constants in filtered (R2 = 0.43; p = 0.08) and unfiltered (R2 = 0.02; p = 0.71) samples; DOC was also not significantly related to gross photooxidation rate constants in filtered or unfiltered samples. However, DOC was significantly negatively related with Hg(II)RED in unfiltered (R2 = 0.53; p = 0.04), but not in filtered samples (R2 = 0.04; p = 0.60). These trends indicate that DOC is a factor in determining dissolved mercury photoreduction rates and particles partially control available Hg(II)RED in lake water. This research also demonstrates that within these lakes gross photoreduction and photooxidation processes are close to being in balance. Changes to catchment inputs of particulate matter and DOC may alter mercury retention in these lakes and could partially explain observed increases of mercury accumulation in biota.

Mercury (Hg) dynamics was evaluated in contaminated sediments and overlying waters from Tagus estuary, in two sites with different Hg anthropogenic sources: Cala Norte (CNOR) and Barreiro (BRR). Environmental factors affecting methylmercury (MMHg) production and Hg and MMHg fluxes across sediment/water interface were reported. [THg] and [MMHg] in solids (0.31–125 μg g−1 and 0.76–201 ng g−1, respectively) showed high variability with higher values in BRR. Porewater [MMHg] (0.1–63 ng L−1, 0.5–86% of THg) varied local and seasonally; higher contents were observed in the summer campaign, thus increasing sediment toxicity affecting the sediment/water Hg (and MMHg) fluxes. In CNOR and BRR sediments, Hg availability and organic carbon were the main factors controlling MMHg production. Noteworthy, an upward MMHg diffusive flux was observed in winter that was inverted in summer. Although MMHg production increases in warmer month, the MMHg concentrations in overlying water increase in a higher proportion compared to the levels in porewaters. This opposite trend could be explained by different extension of MMHg demethylation in the water column. The high concentrations of Hg and MMHg and their dynamics in sediments are of major concern since they can cause an exportation of Hg from the contaminated areas up to ca. 14,600 mg year−1 and an MMHg deposition of up to ca. 6000 mg year−1. The results suggest that sediments from contaminated areas of Tagus estuary should be considered as a primary source of Hg for the water column and a sink of MMHg to the sedimentary column.

Environmental contamination by mercury is a concern in marine food webs, and especially for large fish. We examined methylmercury (MeHg) levels in blood, muscle and liver of 35 individual Atlantic sturgeon (Acipenser oxyrhynchus), a commercially harvested, anadromous fish eastern Canada. Females had higher blood and liver MeHg levels than males, and in some tissues there was a suggestion of higher mercury in longer fish. Collectively, sturgeon MeHg levels were far below Canadian and international guidelines for safe consumption of fish meat.

This study examines, for the first time, the neurotoxicity of Hg(II) and MeHg in fish (Diplodus sargus) in a time-course comparative perspective and considering realistic exposure levels and routes. Both forms followed an identical time-variation pattern of accumulation in the brain, but dietary MeHg was more efficiently transported to the brain. MeHg was substantially eliminated from the brain in 28days of depuration, which did not occur for Hg(II). Moreover, Hg(II) displayed a high neurotoxicity potential, as unveiled by the poor activation of brain antioxidant defenses and recurrent oxidative damage (as protein oxidation), while the opposite was recorded upon MeHg exposure. These results highlight the need to include Hg(II) in future environmental health assessment plans, preventing an underestimation of the risk for wild fish populations, which has probably been occurring due to the long-standing idea of the higher toxicity of MeHg in comparison with inorganic Hg forms., Patrícia Pereira benefited from post-doctoral grant (SFRH/BPD/ 107718/2015) supported by “Fundação para a Ciência e a Tecnologia” (FCT). This work has been supported by the Research project financed by FCT PTDC/AAG-REC/2488/2012 (NEUTOXMER - Neurotoxicity of mercury in fish and association with morphofunctional brain alterations and behavior shifts), as well as by the Centre for Environmental and Marine Studies (CESAM).

Intertidal sediments of Tagus estuary regularly experiences complex redistribution due to tidal forcing, which affects the cycling of mercury (Hg) between sediments and the water column. This study quantifies total mercury (Hg) and methylmercury (MMHg) concentrations and fluxes in a flooded mudflat as well as the effects on water-level fluctuations on the air-surface exchange of mercury. A fast increase in dissolved Hg and MMHg concentrations was observed in overlying water in the first 10min of inundation and corresponded to a decrease in pore waters, suggesting a rapid export of Hg and MMHg from sediments to the water column. Estimations of daily advective transport exceeded the predicted diffusive fluxes by 5 orders of magnitude. A fast increase in dissolved gaseous mercury (DGM) concentration was also observed in the first 20-30min of inundation (maximum of 40pg L-1). Suspended particulate matter (SPM) concentrations were inversely correlated with DGM concentrations. Dissolved Hg variation suggested that biotic DGM production in pore waters is a significant factor in addition to the photochemical reduction of Hg. Mercury volatilization (ranged from 1.1 to 3.3ngm-2h-1; average of 2.1ngm-2h-1) and DGM production exhibited the same pattern with no significant time-lag suggesting a fast release of the produced DGM. These results indicate that Hg sediment/water exchanges in the physical dominated estuaries can be underestimated when the tidal effect is not considered.