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.

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.

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.

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.

Dissolved Gaseous Mercury Production at a Marine Aquaculture Site in the Mercury-Contaminated Marano and Grado Lagoon, Italy.

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.

Mercury concentrations in blood, brain and muscle tissues of coastal and pelagic birds from northeastern Canada.

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 Biogeochemistry in Freshwater Ecosystems: A Review Focusing on DOM and Photodemethylation.

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.

Mercury photoreduction and photooxidation in lakes: Effects of filtration and dissolved organic carbon concentration.

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: 2.6-15.4mg/L). Filtered (0.2µm) 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±253pg/L) than filtered samples (mean of 482±206pg/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.

Assessing the utility of dissolved organic matter photoreactivity as a predictor of in situ methylmercury concentration.

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 24hr. Dissolved organic matter photoreactivity, measured as the loss of absorbance at 350nm 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 bioaccumulation in aquatic biota along a salinity gradient in the Saint John River estuary.

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.

Relationships between blood mercury levels, reproduction, and return rate in a small seabird.

Mercury (Hg) is a ubiquitous heavy metal that occurs naturally in the environment, but its levels have been supplemented for decades by a variety of human activities. Mercury can have serious deleterious effects on a variety of organisms, with top predators being particularly susceptible because methylmercury bioaccumulates and biomagnifies in food webs. Among birds, seabirds can have especially high levels of Hg contamination and Leach's storm-petrels (Oceanodroma leucorhoa), in particular, have amongst the highest known levels. Several populations of Leach's storm-petrels have declined recently in the Northwest Atlantic. The causes of these declines remain uncertain, but the toxic effects of Hg could be a potential factor in this decline. Here, we tested for relationships between adult blood total Hg (THg) concentration and several offspring development parameters, and adult return rate of Leach's storm-petrels breeding on Bon Portage Island (43° 28' N, 65° 44' W), Nova Scotia, Canada, between 2011 and 2015 (blood samples n = 20, 36, 6, 15, and 13 for each year, respectively). Overall, THg levels were elevated (0.78 ± 0.43 µg/g wet wt.) compared to other species of seabirds in this region, and varied significantly among years. However, we found no associations between THg levels and reproductive parameters or adult return rate. Our results indicate that levels of mercury observed in Leach's storm-petrel blood, although elevated, appear not to adversely affect their offspring development or adult return rate on Bon Portage Island.

Aerobic Mercury-resistant bacteria alter Mercury speciation and retention in the Tagus Estuary (Portugal).

Aerobic mercury-resistant bacteria were isolated from the sediments of two highly mercury-polluted areas of the Tagus Estuary (Barreiro and Cala do Norte) and one natural reserve area (Alcochete) in order to test their capacity to transform mercury. Bacterial species were identified using 16S rRNA amplification and sequencing techniques and the results indicate the prevalence of Bacillus sp. Resistance patterns to mercurial compounds were established by the determination of minimal inhibitory concentrations. Representative Hg-resistant bacteria were further tested for transformation pathways (reduction, volatilization and methylation) in cultures containing mercury chloride. Bacterial Hg-methylation was carried out by Vibrio fluvialis, Bacillus megaterium and Serratia marcescens that transformed 2-8% of total mercury into methylmercury in 48h. In addition, most of the HgR bacterial isolates showed Hg(2+)-reduction andHg(0)-volatilization resulting 6-50% mercury loss from the culture media. In summary, the results obtained under controlled laboratory conditions indicate that aerobic Hg-resistant bacteria from the Tagus Estuary significantly affect both the methylation and reduction of mercury and may have a dual face by providing a pathway for pollution dispersion while forming methylmercury, which is highly toxic for living organisms.

Photoreducible Mercury Loss from Arctic Snow Is Influenced by Temperature and Snow Age.

Mercury (Hg) is an important environmental contaminant, due to its neurotoxicity and ability to bioaccumulate. The Arctic is a mercury-sensitive region, where organisms can accumulate high Hg concentrations. Snowpack mercury photoredox reactions may control how much Hg is transported with melting Arctic snow. This work aimed to (1) determine the significance of temperature combined with UV irradiation intensity and snow age on Hg(0) flux from Arctic snow and (2) elucidate the effect of temperature on snowpack Hg photoreduction kinetics. Using a Teflon flux chamber, snow temperature, UV irradiation, and snow age were found to significantly influence Hg(0) flux from Arctic snow. Cross-correlation analysis results suggest that UV radiation has a direct effect on Hg(0)flux, while temperature may indirectly influence flux. Laboratory experiments determined that temperature influenced Hg photoreduction kinetics when snow approached the melting point (>-2 °C), where the pseudo-first-order reduction rate constant, k, decreased twofold, and the photoreduced Hg amount, Hg(II)red, increased 10-fold. This suggests that temperature influences Hg photoreduction kinetics indirectly, likely by altering the solid:liquid water ratio. These results imply that large mass transfers of Hg from snow to air may take place during the Arctic snowmelt period, altering photoreducible Hg retention and transport with snow meltwater.

Mercury in bats from the northeastern United States.

This study examines mercury exposure in bats across the northeast U.S. from 2005 to 2009. We collected 1,481 fur and 681 blood samples from 8 states and analyzed them for total Hg. A subset (n = 20) are also analyzed for methylmercury (MeHg). Ten species of bats from the northeast U.S. are represented in this study of which two are protected by the Endangered Species Act (ESA 1973) and two other species are pending review. There are four objectives in this paper: (1) to examine correlates to differences in fur-Hg levels among all of the sampling sites, including age, sex, species, and presence of a Hg point source; (2) define the relationship between blood and fur-Hg levels and the factors that influence that relationship including age, sex, species, reproductive status, and energetic condition; (3) determine the relationships between total Hg and MeHg in five common eastern bat species; and (4) assess the distribution of Hg across bat populations in the northeast. We found total blood and fur mercury was eight times higher in bats captured near point sources compared to nonpoint sources. Blood-Hg and fur-Hg were well correlated with females on average accumulating two times more Hg in fur than males. On average fur MeHg accounted for 86 % (range 71-95 %) of the total Hg in bat fur. Considering that females had high Hg concentrations, beyond that of established levels of concern, suggests there could be negative implications for bat populations from high Hg exposure since Hg is readily transferred to pups via breast milk. Bats provide an integral part of the ecosystem and their protection is considered to be of high priority. More research is needed to determine if Hg is a stressor that is negatively impacting bat populations.

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.

Mercury biomagnification through food webs is affected by physical and chemical characteristics of lakes.

Mercury (Hg) contamination in aquatic systems remains a global concern because the organic form, methyl Hg (MeHg), can biomagnify to harmful concentrations in fish, fish-eating wildlife, and humans. Food web transfer of MeHg has been explored using models of log MeHg versus relative trophic position (nitrogen isotopes, δ(15)N), but regression slopes vary across systems for unknown reasons. In this study, MeHg biomagnification was determined for 11 lake food webs in Kejimkujik National Park, Nova Scotia, Canada, and compared to physical and chemical lake characteristics using principal component and multiple regression analyses. MeHg biomagnification (regression slopes of log MeHg versus baseline-adjusted δ(15)N for fishes and invertebrates) varied significantly across lakes and was higher in systems with lower aqueous nutrient/MeHg/chloride scores. This is one of the largest, consistent data sets available on MeHg biomagnification through temperate lake food webs and the first study to use a principal component and multiple regression approach to understand how lake chemical and physical characteristics interact to affect biomagnification among systems. Overall, our results show that the magnitude of MeHg biomagnification through lake food webs is related to the chemical and physical characteristics of the systems, but the underlying mechanisms warrant further investigation.

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.

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.

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.