Geology topics

David P. Krabbenhoft

Publications and source records attributed to David P. Krabbenhoft.

At least 55 records · Page 3Linked to original sources

USGS2020

Disentangling the effects of habitat biogeochemistry, food web structure, and diet composition on mercury bioaccumulation in a wetland bird

Methylmercury (MeHg) is a globally pervasive contaminant with known toxicity to humans and wildlife. Several sources of variation can lead to spatial differences in MeHg bioaccumulation within a species including: biogeochemical processes that influence MeHg production and availability within an organism’s home range; trophic positions of consumers and MeHg biomagnification efficiency in food webs; and individual prey preferences that influence diet composition. To better understand spatial variation in MeHg bioaccumulation within a species, we evaluated the effects of habitat biogeochemistry, food web structure, and diet composition in the wetland-obligate California black rail ( Laterallus jamaicensis coturniculus ) at three wetlands along the Petaluma River in northern San Francisco Bay, California, USA. The concentration of MeHg in sediments differed significantly among wetlands. We identified three sediment and porewater measurements that contributed significantly to a discriminant function explaining differences in habitat biogeochemistry among wetlands: the porewater concentration of ferrous iron, the percent organic matter, and the sediment MeHg concentration. Food web structure and biomagnification efficiency were similar among wetlands, with trophic magnification factors for MeHg ranging from 1.84 to 2.59. In addition, regurgitation samples indicated that black rails were dietary generalists with similar diets among wetlands (percent similarity indices > 70%). Given the similarities in diet composition, food web structure, and MeHg biomagnification efficiency among wetlands, we concluded that variation in habitat biogeochemistry and associated sediment MeHg production was the primary driver of differences in MeHg concentrations among black rails from different wetlands.

California↗

USGS2019

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 δ 202 Hg 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.

Analytical and Bioanalytical Chemistry↗

USGS2019

Aquatic cycling of mercury

This chapter examines crucial processes in the aquatic cycling of mercury (Hg) that may lead to microbial production of neurotoxic and bioaccumulative methylmercury (MeHg), and highlights environmental conditions in the Everglades that make it ideal for MeHg production and bioaccumulation. The role of complexation of Hg 2+ in surface water, especially by dissolved organic matter (DOM), in the transport of mercury to sites of microbial methylation are discussed. Photochemical reactions important in Hg cycling in surface water are also discussed. A principal focus of the chapter is on the environmental conditions that promote MeHg production, especially the role of sulfide and DOM in transport of inorganic Hg into bacteria for methylation, and the types of bacteria that have the ability to methylate Hg. Finally, perturbations to the ecosystem (e.g., fire and drought) that have important effects on Hg cycling are discussed.

Book chapter↗

USGS2019

Sulfur contamination in the Everglades, a major control on mercury methylation

In this chapter sulfur contamination of the Everglades and its role as a major control on methylmercury (MeHg) production is examined. Sulfate concentrations over large portions of the Everglades (60% of the ecosystem) are elevated or greatly elevated compared to background conditions of <1 mg/L. Land and water management practices in south Florida are the primary reason for the high levels of sulfate loading to the Everglades. Marshes in the northern Everglades that are highly enriched in sulfate have average concentrations of 60 mg/L, but water in canals in the Everglades Agricultural Area (EAA) contain the highest concentrations of sulfate averaging 60–70 mg/L. Studies that examined the mass balance of sulfur to the Everglades have determined that the primary sources of sulfate include: sulfur currently used in agriculture, and natural and legacy agricultural sulfur released by oxidation of organic soil within the EAA. The extensive loading of sulfate to the ecosystem increases microbial sulfate reduction, the dominant microbial process driving mercury methylation and MeHg production. The biogeochemical processes linking sulfate loading and MeHg production, however, are complex. MeHg production increases as sulfate levels rise from levels <1 mg/L up to about 20 mg/L. However, production of sulfide (a byproduct of microbial sulfate reduction) starts to inhibit MeHg production above 20 mg/L. Sulfate loading to canals in the EAA has impacted the northern Everglades the most, but the Everglades canal system can transport sulfate as far as Everglades National Park (ENP), 80 km further south. Plans to deliver more water to ENP as part of restoration may increase overall sulfate loads to the southern Everglades. Reduction of sulfate loading should be a major goal of Everglades restoration because of the many negative effects of sulfate on the ecosystem. The ecosystem has been shown to respond quickly to reductions in sulfate loading, and strategies for reducing sulfate loading may produce positive outcomes for the Everglades in the near-term. Strategies for reducing sulfate loading will need to include: best management practices for agricultural use of sulfate, approaches to minimize soil oxidation in the EAA, and modifications to stormwater treatment areas to improve sulfate retention.

Florida↗

USGS2019

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 δ 202 Hg 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 δ 202 Hg 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.

Lake Michigan↗

USGS2019

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 comparison of isotopic composition between fish and sediment 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.

Environmental Science & Technology↗

USGS2019

Biogeochemical and physical processes controlling mercury methylation and bioaccumulation in Lake Powell, Glen Canyon National Recreation Area, Utah and Arizona, 2014 and 2015

Mercury monitoring results from about 300 Morone saxatilis (striped bass) muscle tissue samples collected by the State of Utah from Lake Powell resulted in a Utah/Arizona fish consumption advisory issued in 2012 for approximately the lower 100 kilometers of the reservoir. Chemical, physical, and biological data were collected during two synoptic sampling cruises on Lake Powell during May/June 2014 and August 2015 to test three hypotheses associated with a conceptual model developed to explain the observed geographic concentration gradient of Hg in fish tissue samples. This model proposes that in the transition from a primarily riverine system to a reservoir, there is a change in the concentration and composition of water-column particulate material, increasing in the proportion of organic content moving downstream, as the larger size fractions of the inorganic particulate load are deposited in the upper reservoir. This change alleviates light limitation of phytoplankton production and leads to a higher proportion of autochthonous primary production in the downstream direction. This, in turn, drives increased microbial methylmercury (MeHg) production in the benthos and potentially the water column, in the downstream direction, and results in the observed elevated fish Hg levels in the lower part of the reservoir. The model also proposes that there are differences between the main stem of Lake Powell and side canyons, embayments, or secondary rivers entering the reservoir, in terms of Hg cycling dynamics and bioaccumulations, driven mainly by differences in hydrology. Finally, seasonal differences in Hg dynamics within the reservoir are proposed, based on seasonal dynamics associated with primary production and the physical process of seasonal stratification. A total of three statistically testable hypotheses were proposed and postulated that measurable differences in key Hg and non-Hg metrics exist between: (1) the upper and lower reservoir; (2) main stem and river arm/side canyon/embayment sites; and (3) early-season (May/June 2014, less stratified) and late-season (August 2015, stratified) conditions. Statistically modeled least square means in combination with the graphical analysis of Hg and non-Hg parameters were used to examine the data collected during the study and test these hypotheses. Data collected during the study are included in a U.S. Geological Survey data release and are available online at https://doi.org/10.5066/F74X560J . In general, water-column, plankton, and surface sediment samples collected during the synoptic sampling cruises are supportive of the three hypotheses associated with the conceptual model. In support of hypothesis 1 (comparing upper and lower reservoir sites), the least square mean for turbidity was higher in the upper reservoir. In contrast, surface water particulate organic carbon (as a percentage of total particulate mass), particulate MeHg (by mass [in nanograms per gram] and as a percentage of total mercury [THg]), and particulate-dissolved partitioning coefficients for THg and MeHg were higher in the lower reservoir. Plankton THg concentrations also were significantly (probability [ p ] less than (<) 0.05) higher in the lower reservoir. Surface sediment metrics in support of hypothesis 1 include higher MeHg production potential rates in the lower reservoir. In contrast, there were no statistically significant differences between the upper and lower reservoir for surface sediment percent of MeHg and MeHg concentration, percent MeHg, or methylation rate constants. These spatial trends associated with hypothesis 1 indicate a pathway for enhanced Hg bioavailability in the lower reservoir. Hypothesis 2, which tested for differences between main stem and river arm/side canyon/embayment sites, was supported by a number of water-column parameters, including particulate THg and MeHg concentrations by mass (in nanograms per gram) and percent particulate MeHg being significantly ( p <0.05) higher in the river arms, side canyons, and embayments relative to the main stem channel. Plankton MeHg concentrations (by mass [in nanograms per gram] and volume [in nanograms per liter] and as a percentage of THg) were elevated in river arm/side canyon/embayment sites compared to main stem sites, indicating an enhanced potential for MeHg bioaccumulation at the base of the pelagic food web in river arms, side canyons, and embayments. In contrast, few of the sediment metrics differed between main stem and river arm/side canyon/embayment sampling sites; however, the potential for MeHg degradation in surface sediment was significantly higher in the main stem. The data indicate that river arm/side canyon/embayment sites may experience enhanced Hg bioaccumulation, compared to the main stem, because of higher MeHg levels at the base of the pelagic food web. This conclusion is supported by the elevated Hg detected in striped bass muscle tissue samples collected in the San Juan Arm during this study (2014). Fish collected from the lower reservoir exhibited a distinct Hg isotopic signature that was enriched in delta (δ) 202 Hg and capital delta (Δ) 199 Hg relative to fish samples collected from either Good Hope Bay or the San Juan Arm. Hypothesis 3 tested for differences between early (May/June) high-flow and late (August) low-flow seasons. This test was supported by a range of non-Hg metrics (nitrate, phosphate, chlorophyll a , dissolved oxygen, fluorescent dissolved organic matter, temperature, and pH) that reflect the increase in chlorophyll a , decrease in nutrients, and buildup of stratified conditions in the transition from early- to late-season sampling periods. Significant seasonal differences also were noted for multiple Hg metrics, including (a) water-column filtered and particulate (by mass) MeHg and THg concentrations; (b) plankton MeHg and THg concentration (by mass); and (c) sediment percent MeHg, Hg(II)-methylation rate constant, and microbial ribosomal ribonucleic acid, small subunit 16 (16S rRNA) abundance, all of which were higher during the late-season synoptic sampling. Overall, the surface sediment metrics are consistent with a seasonal shift from the early-season synoptic results, when the availability of Hg(II) exerts a primary control on MeHg production, to the late-season synoptic sampling, when microbial activity is a dominant driver of MeHg production.

Arizona, Utah↗

USGS2019

Coagulant and sorbent efficacy in removing mercury from surface waters in the Cache Creek watershed, California

Cache Creek drains part of northern California’s Coast Ranges and is an important source of mercury (Hg) to the Sacramento–San Joaquin Delta. Cache Creek is contaminated with Hg from several sources, including historical Hg and gold mines, native Hg in the soils, and active mineral springs. In laboratory experiments in a study conducted by the U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency, the use of coagulants and sorbents to immobilize Hg in water samples from high-concentration sources in the Cache Creek watershed was investigated. Three sites were selected for the collection of surface-water samples containing high and low concentrations of particulate-associated Hg. The high-particulate Hg samples were collected from Cache Creek Settling Basin during stormflow conditions. The low-particulate Hg samples were collected from two geochemically contrasting sites during base-flow conditions (downstream from a geothermal spring and at the emergence point of a connate-water spring). Three coagulants were chosen for laboratory testing with the high-particulate sample— (1) ChitoVan TM HV 1.5 percent (shell based), (2) Ferralyte TM 8131 (ferric sulfate based), and (3) Ultrion TM 8186 (aluminum based). Each coagulant was tested at various dose amounts to determine the optimum dose rate for the high-particulate sample. The low-particulate source samples were passed through three sorbents—(1) chitosan flakes, (2) coconut shell-based activated carbon, and (3) coal-based activated carbon. In-line columns were packed with each material, and the untreated sample was passed through each column at three different flow rates (0.1, 0.5, and 1.0 liter per minute, L/min). For dose rates used in this study, ChitoVan TM reduced turbidity of the particulate sample by 85–91 percent, FerralyteTM reduced turbidity by 54–93 percent, and Ultrion TM reduced turbidity by greater than 90 percent. At the lowest dose rate, ChitoVan TM achieved a 59- to 61-percent reduction in whole-water methylmercury (MeHg) concentrations and a 71- to 75-percent decrease in whole-water total mercury (THg) concentrations. Ferralyte TM achieved a 37- to 48-percent decrease in whole-water MeHg concentrations and a 37- to 48-percent reduction in whole-water THg concentrations. Ultrion TM achieved a greater than 90-percent decrease in whole-water MeHg and THg concentrations. Mercury removal from the low-particulate samples was less efficient for the sorbent materials compared to the coagulants; less than 30 percent of THg was removed from any 500-milliliter aliquot using sorbent materials. The coal-based sorbent was the most versatile of the sorbents, removing THg to a similar extent from both low-particulate source waters. The chitosan sorbent was the most effective at removing THg from the low-particulate stream sample, but less effective for the low-particulate connate-spring sample. The Hg removal efficiency of the coconut sorbent decreased quickly compared to the other two sorbents, indicating that sorption may be limited by the short contact times evaluated in this study.

California↗

USGS2019

Rapid pre-concentration of mercury in solids and water for isotopic analysis

The precise quantification of mercury (Hg) stable isotope compositions in low concentration or dilute samples poses analytical challenges due to Hg mass limitations. Common Hg pre-concentration procedures require extended processing times, making rapid Hg stable isotope measurements challenging. Here we present a modified pre-concentration method that combines commonly used Hg reduction and gold trap amalgamation followed by semi-rapid thermal desorption (less than 1 h) and chemical trapping. This custom designed system was demonstrated to perform adequately on multiple trapping matrices including a new bromine monochloride (BrCl) wet oxidant trap (40% 3HNO 3 :BrCl), capable of trapping consistently in 2 mL volume over a wide range of Hg masses (5–200 ng). The procedure was also shown to work effectively on natural matrices, waters and sediments, producing comparable isotope results to the direct digestion analyses. Here, we present a method that can effectively triple sample throughput in comparison to traditional procedures, and also access lower concentration matrices without compromising the accuracy or precision of Hg isotope measurements.

Analytica Chimica Acta↗

USGS2019

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.

Oregon↗

USGS2018

Mercury isotopes reveal an ontogenetic shift in habitat use by walleye in lower Green Bay of Lake Michigan

In general, fish residing in rivers differ from fish residing in lakes in their mercury (Hg) isotope ratios. Specifically, fish residing in lakes typically show enriched values for the isotope ratios of δ 202 Hg (mass-dependent fractionation of isotope 202 Hg) and Δ 199 Hg (mass-independent fractionation of isotope 199 Hg) compared with fish residing in rivers, because photochemical effects acting on Hg isotope ratios are stronger in lakes than in rivers. Whole-fish determinations of Hg isotope ratios in age-0 and adult (ages 4–11) walleye ( Sander vitreus ) caught in the Fox River, the main tributary to lower Green Bay of Lake Michigan, were dissimilar. Age-0 fish exhibited a river signature for δ 202 Hg and Δ 199 Hg, with means equal to 0.00 and 0.26‰, respectively. Significantly elevated levels of δ 202 Hg and Δ 199 Hg were observed in adult fish, indicating that adult fish primarily resided in the bay. Our results implied that the Fox River serves as a nursery area for juvenile walleye in the Fox River–lower Green Bay ecosystem. Moreover, corrections for photochemical fractionation of δ 202 Hg revealed that age-0 and adult walleye shared the same source of Hg in this ecosystem. In addition, Hg isotope ratios did not significantly differ between the sexes of adult walleye, suggesting that these ratios did not fractionate during the Hg elimination process.

Environmental Science & Technology Letters↗

USGS2018

Ratio of mercury concentration to PCB concentration varies with sex of white sucker (Catostomus commersonii)

The whole-fish total mercury (Hg) concentrations were determined in 25 mature female and 26 mature male white suckers ( Catostomus commersonii ) caught during their spawning run in the Kewaunee River, a tributary to Lake Michigan. The age of each fish was estimated using thin-sectioned otoliths, and total length (TL) and weight were determined for each fish. When adjusted for the effect of age, males were found to be 7% higher in Hg concentration than females. Nearly all (about 98%) of the Hg found in the white suckers was determined to be methylmercury. In an earlier study on the same 51 white suckers from the Kewaunee River spawning run, males were found to be 18% higher than females in polychlorinated biphenyl (PCB) concentration. We determined that the ratio of Hg concentration to PCB concentration in females was significantly higher than that in males. Thus, sex significantly interacted with contaminant type (Hg or PCBs) in determining contaminant concentrations. The most plausible explanation for this interaction was that males eliminated Hg at a faster rate than females, most likely due to the boosting of the Hg-elimination rate by certain androgens such as testosterone and 11-ketotestosterone. Hg concentrations in the white suckers were well below federal guidelines for fish consumption.

Environments↗

USGS2018

Mercury methylation and bioaccumulation in Sinclair Inlet, Kitsap County, Washington

The U.S. Geological Survey evaluated the transformation of mercury to bioavailable methylmercury in Sinclair Inlet, Kitsap County, Washington, and assessed the effect of the transformation processes on the mercury burden in marine organisms and sediment. In August 2008, samples of sediment, water, and biota from six sites in Sinclair Inlet and three bays representative of Puget Sound embayments were collected. The extensive sediment sampling included analysis of methylmercury in sediment and porewater, estimates of methylation production potential, and analyses of ancillary constituents associated with organic carbon and reduction-oxidation (redox) conditions to assist in interpreting the mercury results. Analyses of methylmercury in water overlying incubated cores provided an estimate of the release of methylmercury to the water column. Collection of samples for mercury species in the aqueous, particulate (suspended solids), and biological phases, and for ancillary carbon and nitrogen constituents in surface water, continued, on about a monthly schedule, at four stations through August 2009. In February, June, and August 2009, seasonal sediment samples were collected at 20 stations distributed between greater Sinclair Inlet and Operable Unit B Marine of the Bremerton naval complex, Bremerton, Washington, to examine geographical and seasonal patterns of mercury biogeochemistry of sediment in Sinclair Inlet. At six of these seasonal sediment stations, porewater was collected and triplicate core incubation experiments were done. Median sediment-methylmercury concentrations were not statistically different between the representative bays and Sinclair Inlet. The percentage of sediment methylmercury (relative to total mercury) was actually lower in the Sinclair Inlet sites compared with the representative bays, reflecting the higher sediment total mercury concentration for the Sinclair Inlet stations compared with the representative bays. Likewise, median sediment methylmercury concentrations were not statistically different between the greater Sinclair Inlet stations and the Bremerton naval complex stations; whereas the percentage of sediment methylmercury to total mercury was lower in the Bremerton naval complex due to higher sediment total mercury concentrations than the greater Sinclair Inlet stations. The biogeochemical characteristics of each station, measured by redox, organic carbon, and the seasonal availability of nutrients controlled methylmercury biogeochemistry. Mercury methylation production potential was a function of temperature, concentration of total mercury in sediment, and the percentage of ferrous iron (relative to total measured iron) across all sites. Methylmercury porewater concentrations were best described by using concentrations of dissolved organic carbon and reduction-oxidation conditions. Likewise, the variable fluxes of methylmercury from incubated cores were best described using dissolved organic carbon and reduction-oxidation conditions. Sinclair Inlet exhibited the classic Puget Sound biological cycle, with spring and autumn phytoplankton blooms resulting in depletion of nitrate, orthophosphate, and silicate in the surface water. Although variable in timing between 2008 and 2009, a strong corresponding seasonal trend of increased availability, incorporation, and bioaccumulation of methylmercury into the food web of Sinclair Inlet occurred during the early spring and summer growing season.

Washington↗

USGS2018

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 (δ 202 Hg, Δ 199 Hg, and Δ 200 Hg) 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 ( Salvelinus namaycush ) and walleye ( Sander vitreus ), 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 Δ 199 Hg. 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 (Δ 200 Hg), 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.

Environmental Science & Technology↗

USGS2018

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 measured monthly for 1.5 years following logging in three paired harvested and un-harvested catchments. There was no significant difference in particulate-bound Hg concentrations or loads in the harvested and unharvested catchments which may have resulted from the best management 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 both harvested, un-harvested 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. These results have important implications for the role forestry operations have in affecting catchment retention and export of Hg pollution.

Oregon↗

USGS2018

Permafrost stores a globally significant amount of mercury

Changing climate in northern regions is causing permafrost to thaw with major implications for the global mercury (Hg) cycle. We estimated Hg in permafrost regions based on in situ measurements of sediment total mercury (STHg), soil organic carbon (SOC), and the Hg to carbon ratio (R HgC ) combined with maps of soil carbon. We measured a median STHg of 43 ± 30 ng Hg g soil −1 and a median R HgC of 1.6 ± 0.9 μg Hg g C −1 , consistent with published results of STHg for tundra soils and 11,000 measurements from 4,926 temperate, nonpermafrost sites in North America and Eurasia. We estimate that the Northern Hemisphere permafrost regions contain 1,656 ± 962 Gg Hg, of which 793 ± 461 Gg Hg is frozen in permafrost. Permafrost soils store nearly twice as much Hg as all other soils, the ocean, and the atmosphere combined, and this Hg is vulnerable to release as permafrost thaws over the next century. Existing estimates greatly underestimate Hg in permafrost soils, indicating a need to reevaluate the role of the Arctic regions in the global Hg cycle.

Geophysical Research Letters↗

USGS2017

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.

Florida↗

USGS2017

Atmospheric deposition to forests in the eastern USA

Atmospheric mercury (Hg) deposition to forests is important because half of the land cover in the eastern USA is forest. Mercury was measured in autumn litterfall and weekly precipitation samples at a total of 27 National Atmospheric Deposition Program (NADP) monitoring sites in deciduous and mixed deciduous-coniferous forests in 16 states in the eastern USA during 2007–2014. These simultaneous, uniform, repeated, annual measurements of forest Hg include the broadest area and longest time frame to date. The autumn litterfall-Hg concentrations and litterfall mass at the study sites each year were combined with annual precipitation-Hg data. Rates of litterfall-Hg deposition were higher than or equal to precipitation-Hg deposition rates in 70% of the annual data, which indicates a substantial contribution from litterfall to total atmospheric-Hg deposition. Annual litterfall-Hg deposition in this study had a median of 11.7 μg per square meter per year (μg/m 2 /yr) and ranged from 2.2 to 23.4 μg/m 2 /yr. It closely matched modeled dry-Hg deposition, based on land cover at selected NADP Hg-monitoring sites. Mean annual atmospheric-Hg deposition at forest study sites exhibited a spatial pattern partly explained by statistical differences among five forest-cover types and related to the mapped density of Hg emissions. Forest canopies apparently recorded changes in atmospheric-Hg concentrations over time because litterfall-Hg concentrations decreased year to year and litterfall-Hg concentrations were significantly higher in 2007–2009 than in 2012–2014. These findings reinforce reported decreases in Hg emissions and atmospheric elemental-Hg concentrations during this same time period. Methylmercury (MeHg) was detected in all litterfall samples at all sites, compared with MeHg detections in less than half the precipitation samples at selected sites during the study. These results indicate MeHg in litterfall is a pathway into the terrestrial food web where it can accumulate in the prey of songbirds, bats, and raptors.

Environmental Pollution↗