Competition between Dissolved Organic Matter and Freshwater Plankton Control Methylmercury Isotope Fractionation during Uptake and Photochemical Demethylation.

Isotope fractionation related to photochemical reactions and planktonic uptake at the base of the food web is a major uncertainty in the biological application of mercury (Hg) stable isotopes. In freshwater systems, it is unclear how competitive interactions among methylmercury (MeHg), dissolved organic matter (DOM), and phytoplankton govern the magnitude of mass-dependent and mass-independent fractionation. This study investigated how DOM alters rates of planktonic MeHg uptake and photodegradation and corresponding Hg isotope fractionation in the presence of freshwater phytoplankton species, Raphidocelis subcapitata. Outdoor sunlight exposure experiments utilizing R. subcapitata were performed in the presence of different DOM samples using environmentally relevant ratios of MeHg-DOM thiol groups. The extent of Δ199Hg in phytoplankton incubations (2.99‰ St. Louis River HPOA, 1.88‰ Lake Erie HPOA) was lower compared to paired abiotic control experiments (4.29 and 2.86‰, respectively) after ∼30 h of irradiation, resulting from cell shading or other limiting factors reducing the extent of photodemethylation. Although the Δ199Hg/Δ201Hg ratio was uniform across experiments (∼1.4), Δ199Hg/δ202Hg slopes varied dramatically (from -0.96 to 15.4) across incubations with R. subcapitata and DOM. In addition, no evidence of Hg isotope fractionation was observed within R. subcapitata cells. This study provides a refined examination of Hg isotope fractionation markers for key processes occurring in the lower food web prior to bioaccumulation, critical for accurately accounting for the photochemical processing of Hg isotopes across a wide spectrum of freshwater systems.

National-Scale Assessment of Total Gaseous Mercury Isotopes Across the United States.

With the 2011 promulgation of the Mercury and Air Toxics Standards by the U.S. Environmental Protection Agency, and the successful negotiation by the United Nations Environment Program of the Minamata Convention, emissions of mercury (Hg) have declined in the United States. While the declines in atmospheric Hg concentrations in North America are encouraging, linking the declines to changing domestic and global source portfolios remains challenging. To address these research gaps, the U.S. Geological Survey initiated the first national-scale effort to establish a baseline of total gaseous mercury stable isotope values at 31 sites distributed across the United States. Results indicated that unique Hg sources, such as Hg evasion from an elemental Hg contaminated site or free tropospheric intrusions in high altitude sites, were distinguishable from background atmospheric values. Minor gradients were observed across the nation, with regions of heavy industrial activity demonstrating lower δ202Hg, but no consistent changes in other isotopes such as Δ199Hg and Δ200Hg were observed. Furthermore, δ202Hg was impacted by foliar uptake and senescence but trends varied between forested regions in the northeastern and midwestern United States. These data demonstrate regional emission sources and other environmental variables can impact total gaseous Hg (TGM) isotope values, highlighting the need to characterize atmospheric Hg isotopes over larger geographical areas to evaluate changes related to national and international Hg regulations.

Metabolically diverse microorganisms mediate methylmercury formation under nitrate-reducing conditions in a dynamic hydroelectric reservoir.

Brownlee Reservoir is a mercury (Hg)-impaired hydroelectric reservoir that exhibits dynamic hydrological and geochemical conditions and is located within the Hells Canyon Complex in Idaho, USA. Methylmercury (MeHg) contamination in fish is a concern in the reservoir. While MeHg production has historically been attributed to sulfate-reducing bacteria and methanogenic archaea, microorganisms carrying the hgcA gene are taxonomically and metabolically diverse and the major biogeochemical cycles driving mercury (Hg) methylation are not well understood. In this study, Hg speciation and redox-active compounds were measured throughout Brownlee Reservoir across the stratified period in four consecutive years (2016-2019) to identify the location where and redox conditions under which MeHg is produced. Metagenomic sequencing was performed on a subset of samples to characterize the microbial community with hgcA and identify possible links between biogeochemical cycles and MeHg production. Biogeochemical profiles suggested in situ water column Hg methylation was the major source of MeHg. These profiles, combined with genome-resolved metagenomics focused on hgcA-carrying microbes, indicated that MeHg production occurs in this system under nitrate- or manganese-reducing conditions, which were previously thought to preclude Hg-methylation. Using this multidisciplinary approach, we identified the cascading effects of interannual variability in hydrology on the redox status, microbial metabolic strategies, abundance and metabolic diversity of Hg methylators, and ultimately MeHg concentrations throughout the reservoir. This work expands the known conditions conducive to producing MeHg and suggests that the Hg-methylation mitigation efforts by nitrate or manganese amendment may be unsuccessful in some locations.

Biogeochemical and hydrologic synergy control mercury fate in an arid land river-reservoir system.

Reservoirs in arid landscapes provide critical water storage and hydroelectric power but influence the transport and biogeochemical cycling of mercury (Hg). Improved management of reservoirs to mitigate the supply and uptake of bioavailable methylmercury (MeHg) in aquatic food webs will benefit from a mechanistic understanding of inorganic divalent Hg (Hg(II)) and MeHg fate within and downstream of reservoirs. Here, we quantified Hg(II), MeHg, and other pertinent biogeochemical constituents in water (filtered and associated with particles) at high temporal resolution from 2016-2020. This was done (1) at inflow and outflow locations of three successive hydroelectric reservoirs (Snake River, Idaho, Oregon) and (2) vertically and longitudinally within the first reservoir (Brownlee Reservoir). Under spring high flow, upstream inputs of particulate Hg (Hg(II) and MeHg) and filter-passing Hg(II) to Brownlee Reservoir were governed by total suspended solids and dissolved organic matter, respectively. Under redox stratified conditions in summer, net MeHg formation in the meta- and hypolimnion of Brownlee reservoir yielded elevated filter-passing and particulate MeHg concentrations, the latter exceeding 500 ng g-1 on particles. Simultaneously, the organic matter content of particulates increased longitudinally in the reservoir (from 9-29%) and temporally with stratified duration. In late summer and fall, destratification mobilized MeHg from the upgradient metalimnion and the downgradient hypolimnion of Brownlee Reservoir, respectively, resulting in downstream export of elevated filter-passing MeHg and organic-rich particles enriched in MeHg (up to 43% MeHg). We document coupled biogeochemical and hydrologic processes that yield in-reservoir MeHg accumulation and MeHg export in water and particles, which impacts MeHg uptake in aquatic food webs within and downstream of reservoirs.

Environmental formation of methylmercury is controlled by synergy of inorganic mercury bioavailability and microbial mercury-methylation capacity.

Methylmercury (MeHg) production is controlled by the bioavailability of inorganic divalent mercury (Hg(II)i ) and Hg-methylation capacity of the microbial community (conferred by the hgcAB gene cluster). However, the relative importance of these factors and their interaction in the environment remain poorly understood. Here, metagenomic sequencing and a full-factorial MeHg formation experiment were conducted across a wetland sulfate gradient with different microbial communities and pore water chemistries. From this experiment, the relative importance of each factor on MeHg formation was isolated. Hg(II)i bioavailability correlated with the dissolved organic matter composition, while the microbial Hg-methylation capacity correlated with the abundance of hgcA genes. MeHg formation responded synergistically to both factors. Notably, hgcA sequences were from diverse taxonomic groups, none of which contained genes for dissimilatory sulfate reduction. This work expands our understanding of the geochemical and microbial constraints on MeHg formation in situ and provides an experimental framework for further mechanistic studies.

Can preserved museum specimens be used to reconstruct fish mercury burden and sources through time?

To evaluate the utility of preserved fishes for reconstructing historical and spatial patterns of mercury (Hg) exposure, we experimentally tested the stability of Hg concentrations and Hg stable isotope ratios under standard museum practices of specimen preservation. We found that loss of unidentified constituents during preservation increased Hg concentrations in fish muscle. Low-Hg fish reared in the laboratory were susceptible to exogenous contamination with inorganic mercury (iHg) when preservative fluids were intentionally spiked or iHg leached passively from contaminated wild fishes in the same container. This contamination impacted Hg isotope values of total Hg, but the conservative nature of methylmercury allows us to quantitatively correct for iHg contamination. Our findings validate the potential to use fishes from the world's museums to generate spatiotemporal baselines for the Minamata Convention on Mercury, but we recommend a set of precautions to maximize inference strength. Selecting the largest specimens of a target species helps dilute any iHg contamination. Specimens should be drawn from lots that were not comingled with fishes from other collections to minimize risk of iHg transfer among fish with different contamination histories. Finally, focusing on low-lipid species will enhance the comparability of Hg concentrations between historical and contemporary collections.

In-Reservoir Physical Processes Modulate Aqueous and Biological Methylmercury Export from a Seasonally Anoxic Reservoir.

Anoxic conditions within reservoirs related to thermal stratification and oxygen depletion lead to methylmercury (MeHg) production, a key process governing the uptake of mercury in aquatic food webs. Once formed within a reservoir, the timing and magnitude of the biological uptake of MeHg and the relative importance of MeHg export in water versus biological compartments remain poorly understood. We examined the relations between the reservoir stratification state, anoxia, and the concentrations and export loads of MeHg in aqueous and biological compartments at the outflow locations of two reservoirs of the Hells Canyon Complex (Snake River, Idaho-Oregon). Results show that (1) MeHg concentrations in filter-passing water, zooplankton, suspended particles, and detritus increased in response to reservoir destratification; (2) zooplankton MeHg strongly correlated with MeHg in filter-passing water during destratification; (3) reservoir anoxia appeared to be a key control on MeHg export; and (4) biological MeHg, primarily in zooplankton, accounted for only 5% of total MeHg export from the reservoirs (the remainder being aqueous compartments). These results improve our understanding of the role of biological incorporation of MeHg and the subsequent downstream release from seasonally stratified reservoirs and demonstrate that in-reservoir physical processes strongly influence MeHg incorporation at the base of the aquatic food web.

Using carbon, nitrogen, and mercury isotope values to distinguish mercury sources to Alaskan lake trout.

Lake trout (Salvelinus namaycush), collected from 13 remote lakes located in southwestern Alaska, were analyzed for carbon, nitrogen, and mercury (Hg) stable isotope values to assess the importance of migrating oceanic salmon, volcanic activity, and atmospheric deposition to fish Hg burden. Methylmercury (MeHg) bioaccumulation in phytoplankton (5.0 - 6.9 kg L-1) was also measured to quantify the basal uptake of MeHg to these aquatic food webs. Hg isotope values in lake trout revealed that while the extent of precipitation-delivered Hg was similar across the entire study area, volcanic Hg is likely an important additional source to lake trout in proximate lakes. In contrast, migratory salmon (Oncorhynchus nerka) deliver little MeHg to lake trout directly, although indirect delivery processes via decay could exist. A high level of variability in carbon, nitrogen, and Hg isotope values indicate niche partitioning in lake trout populations within each lake and that a complex suite of ecological interactions is occurring, complicating the conceptually linear assessment of contaminant source to receiving organism. Without connecting energy and contaminant isotope axes, we would not have understood why lake trout from these pristine lakes have highly variable Hg burdens despite consistently low water Hg and comparable age-length dynamics.

Decadal trends of mercury cycling and bioaccumulation within Everglades National Park.

Mercury (Hg) contamination has been a persistent concern in the Florida Everglades for over three decades due to elevated atmospheric deposition and the system's propensity for methylation and rapid bioaccumulation. Given declines in atmospheric Hg concentrations in the conterminous United States and efforts to mitigate nutrient release to the greater Everglades ecosystem, it was vital to assess how Hg dynamics responded on temporal and spatial scales. This study used a multimedia approach (water and biota) to examine Hg and methylmercury (MeHg) dynamics across a 76-site network within the southernmost portion of the region, Everglades National Park (ENP), from 2008 to 2018. Hg concentrations across matrices showed that air, water, and biota from the system were inextricably linked. Temporal patterns across matrices were driven primarily by hydrologic and climatic changes in the park and no evidence of a decline in atmospheric Hg deposition from 2008 to 2018 was observed, unlike other regions of the United States. In the Shark River Slough (SRS), excess dissolved organic carbon and sulfate were also consistently delivered from upgradient canals and showed no evidence of decline over the study period. Within the SRS a strong positive correlation was observed between MeHg concentrations in surface water and resident fish. Within distinct geographic regions of ENP (SRS, Marsh, Coastal), the geochemical controls on MeHg dynamics differed and highlighted regions susceptible to higher MeHg bioaccumulation, particularly in the SRS and Coastal regions. This study demonstrates the strong influence that dissolved organic carbon and sulfate loads have on spatial and temporal distributions of MeHg across ENP. Importantly, improved water quality and flow rates are two key restoration targets of the nearly 30-year Everglades restoration program, which if achieved, this study suggests would lead to reduced MeHg production and exposure.

Experimental evidence for recovery of mercury-contaminated fish populations.

Anthropogenic releases of mercury (Hg)1-3 are a human health issue4 because the potent toxicant methylmercury (MeHg), formed primarily by microbial methylation of inorganic Hg in aquatic ecosystems, bioaccumulates to high concentrations in fish consumed by humans5,6. Predicting the efficacy of Hg pollution controls on fish MeHg concentrations is complex because many factors influence the production and bioaccumulation of MeHg7-9. Here we conducted a 15-year whole-ecosystem, single-factor experiment to determine the magnitude and timing of reductions in fish MeHg concentrations following reductions in Hg additions to a boreal lake and its watershed. During the seven-year addition phase, we applied enriched Hg isotopes to increase local Hg wet deposition rates fivefold. The Hg isotopes became increasingly incorporated into the food web as MeHg, predominantly from additions to the lake because most of those in the watershed remained there. Thereafter, isotopic additions were stopped, resulting in an approximately 100% reduction in Hg loading to the lake. The concentration of labelled MeHg quickly decreased by up to 91% in lower trophic level organisms, initiating rapid decreases of 38-76% of MeHg concentration in large-bodied fish populations in eight years. Although Hg loading from watersheds may not decline in step with lowering deposition rates, this experiment clearly demonstrates that any reduction in Hg loadings to lakes, whether from direct deposition or runoff, will have immediate benefits to fish consumers.

Enhanced Susceptibility of Methylmercury Bioaccumulation into Seston of the Laurentian Great Lakes.

Mercury concentrations in the Laurentian Great Lakes waters are among the lowest reported in the literature, while game fish concentrations approach consumption advisory limits, particularly in Lakes Superior, Huron, and Michigan, indicating efficient methylmercury transfer from water to game fish. To determine if increased transfer efficiency is evident within the lower food web, we measured (2010-2018) mercury and dissolved organic carbon (DOC) in water, and in size-sieved seston, dietary tracers (carbon and nitrogen isotope ratios), phytoplankton methylmercury bioaccumulation, and methylmercury biomagnification between increasing seston size fractions. We observed consistently low filter-passing methylmercury (<0.010 ng L-1) and comparatively variable DOC (1.1 to 3.4 mg L-1) concentrations. Methylmercury biomagnification factors between size-sieved seston were similar between lakes. Bioaccumulation factors in phytoplankton were among the highest in the literature (log 5.5 to 6.1), exceeding those in oceans, smaller lakes, and streams, and was influenced by DOC. Higher bioaccumulation rates increase the susceptibility of methylmercury accumulation into the food web. Because mercury is dominantly delivered to the Great Lakes through the atmosphere and the biota therein is highly susceptible to methylmercury uptake, we propose that the Laurentian Great Lakes are excellent sentinels to trace the success of efforts to decrease global mercury emissions (e.g., Minamata Treaty) in the future.

Stable Isotope Fractionation Reveals Similar Atomic-Level Controls during Aerobic and Anaerobic Microbial Hg Transformation Pathways.

Mercury (Hg) is a global pollutant and potent neurotoxin that bioaccumulates in food webs as monomethylmercury (MeHg). The production of MeHg is driven by anaerobic and Hg redox cycling pathways, such as Hg reduction, which control the availability of Hg to methylators. Anaerobes play an important role in Hg reduction in methylation hot spots, yet their contributions remain underappreciated due to how challenging these pathways are to study in the absence of dedicated genetic targets and low levels of Hg0 in anoxic environments. In this study, we used Hg stable isotope fractionation to explore Hg reduction during anoxygenic photosynthesis and fermentation in the model anaerobe Heliobacterium modesticaldum Ice1. We show that cells preferentially reduce lighter Hg isotopes in both metabolisms, leading to mass-dependent fractionation, but mass-independent fractionation commonly induced by UV-visible light is absent. Due to the variability associated with replicate experiments, we could not discern whether dedicated physiological processes drive Hg reduction during photosynthesis and fermentation. However, we demonstrate that fractionation is affected by the interplay between pathways controlling Hg recruitment, accessibility, and availability alongside metabolic redox reactions. The combined contributions of these processes lead to isotopic enrichment during anoxygenic photosynthesis that is in between the values reported for anaerobic respiratory microbial Hg reduction and abiotic photoreduction. Isotope enrichment during fermentation is closer to what has been observed in aerobic bacteria that reduce Hg through dedicated detoxification pathways. Our work suggests that similar controls likely underpin diverse microbe-mediated Hg transformations that affect Hg's fate in oxic and anoxic habitats. IMPORTANCE Anaerobic and photosynthetic bacteria that reduce mercury affect mercury delivery to microbes in methylation sites that drive bioaccumulation in food webs. Anaerobic mercury reduction pathways remain underappreciated in the current view of the global mercury cycle because they are challenging to study, bearing no dedicated genetic targets to establish physiological mechanisms. In this study, we used stable isotopes to characterize the physiological processes that control mercury reduction during photosynthesis and fermentation in the model anaerobe Heliobacterium modesticaldum Ice1. The sensitivity of isotope analyses highlighted the subtle contribution of mercury uptake to the isotope signature associated with anaerobic mercury reduction. When considered alongside the isotope signatures associated with microbial pathways for which genetic determinants have been identified, our findings underscore the narrow range of isotope enrichment that is characteristic of microbial mercury transformations. This suggests that there are common atomic-level controls for biological mercury transformations across a broad range of geochemical conditions.

Examining historical mercury sources in the Saint Louis River estuary: How legacy contamination influences biological mercury levels in Great Lakes coastal regions.

Industrial chemical contamination within coastal regions of the Great Lakes can pose serious risks to wetland habitat and offshore fisheries, often resulting in fish consumption advisories that directly affect human and wildlife health. Mercury (Hg) is a contaminant of concern in many of these highly urbanized and industrialized coastal regions, one of which is the Saint Louis River estuary (SLRE), the second largest tributary to Lake Superior. The SLRE has legacy Hg contamination that drives high Hg concentrations within sediments, but it is unclear whether legacy-derived Hg actively cycles within the food web. To understand the relative contributions of legacy versus contemporary Hg sources in coastal zones, Hg, carbon, and nitrogen stable isotope ratios were measured in sediments and food webs of SLRE and the Bad River, an estuarine reference site. Hg stable isotope values revealed that legacy contamination of Hg was widespread and heterogeneously distributed in sediments of SLRE, even in areas lacking industrial Hg sources. Similar isotope values were found in benthic invertebrates, riparian spiders, and prey fish from SLRE, confirming legacy Hg reaches the SLRE food web. Direct comparison of prey fish from SLRE and the Bad River confirmed that Hg isotope differences between the sites were not attributable to fractionation associated with rapid Hg bioaccumulation at estuarine mouths, but due to the presence of industrial Hg within SLRE. The Hg stable isotope values of game fish in both estuaries were dependent on fish migration and diet within the estuaries and extending into Lake Superior. These results indicate that Hg from legacy contamination is actively cycling within the SLRE food web and, through migration, this Hg also extends into Lake Superior via game fish. Understanding sources and the movement of Hg within the estuarine food web better informs restoration strategies for other impaired Great Lakes coastal zones.

Surface-air mercury fluxes and a watershed mass balance in forested and harvested catchments.

Forest soils are among the world's largest repositories for long-term accumulation of atmospherically deposited mercury (Hg), and understanding the potential for remobilization through gaseous emissions, aqueous dissolution and runoff, or erosive particulate transport to down-gradient aquatic ecosystems is critically important for projecting ecosystem recovery. Forestry operations, especially clear-cut logging where most of the vegetaiton is removed, can influence Hg mobility/fluxes, foodweb dynamics, and bioaccumulation processes. This paper measured surface-air Hg fluxes from catchments in the Pacific Northwest, USA, to determine if there is a difference between forested and logged catchments. These measurements were conducted as part of a larger project on the impact of forestry operations on Hg cycling which include measurements of water fluxes as well as impacts on biota. Surface-air Hg fluxes were measured using a commonly applied dynamic flux chamber (DFC) method that incorporated diel and seasonal variability in elemental Hg (Hg0) fluxes at multiple forested and harvested catchments. The results showed that the forested ecosystem had depositional Hg0 fluxes throughout most of the year (annual mean: -0.26 ng/m2/h). In contrast, the harvested catchments showed mostly emission of Hg0 (annual mean: 0.63 ng/m2/h). Differences in solar radiation reaching the soil was the primary driver resulting in a shift from net deposition to emission in harvested catchments. The surface-air Hg fluxes were larger than the fluxes to water as runoff and accounted for 97% of the differences in Hg sequestered in forested versus harvested catchments.

The influence of legacy contamination on the transport and bioaccumulation of mercury within the Mobile River Basin.

Past industrial use and subsequent release of mercury (Hg) into the environment have resulted in severe cases of legacy contamination that still influence contemporary Hg levels in biota. While the bioaccumulation of legacy Hg is commonly assessed via concentration measurements within fish tissue, this practice becomes difficult in regions of high productivity and methylmercury (MeHg) production, like the Mobile River Basin, Alabama in the southeastern United States. This study applied Hg stable isotope tracers to distinguish legacy Hg from regional deposition sources in sediments, waters, and fish within the Mobile River. Sediments and waters displayed differences in δ202Hg between industrial and background sites, which corresponded to drastic differences in Hg concentration. Sites that were affected by legacy Hg, as defined by δ202Hg, produced largemouth bass with lower MeHg content (59-70%) than those captured in the main rivers (>85%). Direct measurements of Hg isotopes and mathematical estimates of MeHg isotope pools in fish displayed similar distinctions between legacy and watershed sources as observed in other matrices. These results indicate that legacy Hg can accumulate directly into fish tissue as the inorganic species and may also be available for methylation within contaminated zones decades after the initial release.

Resolving Atmospheric Mercury Loading and Source Trends from Isotopic Records of Remote North American Lake Sediments.

The strongest evidence for anthropogenic alterations to the global mercury (Hg) cycle comes from historical records of mercury deposition preserved in lake sediments. Hg isotopes have added a new dimension to these sedimentary archives, promising additional insights into Hg source apportionment and biogeochemical processing. Presently, most interpretations of historical changes are constrained to a small number of locally contaminated ecosystems. Here, we describe changes in natural Hg isotope records from a suite of dated sediment cores collected from various remote lakes of North America. In nearly all cases, the rise in industrial-use Hg is accompanied by an increase in δ202Hg and Δ199Hg values. These trends can be attributed to large-scale industrial emission of Hg into the atmosphere and are consistent with positive Δ199Hg values measured in modern-day precipitation and modeled increases in δ202Hg values from global emission inventories. Despite similar temporal trends among cores, the baseline isotopic values vary considerably among the different study regions, likely attributable to differences in the fractionation produced in situ as well as differing amounts of atmospherically delivered Hg. Differences among the study lakes in precipitation and watershed size provide an empirical framework for evaluating Hg isotopic signatures and global Hg cycling.

Isolation of methylmercury using distillation and anion-exchange chromatography for isotopic analyses in natural matrices.

The development of mercury (Hg) stable isotope measurements has enhanced the study of Hg sources and transformations in the environment. As a result of the mixing of inorganic Hg (iHg) and methylmercury (MeHg) species within organisms of the aquatic food web, understanding species-specific Hg stable isotopic compositions is of significant importance. The lack of MeHg isotope measurements is due to the analytical difficulty in the separation of the MeHg from the total Hg pool, with only a few methods having been tested over the past decade with varying degrees of success, and only a handful of environmentally relevant measurements. Here, we present a novel anion-exchange resin separation method using AG 1-X4 that further isolates MeHg from the sample matrix, following a distillation pretreatment, in order to obtain ambient MeHg stable isotopic compositions. This method avoids the use of organic reagents, does not require complex instrumentation, and is applicable across matrices. Separation tests across sediment, water, and biotic matrices showed acceptable recoveries (98 ± 5%, n = 54) and reproducible δ202Hg isotope results (2 SDs ≤ 0.15‰) down to 5 ng of MeHg. The measured MeHg pools in natural matrices, such as plankton and sediments, showed large deviations from the non-speciated total Hg measurement, indicating that there is an important isotopic shift during methylation that is not recorded by typical measurements, but is vital in order to assess sources of Hg during bioaccumulation. Graphical abstract.

Mercury source changes and food web shifts alter contamination signatures of predatory fish from Lake Michigan.

To understand the impact reduced mercury (Hg) loading and invasive species have had on methylmercury bioaccumulation in predator fish of Lake Michigan, we reconstructed bioaccumulation trends from a fish archive (1978 to 2012). By measuring fish Hg stable isotope ratios, we related temporal changes in Hg concentrations to varying Hg sources. Additionally, dietary tracers were necessary to identify food web influences. Through combined Hg, C, and N stable isotopic analyses, we were able to differentiate between a shift in Hg sources to fish and periods when energetic transitions (from dreissenid mussels) led to the assimilation of contrasting Hg pools (2000 to present). In the late 1980s, lake trout δ202Hg increased (0.4‰) from regulatory reductions in regional Hg emissions. After 2000, C and N isotopes ratios revealed altered food web pathways, resulting in a benthic energetic shift and changes to Hg bioaccumulation. Continued increases in δ202Hg indicate fish are responding to several United States mercury emission mitigation strategies that were initiated circa 1990 and continued through the 2011 promulgation of the Mercury and Air Toxics Standards rule. Unlike archives of sediments, this fish archive tracks Hg sources susceptible to bioaccumulation in Great Lakes fisheries. Analysis reveals that trends in fish Hg concentrations can be substantially affected by shifts in trophic structure and dietary preferences initiated by invasive species in the Great Lakes. This does not diminish the benefits of declining emissions over this period, as fish Hg concentrations would have been higher without these actions.

Chemical and Physical Controls on Mercury Source Signatures in Stream Fish from the Northeastern United States.

Streams in the northeastern U.S. receive mercury (Hg) in varying proportions from atmospheric deposition and legacy point sources, making it difficult to attribute shifts in fish concentrations directly back to changes in Hg source management. Mercury stable isotope tracers were utilized to relate sources of Hg to co-located fish and bed sediments from 23 streams across a forested to urban-industrial land-use gradient within this region. Mass-dependent isotopes (δ202Hg) in prey and game fish at forested sites were depleted (medians -0.95 and -0.83 ‰, respectively) in comparison to fish from urban-industrial settings (medians -0.26 and -0.38 ‰, respectively); the forested site group also had higher prey fish Hg concentrations. The separation of Hg isotope signatures in fish was strongly related to in-stream and watershed land-use indicator variables. Fish isotopes were strongly correlated with bed sediment isotopes, but the isotopic offset between the two matrices was variable due to differing ecosystem-specific drivers controlling the extent of MeHg formation. The multivariable approach of analyzing watershed characteristics and stream chemistry reveals that the Hg isotope composition in fish is linked to current and historic Hg sources in the northeastern U.S. and can be used to trace bioaccumulated Hg.

Timber harvest alters mercury bioaccumulation and food web structure in headwater streams.

Timber harvest has many effects on aquatic ecosystems, including changes in hydrological, biogeochemical, and ecological processes that can influence mercury (Hg) cycling. Although timber harvest's influence on aqueous Hg transformation and transport are well studied, the effects on Hg bioaccumulation are not. We evaluated Hg bioaccumulation, biomagnification, and food web structure in 10 paired catchments that were either clear-cut in their entirety, clear-cut except for an 8-m wide riparian buffer, or left unharvested. Average mercury concentrations in aquatic biota from clear-cut catchments were 50% higher than in reference catchments and 165% higher than in catchments with a riparian buffer. Mercury concentrations in aquatic invertebrates and salamanders were not correlated with aqueous THg or MeHg concentrations, but rather treatment effects appeared to correspond with differences in the utilization of terrestrial and aquatic basal resources in the stream food webs. Carbon and nitrogen isotope data suggest that a diminished shredder niche in the clear-cut catchments contributed to lower basal resource diversity compared with the reference of buffered treatments, and that elevated Hg concentrations in the clear-cut catchments reflect an increased reliance on aquatic resources in clear-cut catchments. In contrast, catchments with riparian buffers had higher basal resource diversity than the reference catchments, indicative of more balanced utilization of terrestrial and aquatic resources. Further, following timber harvest THg concentrations in riparian songbirds were elevated, suggesting an influence of timber harvest on Hg export to riparian food webs. These data, coupled with comparisons of individual feeding guilds, indicate that changes in organic matter sources and associated effects on stream food web structure are important mechanisms by which timber harvest modifies Hg bioaccumulation in headwater streams and riparian consumers.