Coastal Mussel (Mytilus spp.) Soft Tissues as Bioindicators of Methylmercury: Exploring the Relationship Between Condition Index and Methylmercury Concentrations.

We investigated total mercury (THg) and methylmercury (MeHg) concentrations in coastal mussels (Mytilus spp.) sampled from the Minas Basin, Bay of Fundy and evaluated the relationship with condition index (CI). THg concentrations were low in sediment (mean THg = 5.15 ± 2.11 ng/g dw; n = 6) and soft tissues (mean THg = 62.3 ± 13.7 ng/g; mean MeHg = 13.2 ± 6.3 ng/g; n = 57). The THg in tissues had no significant relationship with CI (Rs= -0.205, p = 0.126). MeHg in tissues were significantly and negatively correlated with condition index (Rs = -0.361, p = 0.006) indicating that healthier mussels (higher CI) have lower mercury content possibly due to elimination strategies or growth dilution.

Ecology and environmental characteristics influence methylmercury bioaccumulation in coastal invertebrates.

Quantifying mercury (Hg) concentrations in invertebrates is fundamental to determining risk for bioaccumulation in higher trophic level organisms in coastal food webs. Bioaccumulation is influenced by local mercury concentrations, site geochemistry, individual feeding ecologies, and trophic position. We sampled seven species of invertebrates from five coastal sites in the Minas Basin, Bay of Fundy, and determined body concentrations of methylmercury (MeHg), total mercury (THg), and stable isotopes of nitrogen (δ15N) and carbon (δ13C). To evaluate the effects of environmental chemistry on Hg production and bioaccumulation, bulk sediments from all sites were analysed for THg, %Loss on ignition (LOI) (carbon), and sulfur isotopes (δ34S), and concentrations of MeHg, Total Organic Carbon (TOC), sulfate, and sulfide were measured in porewaters. The mean concentration of MeHg in tissues for all invertebrates sampled was 10.03 ± 7.04 ng g-1). MeHg in porewater (mean = 0.22-1.59 ng L-1) was the strongest predictor of invertebrate MeHg, but sediment δ34S (-0.80-14.1‰) was also a relatively strong predictor. δ34S in tissues (measured in three species; Corophium volutator, Ilyanassa obsoleta, and Littorina littorea) were positively related to MeHg in invertebrates (r = 0.55, 0.22, and 0.71 respectively), and when used in combination with δ15N and δ13C values improved predictions of Hg concentrations in biota. Hg concentrations in the amphipod Corophium volutator (mean MeHg = 10.60 ± 1.90 ng g-1) were particularly well predicted using porewater and sediment chemistry, highlighting this species as a useful bioindicator of Hg contamination in sediments of the Bay of Fundy.

Salinity and total suspended solids control mercury speciation in a tidal river: Comparisons with a photochemical mercury model.

Daytime volatilization of gaseous elemental mercury (Hg(0)aq) is a significant mechanism for mercury removal from aquatic systems and potentially limits the production and bioaccumulation of methylmercury. Changes in incoming solar radiation (in the ultraviolet range), dissolved organic matter, salinity, and total suspended particles were investigated concurrently with several mercury species (Hg(0)aq, dissolved total mercury (THg), easily reducible mercury (ERM), and mercury associated with total suspended solids (THgTSS)) during daylight hours near the mouth of a hypertidal river. There were no predictable temporal changes observed for Hg(0)aq in unfiltered surface water. Hg(0)aq ranged from 0 to 12 pg L-1, THg ranged from 0 to 492 pg L-1, ERM ranged from 13 to 381 pg L-1, and THgTSS ranged from <1.58 ng g-1 to 261.32 ng g-1. The range of Hg(0)aq predicted by the empirical model was similar to measured ERM concentrations, but it was shown that ERM did not significantly predict in-situ photoreducible Hg(II) (Hg(II)RED). Production of Hg(0)aq appears to largely be suppressed by suspended solids, which limits ultraviolet radiation transmission through surface water. Comparison of these results to an empirical model developed for this site to predict Hg(0)aq indicates that significantly more mercury is available for photoreduction near the mouth of the tidal river, and that Hg(II) will likely photoreduce quickly when TSS levels decrease with ocean mixing.

Concentration of fifty-six elements in excreta of penguins from the Antarctic Peninsula area.

Seabird feces as indicators of the exposure to environmental contaminants have been studied worldwide. Penguins are indicator species for marine pollution, but their role as biovectors of rare earth elements (REEs) to ecosystems have been little studied. The present study quantified the concentration of REEs and trace elements (TEs) in feces of gentoo penguin (Pygoscelis papua). Adult penguin excreta from Fildes Bay (King George Island) and Yelcho Base (Palmer Archipelago) were collected and then analyzed by ICP-MS. Among REEs, levels ranged from 0.0038 to 1.02 µg g-1 d.w. for Lu and Ce, respectively. For TEs, the levels varied widely through the sample set, with Al, Fe, Sr, Zn and Ti as the highest mean levels, particularly at Fildes Bay. The data show that gentoo penguins act as a biovector organism by transporting TEs and REEs from the sea to land via excreta, reaffirming that this species acts as an important biovector organism in Antarctic ecosystems. The potential impacts of this process on Antarctic ecosystems needs further research.

Mercury bioaccumulation and speciation in coastal invertebrates: Implications for trophic magnification in a marine food web.

Studies on mercury bioaccumulation and biomagnification in coastal invertebrates in eastern Canada are limited, but these data are necessary to determine risk of mercury exposure effects in upper trophic level organisms. We quantified methylmercury (MeHg), total mercury (THg), and stable isotopes of δ13C and δ15N in 14 species of invertebrates in the Minas Basin. The overall mean concentration of MeHg (12.78 ± 11.23 ng/g dw) was approximately 10 times below the Canadian guideline for the protection of wildlife consumers like fish and birds of 157.20 ng/g dry weight (dw). Invertebrates at higher trophic positions (δ15N) had greater THg and particularly MeHg. The Trophic Magnification Factors (TMF) for MeHg and THg (1.59 and 1.21 respectively) were similar to others reported in studies of food webs containing higher trophic level organisms.

Occurrence of rare earth elements (REEs) and trace elements (TEs) in feathers of adult and young Gentoo penguins from King George Island, Antarctica.

Penguins are sentinel species for marine pollution, but their role as potential biovectors of REEs or TEs to ecosystems has been poorly studied. The present study analyzed (ICP-MS) feathers of young and adult Gentoo penguins from Fildes Bay, for 63 elements (including 15 REEs). Most of the REEs were present at very low levels, ranging from 0.002 (Lu) to 0.452 (Sm) µg g-1 d.w., several orders of magnitude lower than TEs. The content of TEs varied widely, with Al, Fe, Zn, Sr, Ba, Ti and Mn as the seven having the highest concentrations in the feathers of both age groups. The results show that P. papua deposits REEs and TEs through the feathers on the penguin rockery, whose potential actual impacts and long-term fate in remote regions need deeper research. This work presents essential baseline data that will be useful for further studies on Antarctic penguins.

Mercury photoreduction and photooxidation kinetics in estuarine water: Effects of salinity and dissolved organic matter.

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-1 and 0.73 h-1. The amount of mercury available for photoreduction (Hg(II)RED) ranged between 67.2 and 265.9 pg. Pseudo first-order rate constants decreased with increasing salinity treatments (0-13.5 g L-1), with minimal change in rate constants occurring in higher salinity treatments (e.g. 20.3 or 26.8 g L-1), while Hg(II)RED increased with salinity. In lower salinity treatments, DOM was more photoactive. Taken together, results suggest changes in the mercury photoreduction mechanism from DOM-bound electron transfer to photochemically produced secondary reduction products with increasing salinity. Experiments examining photooxidation showed decreases in Hg (0) with longer exposure time, suggesting transformation of Hg(II)RED into a non-reducible form. This research highlights the importance of salinity and DOM interactions in estuarine surface water and their effects on mercury photochemistry.

The Complex Interactions Between Sediment Geochemistry, Methylmercury Production, and Bioaccumulation in Intertidal Estuarine Ecosystems: A Focused Review.

Due to their natural geochemistry, intertidal estuarine ecosystems are vulnerable to bioaccumulation of methylmercury (MeHg), a neurotoxin that readily bioaccumulates in organisms. Determining MeHg concentrations in intertidal invertebrates at the base of the food web is crucial in determining MeHg exposure in higher trophic level organisms like fish and birds. The processes that govern the production of MeHg in coastal ecosystems are influenced by many geochemical factors including sulfur species, organic matter, and salinity. The interactions of these factors with mercury are complex, and a wide variety of results have been reported in the literature. This paper reviews conceptual models to better clarify the various geochemical and physical factors that impact MeHg production and bioavailability in intertidal ecosystems.

Trace and rare earth elements in excreta of two species of marine mammals from South Shetland Islands, Antarctica.

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-1 d.w. The results show that both species act as biovector organisms of TEs and REEs through feces in remote environments, whose actual impacts and long-term fate need further exploration.

Using tissue cysteine to predict the trophic transfer of methylmercury and selenium in lake food webs.

The biomagnification of toxic methylmercury (MeHg) and selenium (Se) through aquatic food webs using nitrogen stable isotopes (δ15N) varies among ecosystems but underlying mechanisms are yet unexplained. Given the strong links between MeHg and thiol-containing amino acids and proteins containing selenocysteine, our hypothesis was that cysteine content is a better predictor of MeHg and Se transfer through lake food webs than δ15N. Food web samples were collected from six lakes in Kejimkujik National Park, Nova Scotia, Canada, and the regression slopes of log MeHg or Se versus protein-bound cysteine or bulk δ15N were compared. Across all six lakes, MeHg varied by a factor of 10 among taxa and was significantly and positively related to both cysteine (R2 = 0.65-0.80, p < 0.001) and δ15N (R2 = 0.88-0.94, p < 0.001), with no among-system differences in these slopes. In contrast, total Se concentrations varied by less than a factor of 2 among taxa in four lakes and were significantly related to cysteine in only two food webs (R2 = 0.20 & 0.37, p = 0.014 & < 0.001); however, δ15N was not a predictor of Se in any lake (p = 0.052-0.777). Overall, these novel results indicate that cysteine content predicts MeHg, and sometimes Se, across trophic levels, providing a potential mechanism for among-system differences in their biomagnification.

Scavenging gulls are biovectors of mercury from industrial wastes in Nova Scotia, Canada.

Seabirds are important biovectors of contaminants, like mercury, moving them from marine to terrestrial environments around breeding colonies. This transfer of materials can have marked impacts on receiving environments and biota. Less is known about biotransport of contaminants by generalist seabirds that exploit anthropogenic wastes compared to other seabird species. In this study, we measured total mercury (THg) in O-horizon soils at four herring gull (Larus smithsoniansus) breeding colonies in southern Nova Scotia, Canada. At colonies with dry substrate, THg was significantly higher in soils collected from gull colonies compared to nearby reference soils with no nesting gulls. Further, THg was distinct in soils among study colonies and was likely influenced by biotransport from other nesting seabird species, most notably Leach's storm-petrels (Hydrobates leucorhous). Our research suggests gulls that scavenge on anthropogenic wastes at local industrial sites are biovectors moving THg acquired at these sites to their colonies and may increase the spatial footprint of contaminants from these industries.

Are There Longitudinal Effects of Forest Harvesting on Carbon Quality and Flow and Methylmercury Bioaccumulation in Primary Consumers of Temperate Stream Networks?

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 δ2 H), and methylmercury (MeHg) concentrations in stream water and the caddisfly along a longitudinal gradient (first- to fourth-order streams, subcatchments of 50-1900 ha) in paired partially harvested and reference catchments in central Ontario, Canada. Although measures of DOM quality (specific ultraviolet absorbance at 254 nm 2.20-11.62) and autochthony in caddisflies (4.9%-34.0%) varied among sites, no upstream-to-downstream differences in these measures were observed between the paired harvested and reference catchments. In contrast, MeHg levels in stream water (0.06-0.35 ng/L) and caddisflies (29.7-192 µg/kg dry wt) were significantly higher in the upstream sites but not the farthest downstream sites in the harvested catchments compared to the reference catchments. This suggests that while current mitigation measures used by forestry companies did not prevent elevated MeHg in water and invertebrates at smaller spatial scales (subcatchments of 50-400 ha), these upstream impacts did not manifest at larger spatial scales (subcatchments of 800-1900 ha). The present study advances our understanding of spatially cumulative impacts within harvested catchments, which is critical to help forest managers maintain healthy forest streams and their provisioning of aquatic ecosystem services. Environ Toxicol Chem 2022;41:1490-1507. © 2022 SETAC.

Methylmercury in caddisflies and mayflies: Influences of water and sediment chemistry.

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.

A Review of Freshwater Invertebrates as Biomonitors of Methylmercury: the Importance of More Complete Physical and Chemical Reporting.

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.

Marine pollution in fledged Leach's storm-petrels (Hydrobates leucorhous) from Baccalieu Island, Newfoundland and Labrador, Canada.

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.

Methylmercury biomagnification in coastal aquatic food webs from western Patagonia and western Antarctic Peninsula.

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.

Historical patterns in mercury exposure for North American songbirds.

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.

Spatial distribution of mercury and other potentially toxic elements using epiphytic lichens in Nova Scotia.

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 Potentially Toxic Elements in intertidal sediments and their bioaccumulation by benthic invertebrates.

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.