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Jacob A. Fleck

Publications and source records attributed to Jacob A. Fleck.

16 recordsLinked to original sources

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

Geochemical data for water, streambed sediment, and fish tissue from the Sierra Nevada Mercury Impairment Project, 2011–12

This report presents geochemical data for surface water, streambed sediment, and fish tissue samples collected during low-flow conditions in 20 to 24 Sierra Nevada streams during 2011 and 2012. The dataset is part of a larger study designed to assess the factors that control mercury concentrations in fish tissue and to develop a model that predicts mercury concentration in the tissue of selected fish species in Sierra Nevada streams. The ranges of total mercury concentration observed in different matrices of water and sediment from 24 locations were as follows: below detection to 0.86 nanograms per liter in filtered water, below detection to 4.06 nanograms per liter in suspended particulates (greater than 0.3 micrometer in diameter), 1.1 to 381 nanograms per gram in bed sediment less than 2 millimeters, and 28.1 to 1,410 nanograms per gram in bed sediment less than 0.063 millimeters. The ratio of monomethyl mercury to total mercury ranged as follows: below detection to 19.2 percent in filtered water, below detection to 51.7 percent in suspended particles (greater than 0.3 micrometer), and below detection to 7.6 percent in streambed sediment less than 2 millimeters. Fish from 3 species collected at 20 locations had the following range in total mercury concentration (all concentrations wet weight): 10 to 292 nanograms per gram in rainbow trout (293 fish, 19 locations), 13 to 386 nanograms per gram in brown trout (33 fish, 10 locations), and 159 nanograms per gram in hardhead (1 fish). Concentrations of selenium in fish (wet weight) ranged from 60 to 420 nanograms per gram in rainbow trout (66 fish, 19 locations) and from 180 to 240 nanograms per gram in brown trout (6 fish, 2 locations).

Sierra Nevada

Mercury on a landscape scale—Balancing regional export with wildlife health

The Cosumnes River watershed requires a 57–64 percent reduction in loads to meet the new Delta methylmercury (MeHg) total maximum daily load allocation, established by the Central Valley Regional Water Quality Control Board. Because there are no large point sources of MeHg in the watershed, the focus of MeHg load reductions will fall upon non-point sources, particularly the expansive wetlands considered to be a primary source of MeHg in the region. Few management practices have been implemented and tested in order to meet load reductions in managed wetlands, but recent efforts have shown promise. This project examines a treatment approach to reduce MeHg loads to the Sacramento-San Joaquin River Delta by creating open-water deep cells with a small footprint at the downstream end of wetlands to promote net demethylation of MeHg and to minimize MeHg and Hg loads exiting wetlands at the Cosumnes River Preserve. Specifically, the deep cells were were located immediately up gradient of the wetland’s outflow weir and were deep enough (75–91 centimeter depth) to be vegetation-free. The topographic and hydrologic structure of each treatment wetland was modified to include open-water deep cells so that the removal of aqueous MeHg might be enhanced through (1) particle settling, (2) photo-degradation, and (3) benthic microbial demethylation. These deep cells were, therefore, expected to clean MeHg from surface water prior to its discharge to the Cosumnes River and the downstream Delta. Our goal was to test whether the implementation of the deep cells within wetlands would minimize MeHg and total Hg export. Further, we sought to test whether continuous flow-through hydrology, would lower MeHg concentrations in resident biota, compared to traditional wetland management operations. The dominant practice in seasonal wetlands management is the “fill-and-maintain” approach, in which wetlands are filled with water and the water levels maintained without substantial draining until drawdown. Our approach was to create and characterize replicate treatment wetland complexes, in conjunction with monitoring of hydrologic, biologic, and chemical indicators of MeHg exposure for two full annual cycles within winter-spring flooded seasonal wetlands. In addition to the creation of deep cells within treatment wetlands, hydrology was manipulated so that there was a constant flow-through of water, while the control wetlands utilized the fill-and-maintain approach. Specifically, the treatment wetlands were maintained in a flow-through manner, while the control wetlands were maintained in a fill-and-maintain manner from September through May, to test the hypothesis that the flow of water through the seasonal wetland can lower fish bioaccumulation through dilution of MeHg-concentrated water within the wetland by constant inflows of water into the wetland. The major tasks of this study included: (1) field design and implementation, (2) water and wetland management, (3) hydrologic monitoring and water quality sampling, (4) MeHg export and load estimates, (5) caged fish experiments for examining MeHg bioaccumulation, (6) site and process characterization to improve understanding and transferability of results, (7) adaptive management, transferability, and outreach, and (8) reporting of results and conclusions. This report summarizes the key findings of this study, which focuses on MeHg load estimates from control and treatment wetlands, quantification of three MeHg removal mechanisms (particulate settling, benthic demethylation, and photo-demethylation) in the deep cells within the treatment wetlands, and MeHg bioaccumulation in wetland fishes. Key findings include: Over two years of study, mean whole-water MeHg load decreased 37 percent in deep cells, when comparing inlet of check weir flows to outlet. Of the 37 percent MeHg load removed within the deep cell, photodegradation accounted for 7 percent and particle flux to the benthos accounted for 24 percent of the mass removed, with the remaining 6 percent apparent MeHg loss unexplained. Benthic MeHg degradation did not appear to be a major MeHg removal process in the deep cells, as changes in the ambient MeHg pool over 7-day bottle incubations showed that the surface sediment exhibited net MeHg production in the majority (87 percent) of incubation experiments. In only 13 percent of the incubations (3 out of 24) was net MeHg degradation observed. Estimates of benthic diffusive flux of MeHg across the sediment/water interface were small relative to particulate flux and variable (positive or negative), suggesting this is likely a minor term in the overall MeHg budget within the deep cells. Although the deep cells served as net MeHg sink overall, MeHg export from the flow-through treatment wetlands (shallow and deep combined) exceeded export from the fill-and-maintain managed control wetlands, because of the differences in hydrologic management between the two wetland types. Shallow wetlands under flow-through conditions generated a net export of MeHg. Most of the annual MeHg export from the treatment wetlands occurred within the first 3 months of flood up (September to November), shortly after hydrologic management began. Despite the effectiveness of the deep cell in lowering MeHg export concentrations, total mercury (THg) concentration did not decrease in biosentinel fish ( Gambusia affinis , Mosquitofish) between the deep cell inlet and outlet. Mosquitofish THg concentrations were higher in treatment wetlands than in control wetlands during the first year of study, likely because of an associated increase in MeHg availability immediately following wetland construction activities. Mosquitofish THg concentrations declined in the treatment wetlands during the second year of study, and fish THg concentrations in treatment wetlands were no different from those in the control. Similarly, the increased hydrologic flow rates in the treatment wetlands did not lower fish THg concentrations nor aqueous MeHg concentrations in the shallow cells, suggesting that MeHg flux from the sediment to water column exceeded the flow-through flushing rate in the shallow portion of the treatment wetlands. Reductions in MeHg concentrations of surface water and fish may require higher flow rates than used in the study to achieve the region’s regulatory goals. However, the flow rates necessary may not be feasible for these managed wetlands because of limited water supply and the associated costs for water and pumping. The use of deep cells in seasonal wetlands were effective in lowering MeHg exports under continuous water flow-through hydrology. However, fill-and-maintain hydrology had lower exports overall, because of a single major drainage event at the end of the flood season. Future studies focused on limiting MeHg export should consider combining deep cells with the fill-and-maintain or fill-and-trickle hydrologic management approach.

California

Mercury, monomethyl mercury, and dissolved organic carbon concentrations in surface water entering and exiting constructed wetlands treated with metal-based coagulants, Twitchell Island, California

Coagulation with metal-based salts is a practice commonly employed by drinking-water utilities to decrease particle and dissolved organic carbon concentrations in water. In addition to decreasing dissolved organic carbon concentrations, the effectiveness of iron- and aluminum-based coagulants for decreasing dissolved concentrations both of inorganic and monomethyl mercury in water was demonstrated in laboratory studies that used agricultural drainage water from the Sacramento–San Joaquin Delta of California. To test the effectiveness of this approach at the field scale, nine 15-by-40 ‑ meter wetland cells were constructed on Twitchell Island that received untreated water from island drainage canals (control) or drainage water treated with polyaluminum chloride or ferric sulfate coagulants. Surface-water samples were collected approximately monthly during November 2012–September 2013 from the inlets and outlets of the wetland cells and then analyzed by the U.S. Geological Survey for total concentrations of mercury and monomethyl mercury in filtered (less than 0.3 micrometers) and suspended-particulate fractions and for concentrations of dissolved organic carbon. In the control wetland cells, total mercury concentrations in filtered water samples ranged from 0.94 to 2.47 nanograms per liter (ng/L) at the control inlets and from 0.84 to 2.63 ng/L at the control outlets, and particulate total mercury concentrations in water ranged from 0.27 to 1.49 ng/L at the control inlets and from 0.17 to 1.11 ng/L at the control outlets. Monomethyl mercury concentrations in filtered water ranged from 0.16 to 0.88 ng/L at the control inlets and from 0.13 to 1.30 ng/L at the control outlets; particulate monomethyl mercury concentrations in water ranged from 0.03 to 0.24 ng/L at the control inlets and from 0.03 to 0.23 ng/L at the control outlets. Dissolved organic carbon concentrations in water ranged from 7.9 to 26.7 milligrams per liter at the control inlets and from 8.5 to 28.0 milligrams per liter at the control outlets. Following coagulation, but prior to passage through the wetland cells, coagulation treatments transferred dissolved mercury and carbon to the particulate fraction relative to untreated source water: at the wetland cell inlets, the coagulation treatments decreased concentrations of filtered total mercury by 59–76 percent, filtered monomethyl mercury by 40–70 percent, and dissolved organic carbon by 65–86 percent. Passage through the wetland cells decreased the particulate fraction of mercury in wetland cells that received coagulant-treated water. Changes in total mercury, monomethyl mercury, and dissolved organic carbon concentrations resulting from wetland passage varied both by treatment and season. Despite increased monomethyl mercury in the filtered fraction during wetland passage between March and August, the coagulation-wetland systems generally decreased total mercury (filtered plus particulate) and monomethyl mercury (filtered plus particulate) concentrations relative to source water. Coagulation—either alone or in association with constructed wetlands—could be an effective way to decrease concentrations of mercury and dissolved organic carbon in surface water as well as the bioavailability of mercury in the Sacramento–San Joaquin Delta.

California

Experimental dosing of wetlands with coagulants removes mercury from surface water and decreases mercury bioaccumulation in fish

Mercury pollution is widespread globally, and strategies for managing mercury contamination in aquatic environments are necessary. We tested whether coagulation with metal-based salts could remove mercury from wetland surface waters and decrease mercury bioaccumulation in fish. In a complete randomized block design, we constructed nine experimental wetlands in California’s Sacramento–San Joaquin Delta, stocked them with mosquitofish ( Gambusia affinis ), and then continuously applied agricultural drainage water that was either untreated (control), or treated with polyaluminum chloride or ferric sulfate coagulants. Total mercury and methylmercury concentrations in surface waters were decreased by 62% and 63% in polyaluminum chloride treated wetlands and 50% and 76% in ferric sulfate treated wetlands compared to control wetlands. Specifically, following coagulation, mercury was transferred from the filtered fraction of water into the particulate fraction of water which then settled within the wetland. Mosquitofish mercury concentrations were decreased by 35% in ferric sulfate treated wetlands compared to control wetlands. There was no reduction in mosquitofish mercury concentrations within the polyaluminum chloride treated wetlands, which may have been caused by production of bioavailable methylmercury within those wetlands. Coagulation may be an effective management strategy for reducing mercury contamination within wetlands, but further studies should explore potential effects on wetland ecosystems.

California

Concurrent photolytic degradation of aqueous methylmercury and dissolved organic matter

Monomethyl mercury (MeHg) is a potent neurotoxin that threatens ecosystem viability and human health. In aquatic systems, the photolytic degradation of MeHg (photodemethylation) is an important component of the MeHg cycle. Dissolved organic matter (DOM) is also affected by exposure to solar radiation (light exposure) leading to changes in DOM composition that can affect its role in overall mercury (Hg) cycling. This study investigated changes in MeHg concentration, DOM concentration, and the optical signature of DOM caused by light exposure in a controlled field-based experiment using water samples collected from wetlands and rice fields. Filtered water from all sites showed a marked loss in MeHg concentration after light exposure. The rate of photodemethylation was 7.5 × 10 -3 m 2 mol -1 (s.d. 3.5 × 10 -3 ) across all sites despite marked differences in DOM concentration and composition. Light exposure also caused changes in the optical signature of the DOM despite there being no change in DOM concentration, indicating specific structures within the DOM were affected by light exposure at different rates. MeHg concentrations were related to optical signatures of labile DOM whereas the percent loss of MeHg was related to optical signatures of less labile, humic DOM. Relationships between the loss of MeHg and specific areas of the DOM optical signature indicated that aromatic and quinoid structures within the DOM were the likely contributors to MeHg degradation, perhaps within the sphere of the Hg-DOM bond. Because MeHg photodegradation rates are relatively constant across freshwater habitats with natural Hg–DOM ratios, physical characteristics such as shading and hydrologic residence time largely determine the relative importance of photolytic processes on the MeHg budget in these mixed vegetated and open-water systems.

Science of the Total Environment

Methylmercury production in sediment from agricultural and non-agricultural wetlands in the Yolo Bypass, California, USA

As part of a larger study of mercury (Hg) biogeochemistry and bioaccumulation in agricultural (rice growing) and non-agricultural wetlands in California's Central Valley, USA, seasonal and spatial controls on methylmercury (MeHg) production were examined in surface sediment. Three types of shallowly-flooded agricultural wetlands (white rice, wild rice, and fallow fields) and two types of managed (non-agricultural) wetlands (permanently and seasonally flooded) were sampled monthly-to-seasonally. Dynamic seasonal changes in readily reducible ‘reactive’ mercury (Hg(II) R ), Hg(II)-methylation rate constants (k meth ), and concentrations of electron acceptors (sulfate and ferric iron) and donors (acetate), were all observed in response to field management hydrology, whereas seasonal changes in these parameters were more muted in non-agricultural managed wetlands. Agricultural wetlands exhibited higher sediment MeHg concentrations than did non-agricultural wetlands, particularly during the fall through late-winter (post-harvest) period. Both sulfate- and iron-reducing bacteria have been implicated in MeHg production, and both were demonstrably active in all wetlands studied. Stoichiometric calculations suggest that iron-reducing bacteria dominated carbon flow in agricultural wetlands during the growing season. Sulfate-reducing bacteria were not stimulated by the addition of sulfate-based fertilizer to agricultural wetlands during the growing season, suggesting that labile organic matter, rather than sulfate, limited their activity in these wetlands. Along the continuum of sediment geochemical conditions observed, values of k meth increased approximately 10,000-fold, whereas Hg(II) R decreased 100-fold. This suggests that, with respect to the often opposing trends of Hg(II)-methylating microbial activity and Hg(II) availability for methylation, microbial activity dominated the Hg(II)-methylation process, and that along this biogeochemical continuum, conditions that favored microbial sulfate reduction resulted in the highest calculated MeHg production potential rates. Rice straw management options aimed at limiting labile carbon supplies to surface sediment during the post-harvest fall–winter period may be effective in limiting MeHg production within agricultural wetlands.

California

Mercury cycling in agricultural and managed wetlands, Yolo Bypass, California: Spatial and seasonal variations in water quality

The seasonal and spatial variability of water quality, including mercury species, was evaluated in agricultural and managed, non-agricultural wetlands in the Yolo Bypass Wildlife Area, an area managed for multiple beneficial uses including bird habitat and rice farming. The study was conducted during an 11-month period (June 2007 to April 2008) that included a summer growing season and flooded conditions during winter. Methylmercury (MeHg) concentrations in surface water varied over a wide range (0.1 to 37 ng L−1 unfiltered; 0.04 to 7.3 ng L−1 filtered). Maximum MeHg values are among the highest ever recorded in wetlands. Highest MeHg concentrations in unfiltered surface water were observed in drainage from wild rice fields during harvest (September 2007), and in white rice fields with decomposing rice straw during regional flooding (February 2008). The ratio of MeHg to total mercury (MeHg/THg) increased about 20-fold in both unfiltered and filtered water during the growing season (June to August 2007) in the white and wild rice fields, and about 5-fold in fallow fields (July to August 2007), while there was little to no change in MeHg/THg in the permanent wetland. Sulfate-bearing fertilizer had no effect on Hg(II) methylation, as sulfate-reducing bacteria were not sulfate limited in these agricultural wetlands. Concentrations of MeHg in filtered and unfiltered water correlated with filtered Fe, filtered Mn, DOC, and two indicators of sulfate reduction: the SO4 2 −/Cl− ratio, and δ34S in aqueous sulfate. These relationships suggest that microbial reduction of SO4 2−, Fe(III), and possibly Mn(IV) may contribute to net Hg(II)-methylation in this setting.

California

Differentiating transpiration from evaporation in seasonal agricultural wetlands and the link to advective fluxes in the root zone

The current state of science and engineering related to analyzing wetlands overlooks the importance of transpiration and risks data misinterpretation. In response, we developed hydrologic and mass budgets for agricultural wetlands using electrical conductivity (EC) as a natural conservative tracer. We developed simple differential equations that quantify evaporation and transpiration rates using flowrates and tracer concentrations atwetland inflows and outflows. We used two ideal reactormodel solutions, a continuous flowstirred tank reactor (CFSTR) and a plug flow reactor (PFR), to bracket real non-ideal systems. From those models, estimated transpiration ranged from 55% (CFSTR) to 74% (PFR) of total evapotranspiration (ET) rates, consistent with published values using standard methods and direct measurements. The PFR model more appropriately represents these nonideal agricultural wetlands in which check ponds are in series. Using a fluxmodel, we also developed an equation delineating the root zone depth at which diffusive dominated fluxes transition to advective dominated fluxes. This relationship is similar to the Peclet number that identifies the dominance of advective or diffusive fluxes in surface and groundwater transport. Using diffusion coefficients for inorganic mercury (Hg) and methylmercury (MeHg) we calculated that during high ET periods typical of summer, advective fluxes dominate root zone transport except in the top millimeters below the sediment–water interface. The transition depth has diel and seasonal trends, tracking those of ET. Neglecting this pathway has profound implications: misallocating loads along different hydrologic pathways; misinterpreting seasonal and diel water quality trends; confounding Fick's First Law calculations when determining diffusion fluxes using pore water concentration data; and misinterpreting biogeochemicalmechanisms affecting dissolved constituent cycling in the root zone. In addition,our understanding of internal root zone cycling of Hg and other dissolved constituents, benthic fluxes, and biological irrigation may be greatly affected.

Science of the Total Environment

Methylmercury production in and export from agricultural wetlands in California, USA: the need to account for physical transport processes into and out of the root zone

Concentration and mass balance analyses were used to quantify methylmercury (MeHg) loads from conventional (white) rice, wild rice, and fallowed fields in northern California's Yolo Bypass. These analyses were standardized against chloride to distinguish transport pathways and net ecosystem production (NEP). During summer, chloride loads were both exported with surface water and moved into the root zone at a 2:1 ratio. MeHg and dissolved organic carbon (DOC) behaved similarly with surface water and root zone exports at ~ 3:1 ratio. These trends reversed in winter with DOC, MeHg, and chloride moving from the root zone to surface waters at rates opposite and exceeding summertime root zone fluxes. These trends suggest that summer transpiration advectively moves constituents from surface water into the root zone, and winter diffusion, driven by concentration gradients, subsequently releases those constituents into surface waters. The results challenge a number of paradigms regarding MeHg. Specifically, biogeochemical conditions favoring microbial MeHg production do not necessarily translate to synchronous surface water exports; MeHg may be preserved in the soils allowing for release at a later time; and plants play a role in both biogeochemistry and transport. Our calculations show that NEP of MeHg occurred during both summer irrigation and winter flooding. Wild rice wet harvesting and winter flooding of white rice fields were specific practices that increased MeHg export, both presumably related to increased labile organic carbon and disturbance. Outflow management during these times could reduce MeHg exports. Standardizing MeHg outflow:inflow concentration ratios against natural tracers (e.g. chloride, EC) provides a simple tool to identify NEP periods. Summer MeHg exports averaged 0.2 to 1 μg m − 2 for the different agricultural wetland fields, depending upon flood duration. Average winter MeHg exports were estimated at 0.3 μg m − 2 . These exports are within the range reported for other shallow aquatic systems.

California

Mercury cycling in agricultural and managed wetlands: a synthesis of methylmercury production, hydrologic export, and bioaccumulation from an integrated field study

With seasonal wetting and drying, and high biological productivity, agricultural wetlands (rice paddies) may enhance the conversion of inorganic mercury (Hg(II)) to methylmercury (MeHg), the more toxic, organic form that biomagnifies through food webs. Yet, the net balance of MeHg sources and sinks in seasonal wetland environments is poorly understood because it requires an annual, integrated assessment across biota, sediment, and water components. We examined a suite of wetlands managed for rice crops or wildlife during 2007–2008 in California's Central Valley, in an area affected by Hg contamination from historic mining practices. Hydrologic management of agricultural wetlands for rice, wild rice, or fallowed — drying for field preparation and harvest, and flooding for crop growth and post-harvest rice straw decay — led to pronounced seasonality in sediment and aqueous MeHg concentrations that were up to 95-fold higher than those measured concurrently in adjacent, non-agricultural permanently-flooded and seasonally-flooded wetlands. Flooding promoted microbial MeHg production in surface sediment of all wetlands, but extended water residence time appeared to preferentially enhance MeHg degradation and storage. When incoming MeHg loads were elevated, individual fields often served as a MeHg sink, rather than a source. Slow, horizontal flow of shallow water in the agricultural wetlands led to increased importance of vertical hydrologic fluxes, including evapoconcentration of surface water MeHg and transpiration-driven advection into the root zone, promoting temporary soil storage of MeHg. Although this hydrology limited MeHg export from wetlands, it also increased MeHg exposure to resident fish via greater in situ aqueous MeHg concentrations. Our results suggest that the combined traits of agricultural wetlands — slow-moving shallow water, manipulated flooding and drying, abundant labile plant matter, and management for wildlife — may enhance microbial methylation of Hg(II) and MeHg exposure to local biota, as well as export to downstream habitats during uncontrolled winter-flow events.

California

Mercury cycling in agricultural and managed wetlands of California: seasonal influences of vegetation on mercury methylation, storage, and transport

Plants are a dominant biologic and physical component of many wetland capable of influencing the internal pools and fluxes of methylmercury (MeHg). To investigate their role with respect to the latter, we examined the changing seasonal roles of vegetation biomass and Hg, C and N composition from May 2007-February 2008 in 3 types of agricultural wetlands (domesticated or white rice, wild rice, and fallow fields), and in adjacent managed natural wetlands dominated by cattail and bulrush (tule). We also determined the impact of vegetation on seasonal microbial Hg methylation rates, and Hg and MeHg export via seasonal storage in vegetation, and biotic consumption of rice seed. Despite a compressed growing season of ~ 3 months, annual net primary productivity (NPP) was greatest in white rice fields and carbon more labile (leaf median C:N ratio = 27). Decay of senescent litter (residue) was correlated with microbial MeHg production in winter among all wetlands. As agricultural biomass accumulated from July to August, THg concentrations declined in leaves but MeHg concentrations remained consistent, such that MeHg pools generally increased with growth. Vegetation provided a small, temporary, but significant storage term for MeHg in agricultural fields when compared with hydrologic export. White rice and wild rice seeds reached mean MeHg concentrations of 4.1 and 6.2 ng g dw - 1 , respectively. In white rice and wild rice fields, seed MeHg concentrations were correlated with root MeHg concentrations (r = 0.90, p < 0.001), suggesting transport of MeHg to seeds from belowground tissues. Given the proportionally elevated concentrations of MeHg in rice seeds, white and wild rice crops may act as a conduit of MeHg into biota, especially waterfowl which forage heavily on rice seeds within the Central Valley of California, USA. Thus, while plant tissues and rhizosphere soils provide temporary storage for MeHg during the growing season, export of MeHg is enhanced post-harvest through increased hydrologic and biotic export.

California

Mercury dynamics in a San Francisco estuary tidal wetland: assessing dynamics using in situ measurements

We used high-resolution in situ measurements of turbidity and fluorescent dissolved organic matter (FDOM) to quantitatively estimate the tidally driven exchange of mercury (Hg) between the waters of the San Francisco estuary and Browns Island, a tidal wetland. Turbidity and FDOM—representative of particle-associated and filter-passing Hg, respectively—together predicted 94 % of the observed variability in measured total mercury concentration in unfiltered water samples (UTHg) collected during a single tidal cycle in spring, fall, and winter, 2005–2006. Continuous in situ turbidity and FDOM data spanning at least a full spring-neap period were used to generate UTHg concentration time series using this relationship, and then combined with water discharge measurements to calculate Hg fluxes in each season. Wetlands are generally considered to be sinks for sediment and associated mercury. However, during the three periods of monitoring, Browns Island wetland did not appreciably accumulate Hg. Instead, gradual tidally driven export of UTHg from the wetland offset the large episodic on-island fluxes associated with high wind events. Exports were highest during large spring tides, when ebbing waters relatively enriched in FDOM, dissolved organic carbon (DOC), and filter-passing mercury drained from the marsh into the open waters of the estuary. On-island flux of UTHg, which was largely particle-associated, was highest during strong winds coincident with flood tides. Our results demonstrate that processes driving UTHg fluxes in tidal wetlands encompass both the dissolved and particulate phases and multiple timescales, necessitating longer term monitoring to adequately quantify fluxes.

California

The effects of sediment and mercury mobilization in the South Yuba River and Humbug Creek confluence area, Nevada County, California: Concentrations, speciation, and environmental fate – Part 1: Field characterization

Millions of pounds of mercury (Hg) were deposited in the river and stream channels of the Sierra Nevada from placer and hard-rock mining operations in the late 1800s and early 1900s. The resulting contaminated sediments are relatively harmless when buried and isolated from the overlying aquatic environment. The entrained Hg in the sediment constitutes a potential risk to human and ecosystem health should it be reintroduced to the actively cycling portion of the aquatic system, where it can become methylated and subsequently bioaccumulated in the food web. Each year, sediment is mobilized within these fluvial systems during high stormflows, transporting hundreds of tons of Hg-laden sediment downstream. The State of California and resource-management agencies, including the Bureau of Land Management (BLM) and the U.S. Forest Service, are concerned about additional disturbances, such as from suction gold dredging activities, which have the potential to mobilize Hg associated with buried sediment layers elevated in Hg that are otherwise likely to remain buried under normal storm conditions. The BLM initiated a study looking at the feasibility of removing Hg-contaminated sediment at the confluence of the South Yuba River and Humbug Creek in the northern Sierra Nevada of California by using standard suction-dredge technology. Additionally, the California State Water Resources Control Board (SWRCB) supported a comprehensive characterization of the intended dredge site. Together, the BLM and SWRCB supported a comprehensive characterization of Hg contamination at the site and the potential effects of sediment disturbance at locations with historical hydraulic mining debris on downstream environments. The comprehensive study consisted of two primary components: field studies and laboratory experiments. The field component, described in this report, had several study elements: 1) a preliminary, smallscale, in-stream dredge test; 2) comprehensive characterization of grain size distribution, Hg speciation, and mineralogy of bed and suspended sediment; 3) a determination of the past and current sources of sediment in the study area; 4) an assessment of Hg bioaccumulation in the local invertebrate population; and 5) a comparison of potential Hg transport caused by natural storm disturbances with potential Hg mobilization caused by suction dredging as a method of Hg removal at the study site. The laboratory component of the study assessed the potential influence of the disturbance of Hg-contaminated sediment through experiments designed to simulate in-stream transport, deposition, and potential methylation of Hg, described in a companion report (see Marvin-DiPasquale and others, 2011). Results of the field studies indicate that the fine-grained fraction (silt-clay, less than 0.063 millimeters) contains the greatest concentration of Hg in contaminated sediment. Because the fine-grained fraction is the most susceptible to longrange fluvial transport, disturbance of Hg-contaminated sediment is likely to increase the concentration and load of Hg in downstream waters. The preliminary, small-scale dredge test showed an increase in the concentration of fine particles and Hg in the water column caused by the dredge activity, despite relatively low concentrations of fine particles and Hg (about 300 nanograms per gram) at the dredge site. Characterization of sediment from two test pits and other sites in the vicinity of the confluence of the South Yuba River and Humbug Creek revealed a highly variable distribution of fine- and coarse-grained sediment. The highest levels of Hg contamination (up to 11,100 ng/g) were associated with the fine-grained fraction of sediment from the bedrock contact zone of Pit 2, a horizon which also yielded grains of gold and gold-Hg amalgam. A closed-circuit tank experiment with a venturi dredge at the base of Pit 1, in a gravel bar within the South Yuba River, resulted in fine-grained suspended sediment remaining in suspension more than 40 hours following the disturbance simulation. Although the volumetric concentration of Hg declined over time as particles settled out, the concentration of Hg on the suspended particles increased over time as the suspended material became finer grained, because Hg is preferentially adsorbed on to clay-sized particles. Mineralogical and chemical analyses indicated that the buried fine-grained material with the greatest Hg contamination was derived from hydraulic mining debris, which consist primarily of Eocene gravels mined in the Malakoff Diggins, North Bloomfield, and Lake City areas within the South Yuba River watershed. Coarse material and more recently deposited sediment were derived primarily from upstream sources on the South Yuba River. The biota assessment indicated that invertebrate taxa collected from all sites on the South Yuba River in 2007, including lower Humbug Creek, had elevated concentrations of total mercury (THg) and methylmercury (MeHg) compared to a reference site on the Bear River, upstream of mining effects. Differences with the reference site were less pronounced in 2008 when a significant reduction in MeHg concentrations was observed in biota across all taxa from concentrations in 2007. It is possible that the inter-annual variation was related to the fact that suction dredging was active in the South Yuba River in 2007 but not in 2008 when a local moratorium was imposed by the BLM. There were significant variations among taxa for both THg and MeHg concentrations, with the water striders (Gerridae) having the highest concentrations of both THg and MeHg; variation among sites was not as strong as between years or among taxa. These results suggest that additional monitoring would be helpful to investigate the possible linkage between variations in MeHg bioaccumulation and levels of suction dredge activity in areas of historical gold mining. Results from the field studies indicate that disturbance of the finegrained Hg-contaminated sediment would likely lead to enhanced mobilization of Hg to downstream environments; therefore, the use of suction dredging to remove Hg at the South Yuba River and Humbug Creek confluence area would likely result in enhanced Hg transport downstream relative to natural conditions.

California

Mercury, methylmercury, and other constituents in sediment and water from seasonal and permanent wetlands in the Cache Creek settling basin and Yolo Bypass, Yolo County, California, 2005-06

This report presents surface water and surface (top 0-2 cm) sediment geochemical data collected during 2005-2006, as part of a larger study of mercury (Hg) dynamics in seasonal and permanently flooded wetland habitats within the lower Sacramento River basin, Yolo County, California. The study was conducted in two phases. Phase I represented reconnaissance sampling and included three locations within the Cache Creek drainage basin; two within the Cache Creek Nature Preserve (CCNP) and one in the Cache Creek Settling Basin (CCSB) within the creek's main channel near the southeast outlet to the Yolo Bypass. Two additional downstream sites within the Yolo Bypass Wildlife Area (YBWA) were also sampled during Phase I, including one permanently flooded wetland and one seasonally flooded wetland, which had began being flooded only 1–2 days before Phase I sampling. Results from Phase I include: (a) a negative correlation between total mercury (THg) and the percentage of methylmercury (MeHg) in unfiltered surface water; (b) a positive correlation between sediment THg concentration and sediment organic content; (c) surface water and sediment THg concentrations were highest at the CCSB site; (d) sediment inorganic reactive mercury (Hg(II) R ) concentration was positively related to sediment oxidation-reduction potential and negatively related to sediment acid volatile sulfur (AVS) concentration; (e) sediment Hg(II) R concentrations were highest at the two YBWA sites; (f) unfiltered surface water MeHg concentration was highest at the seasonal wetland YBWA site, and sediment MeHg was highest at the permanently flooded YBWA site; (g) a 1,000-fold increase in sediment pore water sulfate concentration was observed in the downstream transect from the CCNP to the YBWA; (h) low sediment pore water sulfide concentrations (<1 µmol/L) across all sites; and (i) iron (Fe) speciation data suggest a higher potential for microbial Fe(III)-reduction in the YBWA compared to the CCSB. Phase II sampling did not include the original three Cache Creek sites, but instead focused on the original two sites within the YBWA and a similarly paired set of seasonally and permanently flooded wetland sites within the CCSB. Sediment sampling at the YBWA and CCSB occurred approximately 28 days and 52 days, respectively, after the initial flooding of the respective seasonal wetlands, and again towards the end of the seasonal flooding period (end of May 2006). Results from Phase II sampling include: (a) sediment MeHg concentration and the percentage of THg as MeHg (%MeHg) in unfiltered surface waters were generally higher in the YBWA compared to the CCSB; (b) suspended sediment concentration (SCC) in surface water was positively correlated with both THg and MeHg in unfiltered water across all sites, although the relationship between SCC and MeHg differed for the two regions, suggesting local MeHg sources; (c) MeHg concentration in unfiltered surface water was positively correlated to sediment MeHg concentrations across all sites, supporting the suggestion of unique local (sediment) sources of MeHg to the water column; (d) THg concentration in filtered water was positively correlated with both total Fe and dissolved organic carbon (DOC), offering additional support for the role of these constituents in the partitioning of THg between particulate and dissolved phases; (e) flooding of the YBWA seasonal wetland resulted in a rapid and significant (5-fold) rise in sediment MeHg concentration within 3–4 weeks following inundation; and (f) temporal changes in sediment S and Fe speciation suggest that rates of both microbial sulfate reduction and Fe(III)-reduction were significantly higher at YBWA, compared to CCSB, during the period between flooding and drying. The geochemical data presented in this report indicate that (a) strong spatial and temporal differences in Hg speciation and transformations can occur within the range of wetland habitats found in the lower Sacramento River basin; (b) flooding of seasonal wetlands can be accompanied by a rapid increase in benthic MeHg production and the release of previously formed MeHg (generated during or since the previous flooding season) to the overlying water column; (c) S and Fe chemistry, and associated microbial reduction pathways, play an important role in mediating the speciation and transformation of Hg in these wetland habitats; (d) hydroperiod is a primary forcing function in mediating MeHg production among various wetland types; and (e) MeHg production appears to be more active in the YBWA compared to the CCSB.

California