Geology topics

David P. Krabbenhoft

Publications and source records attributed to David P. Krabbenhoft.

At least 55 records · Page 3Linked to original sources

USGS2020

Aqueous elemental mercury production versus mercury inventories in the Lake Michigan airshed: Deciphering the spatial and diel controls of mercury gradients in air and water

Atmospheric delivery of mercury (Hg) is important to the Upper Great Lakes, and understanding gaseous Hg exchange between surface water and air is critical to predicting the effects of declining mercury emissions. Speciated atmospheric Hg, dissolved gaseous Hg (DGM), and particulate and filter passing total Hg were measured on a cruise in Lake Michigan. Low mercury levels reflected pristine background conditions, especially in offshore regions. In the atmosphere, reactive and particle-associated fractions were low (1.0 ± 0.5%) compared to gaseous elemental Hg (1.34 ± 0.14 ng m–3) and were elevated in the urbanized southern basin. DGM was supersaturated, ranging from 17.5 ± 4.8 pg L–1 (330 ± 80%) in the main lake to 33.2 ± 2.4 pg L–1 (730 ± 70%) in Green Bay. Diel cycling of surface DGM showed strong Hg efflux during the day due to increased winds, and build-up at night from continued DGM production. Epilimnetic DGM is formed from photochemical reduction, while hypolimnetic DGM originates from biological Hg reduction. We found that DGM concentrations were greatest below the thermocline (30.8 ± 13.6 pg L–1), accounting for 68–92% of the total DGM in Lake Michigan, highlighting the importance of nonphotochemical reduction in deep stratified lakes.

Lake Michigan↗

USGS2020

Mercury methylation genes identified across diverse anaerobic microbial guilds in a eutrophic sulfate-enriched lake

Mercury (Hg) methylation is a microbially mediated process that converts inorganic Hg into bioaccumulative, neurotoxic methylmercury (MeHg). The metabolic activity of methylating organisms is highly dependent on biogeochemical conditions, which subsequently influences MeHg production. However, our understanding of the ecophysiology of methylators in natural ecosystems is still limited. Here, we identified potential locations of MeHg production in the anoxic, sulfidic hypolimnion of a freshwater lake. At these sites, we used shotgun metagenomics to characterize microorganisms with the Hg-methylation gene hgcA . Putative methylators were dominated by hgcA sequences divergent from those in well-studied, confirmed methylators. Using genome-resolved metagenomics, we identified organisms with hgcA (hgcA+) within the Bacteroidetes and the recently described Kiritimatiellaeota phyla. We identified hgcA+ genomes derived from sulfate-reducing bacteria, but these accounted for only 22% of hgcA+ genome coverage. The most abundant hgcA+ genomes were from fermenters, accounting for over half of the hgcA gene coverage. Many of these organisms also mediate hydrolysis of polysaccharides, likely from cyanobacterial blooms. This work highlights the distribution of the Hg-methylation genes across microbial metabolic guilds and indicate that primary degradation of polysaccharides and fermentation may play an important but unrecognized role in MeHg production in the anoxic hypolimnion of freshwater lakes.

Environmental Science and Technology↗

USGS2020

Observed and modeled mercury and dissolved organic carbon concentrations and loads at control structure S-12D, Florida Everglades, 2013–17

Mercury (Hg) has been a contaminant of concern for several decades in South Florida, particularly in the Florida Everglades. The transport and bioavailability of Hg in aquatic systems is intimately linked to dissolved organic carbon (DOC). In aquatic systems, Hg can be converted to methylmercury (MeHg), which is the form of Hg that bioaccumulates in food webs. The bioaccumulation of MeHg poses significant health risks to wildlife and humans. Fish consumption advisories triggered by elevated Hg levels first appeared in the 1980s in South Florida. Multiple structures regulate freshwater distribution to Everglades National Park, including S-12D. This report summarizes seasonal and annual concentration and load data from late September 2013 to April 2017 for the total of (1) filter-passing total mercury (FTHg), (2) filter-passing methylmercury (FMeHg), (3) particulate total mercury (PTHg), (4) particulate methylmercury (PMeHg) and, (5) DOC discharged through control structure S-12D. The loads of Hg fractions and DOC at control structure S-12D were determined by pairing discharge data with constituent concentrations estimated by empirical models based on surrogate in situ water-quality measurements. Calculated concentrations of DOC ranged from 12.8 milligrams per liter (mg/L) to 27.9 mg/L with a mean of 18.8 mg/L during the study period. Annual loads of DOC ranged from 3,950 tons in 2015 to 10,900 tons in 2016. DOC loads increased linearly with an increase in flow, and the highest monthly DOC load of 1,630 tons was observed in February 2016. Calculated concentrations of FTHg ranged from 0.35 to 1.55 nanograms per liter (ng/L) with a mean of 0.85 ng/L during the study period. Calculated concentrations of FMeHg ranged from 0.06 ng/L to 0.24 ng/L with a mean of 0.14 ng/L during the study period. Generally, FTHg and FMeHg concentrations were lower during periods of decreased flow and higher during periods of increased flow. Calculated PTHg concentrations ranged from 0.09 ng/L to 4.19 ng/L with a mean of 0.58 ng/L during the study period. Calculated PMeHg concentrations ranged from below the limit of detection <0.01 ng/L to 0.29 ng/L with a mean of 0.03 ng/L during the study period. Loads of Hg were often zero or lowest from November to May, owing to the lack of flow or low-flow conditions. FTHg and FMeHg loads increased linearly with an increase in flow and typically were highest from June to October. During periods of increasing flow or following changes in gate operations, PTHg and PMeHg constituted a greater percentage of the total Hg load. Annual loads of total Hg (filter-passing and particulate) ranged from 254 grams in 2015 to 658 grams in 2016. FTHg was the predominant contributor to the total Hg load. Information presented herein provides the first assessment of DOC and Hg loads to Everglades National Park through control structure S-12D using continuous in situ measurements of discharge and constituent surrogates and compares the surrogate model approach to loads calculated from monthly sampling. Analysis of calculated and observed loads demonstrates the significance of flow data on calculating constituent loads.

Florida↗

USGS2020

Seasonal dynamics and interannual variability in mercury concentrations and loads through a three-reservoir complex

The Hells Canyon Complex (HCC) along the Snake River (Idaho-Oregon border, USA) encompasses three successive reservoirs that seasonally stratify, creating anoxic conditions in the hypolimnion that promote methylmercury (MeHg) production. This study quantified seasonal dynamics and interannual variability in mercury concentrations (inorganic divalent mercury (IHg) and MeHg) and loads at four reservoir inflow and outflow locations through the HCC (2014-2017). We observed (1) that the HCC is a net sink for both IHg and MeHg, (2) interannual variability in IHg and MeHg loads largely reflecting streamflow conditions, and (3) seasonal variability in particulate IHg loading at the inflow (greatest from February to April) and MeHg export from the outflow (greatest from September to December) of the HCC. Seasonal export of MeHg was evidenced by increases in monthly mean concentrations of unfiltered MeHg (approximately twofold) and the percentage of total mercury (THg) as MeHg (≥ fourfold) coincident with reservoir destratification. Despite evidence of seasonal export of MeHg from the HCC, annual loads indicate a 42% decrease in unfiltered MeHg from HCC inflow to outflow. Results from this study improve the understanding of seasonal variability in mercury transport through and transformation within a reservoir complex.

Idaho, Oregon↗

USGS2020

A national-scale assessment of mercury bioaccumulation in United States National Parks using dragonfly larvae as biosentinels through a citizen-science framework

We conducted a national-scale assessment of mercury (Hg) bioaccumulation in aquatic ecosystems using dragonfly larvae as biosentinels, by developing a citizen science network to facilitate biological sampling. Implementing a carefully designed sampling methodology for citizen scientists, we developed an effective framework for landscape-level inquiry that might otherwise be resource limited. We assessed variation in dragonfly Hg concentrations across >450 sites spanning 100 US National Park Service units, and examined intrinsic and extrinsic factors associated with variation in Hg concentrations. Mercury concentrations ranged between 10.4-1,411 ng/g dry weight across sites and varied among habitat types. Dragonfly total Hg (THg) concentrations were up to 1.8-fold higher in lotic habitats than in lentic habitats, and 37% higher in waterbodies with abundant wetlands along their margins than those without wetlands. Mercury concentrations in dragonflies differed among families, but were correlated (R2>0.80) with each other, enabling adjustment to a consistent family to facilitate spatial comparisons among sampling units. Dragonfly THg concentrations were positively correlated with THg in both fish and amphibians from the same locations, indicating that dragonfly larvae are effective indicators of Hg bioavailability in aquatic food webs. Collectively, this continental-scale study demonstrates the utility of dragonfly larvae for estimating potential mercury risk to fish and wildlife in aquatic ecosystems and provides a framework for engaging citizen science as a component of landscape Hg monitoring programs.

Environmental Science and Technology↗

USGS2020

Insights into mercury source identification and bioaccumulation using stable isotope approaches in the Hannibal Pool of the Ohio River

Mercury contamination in river systems due to historic and current Hg releases is a persistent concern for both wildlife and human health. In larger rivers, like the Ohio River, USA, it is difficult to directly link Hg discharges to bioaccumulation due to the existence of multiple industrial Hg sources as well as the varied dietary and migratory habits of biota. To better understand how industrial effluent influences the cycling and bioaccumulation of Hg within the Ohio River, Hg stable isotope analysis was applied to various nonbiological and biological media. High Hg concentrations in suspended particulate matter suggest this vector was the largest contributor of Hg to the water column, and distinct Hg source signatures were observed in effluent particulates from different industrial processes, such as chlor‐alkali activity (δ 202 Hg = −0.52‰) and coal power plant discharge (δ 202 Hg = −1.39‰). Despite this distinction, average sediments (δ 202 Hg = −1.00 ± 0.23‰) showed intermediate isotopic signatures that suggest the accumulation of a mixed Hg source driven by multiple industrial discharges. Biota in the system were shown to have a conserved range of δ 202 Hg and estimation approaches related these signatures back to particulate matter within Hannibal Pool. Mussels were found to conserve Hg isotopes signatures independently of food web drivers and served as ideal water column indicators of bioaccumulated Hg sources. This study highlights the complexity of Hg cycling within an industrialized river and shows that an isotope tracer approach can provide insight to water column sources of Hg. Integr Environ Assess Manag 2021;17:233−242. Published 2020. This article is a US Government work and is in the public domain in the USA.

Ohio↗

USGS2020

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 δ 202 Hg and Δ 199 Hg values. These trends can be attributed to large-scale industrial emission of Hg into the atmosphere and are consistent with positive Δ 199 Hg values measured in modern-day precipitation and modeled increases in δ 202 Hg 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.

North America↗

USGS2020

Mercury export from Arctic great rivers

Land–ocean linkages are strong across the circumpolar north, where the Arctic Ocean accounts for 1% of the global ocean volume and receives more than 10% of the global river discharge. Yet estimates of Arctic riverine mercury (Hg) export constrained from direct Hg measurements remain sparse. Here, we report results from a coordinated, year-round sampling program that focused on the six major Arctic rivers to establish a contemporary (2012–2017) benchmark of riverine Hg export. We determine that the six major Arctic rivers exported an average of 20 000 kg y –1 of total Hg (THg, all forms of Hg). Upscaled to the pan-Arctic, we estimate THg flux of 37 000 kg y –1 . More than 90% of THg flux occurred during peak river discharge in spring and summer. Normalizing fluxes to watershed area (yield) reveals higher THg yields in regions where greater denudation likely enhances Hg mobilization. River discharge, suspended sediment, and dissolved organic carbon predicted THg concentration with moderate fidelity, while suspended sediment and water yields predicted THg yield with high fidelity. These findings establish a benchmark in the face of rapid Arctic warming and an intensifying hydrologic cycle, which will likely accelerate Hg cycling in tandem with changing inputs from thawing permafrost and industrial activity.

Environmental Science & Technology↗

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

Urban stormwater: An overlooked pathway of extensive mixed contaminants to surface and groundwaters in the United States

Increasing global reliance on stormwater control measures to reduce discharge to surface water, increase groundwater recharge, and minimize contaminant delivery to receiving waterbodies necessitates improved understanding of stormwater-contaminant profiles. A multi-agency study of organic and inorganic chemicals in urban stormwater from 50 runoff events at 21 sites across the United States demonstrated that stormwater transports substantial mixtures of polycyclic aromatic hydrocarbons, bioactive contaminants (pesticides and pharmaceuticals), and other organic chemicals known or suspected to pose environmental health concern. Numerous organic-chemical detections per site (median number of chemicals detected = 73), individual concentrations exceeding 10,000 ng/L, and cumulative concentrations up to 263,000 ng/L suggested concern for potential environmental effects during runoff events. Organic concentrations, loads, and yields were positively correlated with impervious surfaces and highly developed urban catchments. Episodic storm-event organic concentrations and loads were comparable to and often exceeded those of daily wastewater plant discharges. Inorganic chemical concentrations were generally dilute in concentration and did not exceed chronic aquatic life criteria. Methylmercury was measured in 90% of samples with concentrations that ranged from 0.05 to 1.0 ng/L.

Environmental Science & Technology↗

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↗