Mark E. Brigham

Mercury trends in fish from rivers and lakes in the United States, 1969-2005

A national dataset on concentrations of mercury in fish, compiled mainly from state and federal monitoring programs, was used to evaluate trends in mercury (Hg) in fish from US rivers and lakes. Trends were analyzed on data aggregated by site and by state, using samples of the same fish species and tissue type, and using fish of similar lengths. Site-based trends were evaluated from 1969 to 2005, but focused on a subset of the data from 1969 to 1987. Data aggregated by state were used to evaluate trends in fish Hg concentrations from 1988 to 2005. In addition, the most recent Hg fish data (1996–2005) were compared to wet Hg deposition data from the Mercury Deposition Network (MDN) over the same period. Downward trends in Hg concentrations in fish from data collected during 1969–1987 exceeded upward trends by a ratio of 6 to 1. Declining Hg accumulation rates in sediment and peat cores reported by many studies during the 1970s and 1980s correspond with the period when the most downward trends in fish Hg concentrations occurred. Downward Hg trends in both sediment cores and fish were also consistent with the implementation of stricter regulatory controls of direct releases of Hg to the atmosphere and surface waters during the same period. The southeastern USA had more upward Hg trends in fish than other regions for both site and state aggregated data. Upward Hg trends in fish from the southeastern USA were associated with increases in wet deposition in the region and may be attributed to a greater influence of global atmospheric Hg emissions in the southeastern USA. No significant trends were found in 62% of the fish species from six states from 1996 to 2005. A lack of Hg trends in fish in the more recent data was consistent with the lack of trends in wet Hg deposition at MDN sites and with relatively constant global emissions during the same time period. Although few significant trends were observed in the more recent Hg concentrations in fish, it is anticipated that Hg concentrations in fish will respond to changes in atmospheric Hg deposition, however, the magnitude and timing of the response is uncertain.

Trends in mercury wet deposition and mercury air concentrations across the U.S. and Canada

This study examined the spatial and temporal trends of mercury (Hg) in wet deposition and air concentrations in the United States (U.S.) and Canada between 1997 and 2013. Data were obtained from the National Atmospheric Deposition Program (NADP) and Environment Canada monitoring networks, and other sources. Of the 19 sites with data records from 1997-2013, 53% had significant negative trends in Hg concentration in wet deposition, while no sites had significant positive trends, which is in general agreement with earlier studies that considered NADP data up until about 2010. However, for the time period 2007-2013 (71 sites), 17% and 13% of the sites had significant positive and negative trends, respectively, and for the time period 2008-2013 (81 sites) 30% and 6% of the sites had significant positive and negative trends, respectively. Non-significant positive tendencies were also widespread. Regional trend analyses revealed significant positive trends in Hg concentration in the Rocky Mountains, Plains, and Upper Midwest regions for the recent time periods in addition to significant positive trends in Hg deposition for the continent as a whole. Sulfate concentration trends in wet deposition were negative in all regions, suggesting a lower importance of local Hg sources. The trend in gaseous elemental Hg from short-term datasets merged as one continuous record was broadly consistent with trends in Hg concentration in wet deposition, with the early time period (1998-2007) producing a significantly negative trend (-1.5±0.2%year(-1)) and the recent time period (2008-2013) displaying a flat slope (-0.3±0.1%year(-1), not significant). The observed shift to more positive or less negative trends in Hg wet deposition primarily seen in the Central-Western regions is consistent with the effects of rising Hg emissions from regions outside the U.S. and Canada and the influence of long-range transport in the free troposphere.

Spatial and Seasonal Variability of Dissolved Methylmercury in Two Stream Basins in the Eastern United States

We assessed methylmercury (MeHg) concentrations across multiple ecological scales in the Edisto (South Carolina) and Upper Hudson (New York) River basins. Out-of-channel wetland/floodplain environments were primary sources of filtered MeHg (F-MeHg) to the stream habitat in both systems. Shallow, open-water areas in both basins exhibited low F-MeHg concentrations and decreasing F-MeHg mass flux. Downstream increases in out-of-channel wetlands/floodplains and the absence of impoundments result in high MeHg throughout the Edisto. Despite substantial wetlands coverage and elevated F-MeHg concentrations at the headwater margins, numerous impoundments on primary stream channels favor spatial variability and lower F-MeHg concentrations in the Upper Hudson. The results indicated that, even in geographically, climatically, and ecologically diverse streams, production in wetland/floodplain areas, hydrologic transport to the stream aquatic environment, and conservative/nonconservative attenuation processes in open water areas are fundamental controls on dissolved MeHg concentrations and, by extension, MeHg availability for potential biotic uptake.

Methylmercury in flood-control impoundments and natural waters of northwestern Minnesota, 1997-99

We studied methylmercury (MeHg) and totalmercury (HgT) in impounded and natural surface waters innorthwestern Minnesota, in settings ranging from agriculturalto undeveloped. In a recently constructed (1995) permanent-pool impoundment, MeHg levels typically increased from inflowto outflow during 1997; this trend broke down from late 1998 toearly 1999. MeHg levels in the outflow reached seasonal maximain mid-summer (maximum of 1.0 ng L-1 in July 1997) andlate-winter (maximum of 6.6 ng L-1 in February 1999), andare comparable to high levels observed in new hydroelectricreservoirs in Canada. Spring and autumn MeHg levels weretypically about 0.1–0.2 ng L-1. Overall, MeHg levels inboth the inflow (a ditch that drains peatlands) and outflowwere significantly higher than in three nearby referencenatural lakes. Eleven older permanent-pool impoundments andsix natural lakes in northwestern Minnesota were sampled fivetimes. The impoundments typically had higher MeHg levels(0.071–8.36 ng L-1) than natural lakes. Five of six lakesMeHg levels typical of uncontaminated lakes (0.014–1.04 ngL-1) with highest levels in late winter, whereas ahypereutrophic lake had high levels (0.37–3.67 ng L-1)with highest levels in mid-summer. Seven temporary-poolimpoundments were sampled during summer high-flow events. Temporary-pool impoundments that retained water for about 10–15days after innundation yielded pronounced increases in MeHgfrom inflow to outflow, in one case reaching 4.6 ng L-1,which was about 2 ng L-1 greater than the mean inflowconcentration during the runoff event.

Shallow groundwater mercury supply in a Coastal Plain stream.

Fluvial methylmercury (MeHg) is attributed to methylation in up-gradient wetland areas. This hypothesis depends on efficient wetland-to-stream hydraulic transport under nonflood and flood conditions. Fluxes of water and dissolved (filtered) mercury (Hg) species (FMeHg and total Hg (FTHg)) were quantified in April and July of 2009 in a reach at McTier Creek, South Carolina to determine the relative importance of tributary surface water and shallow groundwater Hg transport from wetland/floodplain areas to the stream under nonflood conditions. The reach represented less than 6% of upstream main-channel distance and 2% of upstream basin area. Surface-water discharge increased within the reach by approximately 10%. Mean FMeHg and FTHg fluxes increased within the reach by 23–27% and 9–15%, respectively. Mass balances indicated that, under nonflood conditions, the primary supply of water, FMeHg, and FTHg within the reach (excluding upstream surface water influx) was groundwater discharge, rather than tributary transport from wetlands, in-stream MeHg production, or atmospheric Hg deposition. These results illustrate the importance of riparian wetland/floodplain areas as sources of fluvial MeHg and of groundwater Hg transport as a fundamental control on Hg supply to Coastal Plain streams.

Optimizing stream water mercury sampling for calculation of fish bioaccumulation factors.

Mercury (Hg) bioaccumulation factors (BAFs) for game fishes are widely employed for monitoring, assessment, and regulatory purposes. Mercury BAFs are calculated as the fish Hg concentration (Hg(fish)) divided by the water Hg concentration (Hg(water)) and, consequently, are sensitive to sampling and analysis artifacts for fish and water. We evaluated the influence of water sample timing, filtration, and mercury species on the modeled relation between game fish and water mercury concentrations across 11 streams and rivers in five states in order to identify optimum Hg(water) sampling approaches. Each model included fish trophic position, to account for a wide range of species collected among sites, and flow-weighted Hg(water) estimates. Models were evaluated for parsimony, using Akaikes Information Criterion. Better models included filtered water methylmercury (FMeHg) or unfiltered water methylmercury (UMeHg), whereas filtered total mercury did not meet parsimony requirements. Models including mean annual FMeHg were superior to those with mean FMeHg calculated over shorter time periods throughout the year. FMeHg models including metrics of high concentrations (80th percentile and above) observed during the year performed better, in general. These higher concentrations occurred most often during the growing season at all sites. Streamflow was significantly related to the probability of achieving higher concentrations during the growing season at six sites, but the direction of influence varied among sites. These findings indicate that streamwater Hg collection can be optimized by evaluating site-specific FMeHg-UMeHg relations, intra-annual temporal variation in their concentrations, and streamflow-Hg dynamics.

Contaminants of emerging concern in tributaries to the Laurentian Great Lakes: I. Patterns of occurrence

Human activities introduce a variety of chemicals to the Laurentian Great Lakes including pesticides, pharmaceuticals, flame retardants, plasticizers, and solvents (collectively referred to as contaminants of emerging concern or CECs) potentially threatening the vitality of these valuable ecosystems. We conducted a basin-wide study to identify the presence of CECs and other chemicals of interest in 12 U.S. tributaries to the Laurentian Great Lakes during 2013 and 2014. A total of 292 surface-water and 80 sediment samples were collected and analyzed for approximately 200 chemicals. A total of 32 and 28 chemicals were detected in at least 30% of water and sediment samples, respectively. Concentrations ranged from 0.0284 (indole) to 72.2 (cholesterol) μg/L in water and 1.75 (diphenhydramine) to 20,800 μg/kg (fluoranthene) in sediment. Cluster analyses revealed chemicals that frequently co-occurred such as pharmaceuticals and flame retardants at sites receiving similar inputs such as wastewater treatment plant effluent. Comparison of environmental concentrations to water and sediment-quality benchmarks revealed that polycyclic aromatic hydrocarbon concentrations often exceeded benchmarks in both water and sediment. Additionally, bis(2-ethylhexyl) phthalate and dichlorvos concentrations exceeded water-quality benchmarks in several rivers. Results from this study can be used to understand organism exposure, prioritize river basins for future management efforts, and guide detailed assessments of factors influencing transport and fate of CECs in the Great Lakes Basin.

Optimizing fish sampling for fish–mercury bioaccumulation factors

Fish Bioaccumulation Factors (BAFs; ratios of mercury (Hg) in fish (Hgfish) and water (Hgwater)) are used to develop total maximum daily load and water quality criteria for Hg-impaired waters. Both applications require representative Hgfish estimates and, thus, are sensitive to sampling and data-treatment methods. Data collected by fixed protocol from 11 streams in 5 states distributed across the US were used to assess the effects of Hgfish normalization/standardization methods and fish-sample numbers on BAF estimates. Fish length, followed by weight, was most correlated to adult top-predator Hgfish. Site-specific BAFs based on length-normalized and standardized Hgfish estimates demonstrated up to 50% less variability than those based on non-normalized Hgfish. Permutation analysis indicated that length-normalized and standardized Hgfish estimates based on at least 8 trout or 5 bass resulted in mean Hgfish coefficients of variation less than 20%. These results are intended to support regulatory mercury monitoring and load-reduction program improvements.

Lacustrine Responses to Decreasing Wet Mercury Deposition Rates—Results from a Case Study in Northern Minnesota

We present a case study comparing metrics of methylmercury (MeHg) contamination for four undeveloped lakes in Voyageurs National Park to wet atmospheric deposition of mercury (Hg), sulfate (SO4(-2)), and hydrogen ion (H+) in northern Minnesota. Annual wet Hg, SO4(-2), and H+ deposition rates at two nearby precipitation monitoring sites indicate considerable decreases from 1998 to 2012 (mean decreases of 32, 48, and 66%, respectively). Consistent with decreases in the atmospheric pollutants, epilimnetic aqueous methylmercury (MeHgaq) and mercury in small yellow perch (Hgfish) decreased in two of four lakes (mean decreases of 46.5% and 34.5%, respectively, between 2001 and 2012). Counter to decreases in the atmospheric pollutants, MeHgaq increased by 85% in a third lake, whereas Hgfish increased by 80%. The fourth lake had two disturbances in its watershed during the study period (forest fire; changes in shoreline inundation due to beaver activity); this lake lacked overall trends in MeHgaq and Hgfish. The diverging responses among the study lakes exemplify the complexity of ecosystem responses to decreased loads of atmospheric pollutants.

Contaminants of emerging concern in tributaries to the Laurentian Great Lakes: II. Biological consequences of exposure

The Laurentian Great Lakes contain one fifth of the world’s surface freshwater and have been impacted by human activity since the Industrial Revolution. In addition to legacy contaminants, nitrification and invasive species, this aquatic ecosystem is also the recipient of Contaminants of Emerging Concern (CECs) with poorly understood biological consequences. In the current study, we documented the presence, concentrations, and biological effects of CECs across 27 field sites in six Great Lakes tributaries by examining over 2250 resident and caged sunfish (Lepomis ssp.) for a variety of morphological and physiological endpoints and related these results to CEC occurrence. CEC were ubiquitous across studies sites and their presence and concentrations in water and sediment were highest in effluent dominated rivers and downstream of municipal wastewater treatment plant discharges. However, even putative upstream reference sites were not free of CEC presence and fish at these sites exhibited biological effects consistent with CEC exposure. Only the Fox River exhibited consistent adverse biological effects, including increased relative liver size, greater prominence of hepatocyte vacuoles and increased plasma glucose concentrations. Canonical Redundancy Analysis revealed consistent patterns of biological consequences of CEC exposure across all six tributaries. Increasing plasma glucose concentrations, likely as a result of pollutant-induced metabolic stress, were associated with increased relative liver size and greater prominence of hepatocyte vacuoles. These indicators of pollutant exposure were inversely correlated with indicators of reproductive potential including smaller gonad size and less mature gametes. The current study highlights the need for greater integration of chemical and biological studies and suggests that CECs in the Laurentian Great Lakes Basin may adversely affect the reproductive potential of exposed fish populations.