Mercury Cycling in Stream Ecosystems. 1. Water Column Chemistry and Transport

We studied total mercury (THg) and methylmercury (MeHg) in eight streams, located in Oregon, Wisconsin, and Florida, that span large ranges in climate, landscape characteristics, atmospheric Hg deposition, and water chemistry. While atmospheric deposition was the source of Hg at each site, basin characteristics appeared to mediate this source by providing controls on methylation and fluvial THg and MeHg transport. Instantaneous concentrations of filtered total mercury (FTHg) and filtered methylmercury (FMeHg) exhibited strong positive correlations with both dissolved organic carbon (DOC) concentrations and streamflow for most streams, whereas mean FTHg and FMeHg concentrations were correlated with wetland density of the basins. For all streams combined, whole water concentrations (sum of filtered and particulate forms) of THg and MeHg correlated strongly with DOC and suspended sediment concentrations in the water column

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 (MeHg_aq) and mercury in small yellow perch (Hg_fish) 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, MeHg_aq increased by 85% in a third lake, whereas Hg_fish 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 MeHg_aq and Hg_fish. The diverging responses among the study lakes exemplify the complexity of ecosystem responses to decreased loads of atmospheric pollutants

Correction to Organic Carbon Burial in Lakes and Reservoirs of the Conterminous United States

Correction to Organic Carbon Burial in Lakes and Reservoirs of the Conterminous United State

Stable Mercury Isotopes in Polished Rice (<i>Oryza sativa</i> L.) and Hair from Rice Consumers

Mercury (Hg) isotopic signatures were characterized in polished rice samples from China, U.S., and Indonesia (<i>n</i> = 45). Hg isotopes were also analyzed in paired hair samples for participants from China (<i>n</i> = 21). For the latter, we also quantified the proportion of methylmercury intake through rice (range: 31–100%), and the weekly servings of fish meals (range: 0–5.6 servings/weekly). For these participants, 29% (<i>n</i> = 6) never ingested fish, 52% (<i>n</i> = 11) ingested fish < twice/weekly, and 19% (<i>n</i> = 4) ingested fish ≥ twice/weekly. In rice and hair, both mass-dependent fractionation (MDF, reported as δ²⁰²Hg) and mass-independent fractionation (MIF, reported as Δ¹⁹⁹Hg) of Hg isotopes were observed. Compared to rice, hair δ²⁰²Hg values were enriched on average (±1 standard deviation) by 1.9 ± 0.61‰, although the range was wide (range: 0.45‰, 3.0‰). Hair Δ¹⁹⁹Hg was significantly inversely associated with %methylmercury intake from rice (Spearman’s rho = −0.61, <i>p</i> < 0.01, <i>n</i> = 21), i.e., as the proportion of methylmercury intake from rice increased, MIF decreased. Additionally, hair Δ¹⁹⁹Hg was significantly higher for participants ingesting fish ≥ twice/weekly compared to those who did not ingest fish or ingested fish < twice/weekly (ANOVA, <i>p</i> < 0.05, <i>n</i> = 21); Overall, results suggest that Hg isotopes (especially MIF) in human hair can be used to distinguish methylmercury intake from rice versus fish

Organic Carbon Burial in Lakes and Reservoirs of the Conterminous United States

Organic carbon (OC) burial in lacustrine sediments represents an important sink in the global carbon cycle; however, large-scale OC burial rates are poorly constrained, primarily because of the sparseness of available data sets. Here we present an analysis of OC burial rates in water bodies of the conterminous U.S. (CONUS) that takes advantage of recently developed national-scale data sets on reservoir sedimentation rates, sediment OC concentrations, lake OC burial rates, and water body distributions. We relate these data to basin characteristics and land use in a geostatistical analysis to develop an empirical model of OC burial in water bodies of the CONUS. Our results indicate that CONUS water bodies sequester 20.8 (95% CI: 9.4–65.8) Tg C yr^–1, and spatial patterns in OC burial are strongly influenced by water body type, size, and abundance; land use; and soil and vegetation characteristics in surrounding areas. Carbon burial is greatest in the central and southeastern regions of the CONUS, where cultivation and an abundance of small water bodies enhance accumulation of sediment and OC in aquatic environments

Use of Stable Isotope Signatures to Determine Mercury Sources in the Great Lakes

Sources of mercury (Hg) in Great Lakes sediments were assessed with stable Hg isotope ratios using multicollector inductively coupled plasma mass spectrometry. An isotopic mixing model based on mass-dependent (MDF) and mass-independent fractionation (MIF) (δ²⁰²Hg and Δ¹⁹⁹Hg) identified three primary Hg sources for sediments: atmospheric, industrial, and watershed-derived. Results indicate atmospheric sources dominate in Lakes Huron, Superior, and Michigan sediments while watershed-derived and industrial sources dominate in Lakes Erie and Ontario sediments. Anomalous Δ²⁰⁰Hg signatures, also apparent in sediments, provided independent validation of the model. Comparison of Δ²⁰⁰Hg signatures in predatory fish from three lakes reveals that bioaccumulated Hg is more isotopically similar to atmospherically derived Hg than a lake’s sediment. Previous research suggests Δ²⁰⁰Hg is conserved during biogeochemical processing and odd mass-independent fractionation (MIF) is conserved during metabolic processing, so it is suspected even is similarly conserved. Given these assumptions, our data suggest that in some cases, atmospherically derived Hg may be a more important source of MeHg to higher trophic levels than legacy sediments in the Great Lakes

Stream Mercury Export in Response to Contemporary Timber Harvesting Methods (Pacific Coastal Mountains, Oregon, USA)

Land-use activities can alter hydrological and biogeochemical processes that can affect the fate, transformation, and transport of mercury (Hg). Previous studies in boreal forests have shown that forestry operations can have profound but variable effects on Hg export and methylmercury (MeHg) formation. The Pacific Northwest is an important timber producing region that receives large atmospheric Hg loads, but the impact of forest harvesting on Hg mobilization has not been directly studied and was the focus of our investigation. Stream discharge was measured continuously, and Hg and MeHg concentrations were measured monthly for 1.5 years following logging in three paired harvested and unharvested (control) catchments. There was no significant difference in particulate-bound Hg concentrations or loads in the harvested and unharvested catchments which may have resulted from forestry practices aimed at minimizing erosion. However, the harvested catchments had significantly higher discharge (32%), filtered Hg concentrations (28%), filtered Hg loads (80%), and dissolved organic carbon (DOC) loads (40%) compared to forested catchments. MeHg concentrations were low (mostly <0.05 ng L^–1) in harvested, unharvested, and downstream samples due to well-drained/unsaturated soil conditions and steep slopes with high energy eroding stream channels that were not conducive to the development of anoxic conditions that support methylation. These results have important implications for the role forestry operations have in affecting catchment retention and export of Hg pollution

Mercury Cycling in Stream Ecosystems. 2. Benthic Methylmercury Production and Bed Sediment−Pore Water Partitioning

Mercury speciation, controls on methylmercury (MeHg) production, and bed sediment−pore water partitioning of total Hg (THg) and MeHg were examined in bed sediment from eight geochemically diverse streams where atmospheric deposition was the predominant Hg input. Across all streams, sediment THg concentrations were best described as a combined function of sediment percent fines (%fines; particles < 63 μm) and organic content. MeHg concentrations were best described as a combined function of organic content and the activity of the Hg(II)-methylating microbial community and were comparable to MeHg concentrations in streams with Hg inputs from industrial and mining sources. Whole sediment tin-reducible inorganic reactive Hg (Hg(II)_R) was used as a proxy measure for the Hg(II) pool available for microbial methylation. In conjunction with radiotracer-derived rate constants of ²⁰³Hg(II) methylation, Hg(II)_R was used to calculate MeHg production potential rates and to explain the spatial variability in MeHg concentration. The %Hg(II)_R (of THg) was low (2.1 ± 5.7%) and was inversely related to both microbial sulfate reduction rates and sediment total reduced sulfur concentration. While sediment THg concentrations were higher in urban streams, %MeHg and %Hg(II)_R were higher in nonurban streams. Sediment pore water distribution coefficients (log <i>K</i>_d’s) for both THg and MeHg were inversely related to the log-transformed ratio of pore water dissolved organic carbon (DOC) to bed sediment %fines. The stream with the highest drainage basin wetland density also had the highest pore water DOC concentration and the lowest log <i>K</i>_d’s for both THg and MeHg. No significant relationship existed between overlying water MeHg concentrations and those in bed sediment or pore water, suggesting upstream sources of MeHg production may be more important than local streambed production as a driver of water column MeHg concentration in drainage basins that receive Hg inputs primarily from atmospheric sources

Spatial Dependence of Reduced Sulfur in Everglades Dissolved Organic Matter Controlled by Sulfate Enrichment

Sulfate inputs to the Florida Everglades stimulate sulfidic conditions in freshwater wetland sediments that affect ecological and biogeochemical processes. An unexplored implication of sulfate enrichment is alteration of the content and speciation of sulfur in dissolved organic matter (DOM), which influences the reactivity of DOM with trace metals. Here, we describe the vertical and lateral spatial dependence of sulfur chemistry in the hydrophobic organic acid fraction of DOM from unimpacted and sulfate-impacted Everglades wetlands using X-ray absorption spectroscopy and ultrahigh-resolution mass spectrometry. Spatial variation in DOM sulfur content and speciation reflects the degree of sulfate enrichment and resulting sulfide concentrations in sediment pore waters. Sulfur is incorporated into DOM predominantly as highly reduced species in sulfidic pore waters. Sulfur-enriched DOM in sediment pore waters exchanges with overlying surface waters and the sulfur likely undergoes oxidative transformations in the water column. Across all wetland sites and depths, the total sulfur content of DOM correlated with the relative abundance of highly reduced sulfur functionality. The results identify sulfate input as a primary determinant on DOM sulfur chemistry to be considered in the context of wetland restoration and sulfur and trace metal cycling

Factors Affecting Mercury Stable Isotopic Distribution in Piscivorous Fish of the Laurentian Great Lakes

Identifying the sources of methylmercury (MeHg) and tracing the transformations of mercury (Hg) in the aquatic food web are important components of effective strategies for managing current and legacy Hg sources. In our previous work, we measured stable isotopes of Hg (δ²⁰²Hg, Δ¹⁹⁹Hg, and Δ²⁰⁰Hg) in the Laurentian Great Lakes and estimated source contributions of Hg to bottom sediment. Here, we identify isotopically distinct Hg signatures for Great Lakes trout (<i>Salvelinus namaycush</i>) and walleye (<i>Sander vitreus</i>), driven by both food-web and water-quality characteristics. Fish contain high values for odd-isotope mass independent fractionation (MIF) with averages ranging from 2.50 (western Lake Erie) to 6.18‰ (Lake Superior) in Δ¹⁹⁹Hg. The large range in odd-MIF reflects variability in the depth of the euphotic zone, where Hg is most likely incorporated into the food web. Even-isotope MIF (Δ²⁰⁰Hg), a potential tracer for Hg from precipitation, appears both disconnected from lake sedimentary sources and comparable in fish among the five lakes. We suggest that similar to the open ocean, water-column methylation also occurs in the Great Lakes, possibly transforming recently deposited atmospheric Hg deposition. We conclude that the degree of photochemical processing of Hg is controlled by phytoplankton uptake rather than by dissolved organic carbon quantity among lakes