Michael T. Tate

Whole-ecosystem study shows rapid fish-mercury response to changes in mercury deposition

Methylmercury contamination of fisheries from centuries of industrial atmospheric emissions negatively impacts humans and wildlife worldwide. The response of fish methylmercury concentrations to changes in mercury deposition has been difficult to establish because sediments/soils contain large pools of historical contamination, and many factors in addition to deposition affect fish mercury. To test directly the response of fish contamination to changing mercury deposition, we conducted a whole-ecosystem experiment, increasing the mercury load to a lake and its watershed by the addition of enriched stable mercury isotopes. The isotopes allowed us to distinguish between experimentally applied mercury and mercury already present in the ecosystem and to examine bioaccumulation of mercury deposited to different parts of the watershed. Fish methylmercury concentrations responded rapidly to changes in mercury deposition over the first 3 years of study. Essentially all of the increase in fish methylmercury concentrations came from mercury deposited directly to the lake surface. In contrast, <1% of the mercury isotope deposited to the watershed was exported to the lake. Steady state was not reached within 3 years. Lake mercury isotope concentrations were still rising in lake biota, and watershed mercury isotope exports to the lake were increasing slowly. Therefore, we predict that mercury emissions reductions will yield rapid (years) reductions in fish methylmercury concentrations and will yield concomitant reductions in risk. However, a full response will be delayed by the gradual export of mercury stored in watersheds. The rate of response will vary among lakes depending on the relative surface areas of water and watershed.

Comparison of atmospheric mercury speciation and deposition at nine sites across central and eastern North America

[1] This study presents >5 cumulative years of tropospheric mercury (Hg) speciation measurements, over the period of 2003-2009, for eight sites in the central and eastern United States and one site in coastal Puerto Rico. The purpose of this research was to identify local and regional processes that impact Hg speciation and deposition (wet + dry) across a large swath of North America. Sites sampled were selected to represent both a wide range of mercury exposure and environmental conditions. Seasonal mean concentrations of elemental Hg (1.27 ± 0.31 to 2.94 ± 1.57 ng m -3 ; x ± σ), reactive gaseous mercury (RGM; 1.5 ± 1.6 to 63.3 ± 529 pg m -3 ), and fine particulate Hg (1.2 ± 1.4 to 37.9 ± 492 pg m -3 ) were greatest at sites impacted by Hg point sources. Diel bin plots of Hg° and RGM suggest control by a variety of local/regional processes including impacts from Hg point sources and boundary layer/free tropospheric interactions as well as from larger-scale processes affecting Hg speciation (i.e., input of the global Hg pool, RGM formed from oxidation of Hg° by photochemical compounds at coastal sites, and elemental Hg depletion during periods of dew formation). Comparison of wet Hg deposition (measured), RGM and fine particulate Hg dry deposition (calculated using a multiple resistance model), and anthropogenic point source emissions varied significantly between sites. Significant correlation between emission sources and dry deposition was observed but was highly dependant upon inclusion of data from two sites with exceptionally high deposition. Findings from this study highlight the importance of environmental setting on atmospheric Hg cycling and deposition rates.

LITHOSPHERIC EXTENSION AND MAGMATISM IN THE PORCUPINE BASIN WEST OF IRELAND

The Porcupine Seabight Basin is a north-south trending, extensional sedimentary basin situated on the continental shelf west of Ireland. It is filled with sedimentary rocks which range in age from Devonian to present-day. A large amount of geological and geophysical data is now available for this basin, mainly as a result of oil industry exploration. In this paper, information from 23 well logs and from regional seismic reflection surveys is used to determine the lithospheric stretching history of the basin. Subsidence analyses indicate that there was one main phase of stretching which began in late Liassic times (∼ 180 Ma), ending in earliest Cretaceous (∼ 145 Ma). Stretching factors at the northern end of the basin are relatively small (β = 1.1–1.7) but increase rapidly southwards along the axis of the Main Porcupine Basin. In the southern part of the region (the Seabight Basin), β is greater than 6. The simplest way to accommodate this rapid variation in stretching is by clockwise rotation of the Porcupine Ridge through approximately 20°, away from the Irish Shelf. Subsidence-derived stretching values are in reasonable agreement with those determined previously from crustal thicknesses based on gravity models and deep seismic data (normal incidence and wide-angle). The existence, location, and inferred age of the Porcupine Median Volcanic Ridge are also consistent with the subsidence-derived stretching factors. After intermittent Paleocene igneous activity, an anomalous increase in the rate of subsidence occurred in the Eocene, between 55 and 42 Ma. There is little evidence that this rapid increase is caused by lithospheric stretching, and we conclude that it must be associated in some unknown way with melt generated by development of the Iceland hotspot.

The role of terrestrial vegetation in atmospheric Hg deposition: Pools and fluxes of spike and ambient Hg from the METAALICUS experiment

[1] As part of the Mercury Experiment to Assess Atmospheric Loading in Canada and the U.S. (METAALICUS), different stable Hg(II) isotope spikes were applied to the upland and wetland areas of a boreal catchment between 2001 and 2006 to examine retention of newly deposited Hg(II). In the present study, a Geographical Information Systems (GIS)-based approach was used to quantify canopy and ground vegetation pools of experimentally applied upland and wetland spike Hg within the METAALICUS watershed over the terrestrial loading phase of the experiment. A chemical kinetic model was also used to describe the changes in spike Hg concentrations of canopy and ground vegetation over time. An examination of the fate of spike Hg initially present on canopy vegetation using a mass balance approach indicated that the largest percentage flux from the canopy over one year post-spray was emission to the atmosphere (upland: 45%; wetland: 71%), followed by litterfall (upland: 14%; wetland: 10%) and throughfall fluxes (upland: 12%; wetland: 9%) and longer term retention of spike in the forest canopy (11% for both upland and wetland). Average half-lives (t1/2) of spike on deciduous (110 � 30 days) and coniferous (180 � 40 days) canopy and ground vegetation (890 � 620 days) indicated that retention of new atmospheric Hg(II) on terrestrial (especially ground) vegetation delays downward transport of new atmospheric Hg(II) into the soil profile and runoff into lakes.

Spatial and temporal patterns of mercury concentrations in freshwater fish across the Western United States and Canada

Methylmercury contamination of fish is a global threat to environmental health. Mercury (Hg) monitoring programs are valuable for generating data that can be compiled for spatially broad syntheses to identify emergent ecosystem properties that influence fish Hg bioaccumulation. Fish total Hg (THg) concentrations were evaluated across the Western United States (US) and Canada, a region defined by extreme gradients in habitat structure and water management. A database was compiled with THg concentrations in 96,310 fish that comprised 206 species from 4262 locations, and used to evaluate the spatial distribution of fish THg across the region and effects of species, foraging guilds, habitats, and ecoregions. Areas of elevated THg exposure were identified by developing a relativized estimate of fish mercury concentrations at a watershed scale that accounted for the variability associated with fish species, fish size, and site effects. THg concentrations in fish muscle ranged between 0.001 and 28.4 (μg/g wet weight (ww)) with a geometric mean of 0.17. Overall, 30% of individual fish samples and 17% of means by location exceeded the 0.30μg/g ww US EPA fish tissue criterion. Fish THg concentrations differed among habitat types, with riverine habitats consistently higher than lacustrine habitats. Importantly, fish THg concentrations were not correlated with sediment THg concentrations at a watershed scale, but were weakly correlated with sediment MeHg concentrations, suggesting that factors influencing MeHg production may be more important than inorganic Hg loading for determining fish MeHg exposure. There was large heterogeneity in fish THg concentrations across the landscape; THg concentrations were generally higher in semi-arid and arid regions such as the Great Basin and Desert Southwest, than in temperate forests. Results suggest that fish mercury exposure is widespread throughout Western US and Canada, and that species, habitat type, and region play an important role in influencing ecological risk of mercury in aquatic ecosystems.

Microbial mercury methylation in Antarctic sea ice

Atmospheric deposition of mercury onto sea ice and circumpolar sea water provides mercury for microbial methylation, and contributes to the bioaccumulation of the potent neurotoxin methylmercury in the marine food web. Little is known about the abiotic and biotic controls on microbial mercury methylation in polar marine systems. However, mercury methylation is known to occur alongside photochemical and microbial mercury reduction and subsequent volatilization. Here, we combine mercury speciation measurements of total and methylated mercury with metagenomic analysis of whole-community microbial DNA from Antarctic snow, brine, sea ice and sea water to elucidate potential microbially mediated mercury methylation and volatilization pathways in polar marine environments. Our results identify the marine microaerophilic bacterium Nitrospina as a potential mercury methylator within sea ice. Anaerobic bacteria known to methylate mercury were notably absent from sea-ice metagenomes. We propose that Antarctic sea ice can harbour a microbial source of methylmercury in the Southern Ocean.

Surface-air mercury fluxes across Western North America: A synthesis of spatial trends and controlling variables.

Mercury (Hg) emission and deposition can occur to and from soils, and are an important component of the global atmospheric Hg budget. This paper focuses on synthesizing existing surface-air Hg flux data collected throughout the Western North American region and is part of a series of geographically focused Hg synthesis projects. A database of existing Hg flux data collected using the dynamic flux chamber (DFC) approach from almost a thousand locations was created for the Western North America region. Statistical analysis was performed on the data to identify the important variables controlling Hg fluxes and to allow spatiotemporal scaling. The results indicated that most of the variability in soil-air Hg fluxes could be explained by variations in soil-Hg concentrations, solar radiation, and soil moisture. This analysis also identified that variations in DFC methodological approaches were detectable among the field studies, with the chamber material and sampling flushing flow rate influencing the magnitude of calculated emissions. The spatiotemporal scaling of soil-air Hg fluxes identified that the largest emissions occurred from irrigated agricultural landscapes in California. Vegetation was shown to have a large impact on surface-air Hg fluxes due to both a reduction in solar radiation reaching the soil as well as from direct uptake of Hg in foliage. Despite high soil Hg emissions from some forested and other heavily vegetated regions, the net ecosystem flux (soil flux+vegetation uptake) was low. Conversely, sparsely vegetated regions showed larger net ecosystem emissions, which were similar in magnitude to atmospheric Hg deposition (except for the Mediterranean California region where soil emissions were higher). The net ecosystem flux results highlight the important role of landscape characteristics in effecting the balance between Hg sequestration and (re-)emission to the atmosphere.

Reservoirs and water management influence fish mercury concentrations in the western United States and Canada.

Anthropogenic manipulation of aquatic habitats can profoundly alter mercury (Hg) cycling and bioaccumulation. The impoundment of fluvial systems is among the most common habitat manipulations and is known to increase fish Hg concentrations immediately following impoundment. However, it is not well understood how Hg concentrations differ between reservoirs and lakes at large spatial and temporal scales or how reservoir management influences fish Hg concentrations. This study evaluated total Hg (THg) concentrations in 64,386 fish from 883 reservoirs and 1387 lakes, across the western United States and Canada, to assess differences between reservoirs and lakes, as well as the influence of reservoir management on fish THg concentrations. Fish THg concentrations were 1.4-fold higher in reservoirs (0.13±0.011μg/g wet weight±standard error) than lakes (0.09±0.006), though this difference varied among ecoregions. Fish THg concentrations were 1.5- to 2.6-fold higher in reservoirs than lakes of the North American Deserts, Northern Forests, and Mediterranean California ecoregions, but did not differ between reservoirs and lakes in four other ecoregions. Fish THg concentrations peaked in three-year-old reservoirs then rapidly declined in 4-12year old reservoirs. Water management was particularly important in influencing fish THg concentrations, which were up to 11-times higher in reservoirs with minimum water storage occurring in May, June, or July compared to reservoirs with minimum storage occurring in other months. Between-year changes in maximum water storage strongly influenced fish THg concentrations, but within-year fluctuations in water levels did not influence fish THg concentrations. Specifically, fish THg concentrations increased up to 3.2-fold over the range of between-year changes in maximum water storage in all ecoregions except Mediterranean California. These data highlight the role of reservoir creation and management in influencing fish THg concentrations and suggest that water management may provide an effective means of mitigating Hg bioaccumulation in some reservoirs.

Mercury and methylmercury in aquatic sediment across western North America.

Large-scale assessments are valuable in identifying primary factors controlling total mercury (THg) and monomethyl mercury (MeHg) concentrations, and distribution in aquatic ecosystems. Bed sediment THg and MeHg concentrations were compiled for >16,000 samples collected from aquatic habitats throughout the West between 1965 and 2013. The influence of aquatic feature type (canals, estuaries, lakes, and streams), and environmental setting (agriculture, forest, open-water, range, wetland, and urban) on THg and MeHg concentrations was examined. THg concentrations were highest in lake (29.3±6.5μgkg(-1)) and canal (28.6±6.9μgkg(-1)) sites, and lowest in stream (20.7±4.6μgkg(-1)) and estuarine (23.6±5.6μgkg(-1)) sites, which was partially a result of differences in grain size related to hydrologic gradients. By environmental setting, open-water (36.8±2.2μgkg(-1)) and forested (32.0±2.7μgkg(-1)) sites generally had the highest THg concentrations, followed by wetland sites (28.9±1.7μgkg(-1)), rangeland (25.5±1.5μgkg(-1)), agriculture (23.4±2.0μgkg(-1)), and urban (22.7±2.1μgkg(-1)) sites. MeHg concentrations also were highest in lakes (0.55±0.05μgkg(-1)) and canals (0.54±0.11μgkg(-1)), but, in contrast to THg, MeHg concentrations were lowest in open-water sites (0.22±0.03μgkg(-1)). The median percent MeHg (relative to THg) for the western region was 0.7%, indicating an overall low methylation efficiency; however, a significant subset of data (n>100) had percentages that represent elevated methylation efficiency (>6%). MeHg concentrations were weakly correlated with THg (r(2)=0.25) across western North America. Overall, these results highlight the large spatial variability in sediment THg and MeHg concentrations throughout western North America and underscore the important roles that landscape and land-use characteristics have on the MeHg cycle.

Assessing potential health risks to fish and humans using mercury concentrations in inland fish from across western Canada and the United States

Fish represent high quality protein and nutrient sources, but Hg contamination is ubiquitous in aquatic ecosystems and can pose health risks to fish and their consumers. Potential health risks posed to fish and humans by Hg contamination in fish were assessed in western Canada and the United States. A large compilation of inland fish Hg concentrations was evaluated in terms of potential health risk to the fish themselves, health risk to predatory fish that consume Hg contaminated fish, and to humans that consume Hg contaminated fish. The probability that a fish collected from a given location would exceed a Hg concentration benchmark relevant to a health risk was calculated. These exceedance probabilities and their associated uncertainties were characterized for fish of multiple size classes at multiple health-relevant benchmarks. The approach was novel and allowed for the assessment of the potential for deleterious health effects in fish and humans associated with Hg contamination in fish across this broad study area. Exceedance probabilities were relatively common at low Hg concentration benchmarks, particularly for fish in larger size classes. Specifically, median exceedances for the largest size classes of fish evaluated at the lowest Hg concentration benchmarks were 0.73 (potential health risks to fish themselves), 0.90 (potential health risk to predatory fish that consume Hg contaminated fish), and 0.97 (potential for restricted fish consumption by humans), but diminished to essentially zero at the highest benchmarks and smallest fish size classes. Exceedances of benchmarks are likely to have deleterious health effects on fish and limit recommended amounts of fish humans consume in western Canada and the United States. Results presented here are not intended to subvert or replace local fish Hg data or consumption advice, but provide a basis for identifying areas of potential health risk and developing more focused future research and monitoring efforts.