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Jacob A. Fleck

Publications and source records attributed to Jacob A. Fleck.

At least 19 recordsLinked to original sources

Evaluation of turbidity corrections for EXO fluorescent dissolved organic matter (fDOM) sensors

Executive Summary The use of field-deployable fluorescence sensors to better understand dissolved organic matter concentrations and composition has grown immensely in recent years. Applications of these sensors to critical monitoring efforts have also grown, encompassing post-fire monitoring, wastewater tracking, and use as a proxy for various contaminants. Despite the growth, it is well known that these sensors require corrections for temperature (Watras and others, 2011) and are subject to many light-field interferences caused by both scattering and absorbance due to dissolved and particulate substances (Downing and others, 2012; Lee and others, 2015; Booth and others, 2023). The most common fluorescence sensors used by the U.S. Geological Survey (USGS) include those targeting fluorescent dissolved organic matter (fDOM) and chlorophylls. Because fDOM sensors primarily measure fluorescence in the dissolved to colloidal phases, corrections to the interferences caused by particulates can be made relatively easily. By the end of 2024, the USGS had 69 fDOM sensors deployed within official water quality monitoring networks included on the USGS National Water Dashboard ( https://dashboard.waterdata.usgs.gov/app/nwd/en/ ) and numerous others used in surveys and research applications across the Nation. Although temperature corrections are widely applicable across sensor models, interference corrections can be model specific due to differences in design specifications across manufacturers and models (Booth and others, 2023). The corrections are also potentially subject to changes in manufacturing within a specific sensor model. Recently, USGS staff obtained information regarding possible changes in the manufacturing of its most widely-used fDOM sensor model, raising concerns about data consistency and quality in the USGS fDOM sensor networks. Furthermore, changes in turbidity sensors since the corrections guidance was performed may also affect the performance of the corrections. The turbidity sensor used in the original experiments (Downing and others, 2012) was determined to have a signal output approximately 1.3 times higher than the output of the turbidity sensor currently used in an extensive field comparison study (Messner and others, 2023). With these changes, it is imperative that the corrections be reevaluated to maintain data consistency and continuity across the USGS. In this study, we evaluated turbidity corrections for fDOM sensors over a range of serial numbers covering manufacturing dates 2015 through 2022 and turbidity serial numbers covering the range 2013 through 2022. The goal was to determine whether reported changes in the manufacturing process of the fDOM and turbidity sensors affected the correction approach developed by Downing and others (2012) such that additional guidance would be required to address this manufacturing change. To evaluate, we repeated a laboratory-based test similar to that performed by Downing and others (2012) in which a series of tank experiments with multiple sensors were deployed in a suspension of Elliot Silt Loam (ESL). High turbidities of the ESL suspension were maintained throughout the tank by turbulent recirculation using submersible pumps. Particulates were removed using a recirculated line equipped with a capsule filter (0.45 micron). Measurements were collected throughout the filtration until turbidities reached approximately 5 formazin nephelometric units (FNU; data available in Baxter and others, 2023). Each experimental run included a mixture of unique sensor combinations to account for variability imposed by the turbidity and temperature sensors. The fDOM correction factor was calculated for each combination of fDOM and turbidity sensors included in the test. We observed no systematic change in fDOM correction coefficients across serial numbers representing manufacturing years 2015 through 2022. However, the results highlighted questions raised about the corrections for high-turbidity samples, as noted in USGS Techniques and Methods (Booth and others, 2023). Applying the inverse of the commonly-used fDOM ratio with a quadratic fit performed better than the exponential fits when correcting fDOM data for turbidity in the ESL laboratory filtration test and generated a simple scale factor correction equation. This approach also served as a better indicator of data quality than the exponential fit approach. Similar to fDOM, more rigorous quality assurance measures may be necessary to evaluate turbidity sensor calibrations and performance. Sensors exceeding a certain age may need to be replaced despite passing quality assurance checks during calibration. Further testing of the turbidity corrections for different sediment and water types is warranted to better understand the variations in the fits and correctable ranges of turbidity in different systems.

Open-File Report↗

Transient methylmercury formation during wetland soil rewetting is governed by organic matter availability rather than coagulant history

Rewetting of previously drained wetland soils can induce rapid redox shifts that influence mercury (Hg) cycling and methylmercury (MeHg) production. We investigated how prior exposure to common metal-salt and biopolymer coagulants influences Hg transformations during wetland soil rewetting and whether organic matter (OM) availability modulates these effects. Wetland soils (∼300 µg kg −1 total Hg) were incubated in triplicate soil-water microcosms for 16 days following rewetting. Treatments included soils previously exposed to ferric sulfate, polyaluminum chloride, or a chitosan-based coagulant, alongside untreated controls. Upon rewetting without additional OM, redox potential declined to ∼250 mV, consistent with manganese-reducing conditions, and MeHg concentrations remained relatively low in water (0.05–0.18 ng L −1 ) and soils (1–2 µg kg −1 ) across all treatments. In contrast, addition of algal-derived OM (Spirulina powder) rapidly decreased redox potential to 0–100 mV and produced a short-lived pulse of MeHg formation in all treatments, with aqueous MeHg peaking at ∼30–40 ng L −1 and soil MeHg at ∼6–8 µg kg −1 on days 2–4 before declining. Coagulant treatments increased transient inorganic Hg concentrations in overlying water (45–75 ng L −1 ) relative to controls (∼30 ng L −1 ) but did not enhance higher MeHg production. Results demonstrate that OM-driven redox dynamics, rather than prior coagulant exposure, control transient MeHg production during wetland soil rewetting, highlighting how episodic carbon inputs can regulate mercury transformation in managed and natural wetlands.

California↗

An integrated sensor network and data driven approach to satellite remote sensing of dissolved organic matter

Traditional remote sensing retrieval models for water quality have historically relied on limited, localized data sets due to the prohibitive costs of extensive field campaigns and logistical challenges of collecting match-up data with satellite overpasses. As a result, these models often lack generalizability across seasons, tides, and sites. Furthermore, small field data sets limit the utility of modern machine learning techniques to advance remote sensing retrieval models. In situ optical sensors deployed in a sensor network to continuously monitor larger water bodies can drastically increase the number of measurements, providing the opportunity to develop new approaches for building robust remote sensing retrieval models by leveraging both remote sensing data and in situ networks as an integrated monitoring system. This study leverages a large “ground-to-space” sensor network that combines an in situ optical sensor network with satellite-based remote sensing to overcome these limitations. Utilizing a large-scale data set from the U.S. Geological Survey's Sacramento—San Joaquin River Delta monitoring network, of dissolved organic matter fluorescence measurements, and remote sensing data from the European Space Agency's Sentinel-2A and -2B satellites, this study implemented a data driven approach for dissolved organic matter models. The data set, consisting of 982 samples collected between 2018 and 2021 was used to train and validate a random forest model ( R 2 = 0.76, RMSE = 6.1 Quinine Sulfate Equivalents), with demonstrated applicability across diverse site conditions, tidal stages, and seasons. This work provides a scalable solution to address critical challenges in water quality monitoring and offers a replicable framework for global water quality management.

Calfornia↗

Municipal and industrial wastewater treatment plant effluent contributions to per- and polyfluoroalkyl substances in the Potomac River: A basin-scale measuring and modeling approach

Managing per- and polyfluoroalkyl substances (PFAS) in water resources requires a basin-scale approach. Predicted environmental concentrations (PEC) and stream-vulnerability scores for PFAS were determined for the Potomac River watershed in the eastern United States. Approximately 15% of stream reaches contained municipal and/or industrial wastewater treatment plant (WWTP) discharges that are presumptive PFAS sources, comprising from <1 to >90% of streamflow. Mean annual PEC, based on the summed concentrations of eight PFAS detected in WWTP effluents (ΣPFAS PEC ), for all stream reaches in the watershed was 3.8 ng L –1 , and stream reaches impacted by WWTP had perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) PEC of 0.39 and 0.14 ng L –1 . For locations where measured-environmental concentrations (MEC) were determined, municipal and industrial WWTP contributed 7.8% (0 to 65%) of the total annual streamflow and MEC were greater than PEC in 99% of the samples, indicating additional potential PFAS sources. The mean ΣPFAS PEC was 9.1 ng L –1 compared to a mean sum of PFAS MEC of 34 ng L –1 . Under mean-August low-flow, 17% and 9.4% of the water-supply intakes had maximum PFOA and PFOS PEC exceeding drinking water maximum contaminant levels.

Maryland, Pennsylvania, Virginia, West Virginia↗

Using a time-of-travel sampling approach to quantify per- and polyfluoroalkyl substances (PFAS) stream loading and source inputs in a mixed-source, urban catchment

Understanding per- and polyfluoroalkyl substances (PFAS) mass distribution in surface and groundwater systems can support source prioritization, load reduction, and water management. Thirteen sites within an urban catchment were sampled utilizing a time-of-travel sampling approach to minimize the influence of subdaily fluctuations in mass from PFAS point sources and to quantify PFAS and ancillary chemical loads from various PFAS sources. A larger increase in perfluoroalkyl sulfonate (PFSA) loads (8 to 11 μg/s, up to 618%) than in perfluoroalkyl carboxylate (PFCA) loads (no change to 3.4 μg/s, up to 122%) was observed at sites below tributaries influenced by military bases with known groundwater discharge. Point discharges from two sewage treatment plants (STPs) resulted in increases in PFCA and PFSA loads that were similar (6 and 10 μg/s respectively) below the first STP and greater for PFCA compared to PFSA loads (23 and 13 μg/s respectively) below the second STP. Overall, percent increases in total PFAS load ranged from 20 to 277% for military base inputs and 44 to 77% for STP inputs. A focus catchment that represents only 14% (76.9 km 2 ) of the drainage area at the most downstream site (544 km 2 ) accounted for about 70% of PFSA and 40% of PFCA loads observed at the most downstream site. Results show that by using a time-of-travel sampling approach in mixed, urban settings with several PFAS sources, it is possible to quantify stream loads from individual PFAS sources, thereby improving source attribution and providing actionable data for water-resource managers.

ACS ES&T Water↗

Influence of irrigation water and soil on annual mercury dynamics in Sacramento Valley rice fields

Methylmercury (MeHg) is a human and environmental toxin produced in flooded soils. Little is known about MeHg in rice ( Oryza Sativa L.) fields in Sacramento Valley, California. The objectives of this study were to quantify mercury fractions in irrigation water and within rice fields and to determine their mercury pools in surface water, soil, and grain. Soil, grain, and surface water (dissolved and particulate) MeHg and total mercury (THg) were monitored in six commercial rice fields throughout a winter fallow season and subsequent growing season. Both dissolved and particulate mercury fractions were higher in fallow season rice field water. Total suspended solids and particulate mercury concentrations were positively correlated ( r = 0.99 and 0.98 for THg and MeHg, respectively), suggesting that soil MeHg was suspended in the water column and potentially exported. Dissolved THg and MeHg concentrations were positively correlated with absorbance at 254 nm ( r = 0.47 and 0.58, respectively) in fallow season field water. In the growing season, fields with higher irrigation water MeHg concentrations (due to recycled water use) had elevated field-water MeHg ( r = 0.86) and grain MeHg concentrations ( r = 0.96). Based on a mass balance analysis, soil mercury pools were orders of magnitude larger than surface water or grain mercury pools; however, fallow season drainage and grain harvest were the primary pathways for MeHg export. Based on these findings, reducing (1) discharge when water is turbid, (2) straw inputs, and (3) use of recycled irrigation water could help reduce mercury exports in rice field drainage water.

California↗

Temporal variability and sources of PFAS in the Rio Grande, New Mexico through an arid urban area using multiple tracers and high-frequency sampling

Per- and polyfluoroalkyl substances (PFAS) are ubiquitous in the environment but sources are not well defined for temporal and spatial aspects within an urban environment, and especially for an arid urban environment subject to seasonal short term high-intensity precipitation events. A focused diel sampling was conducted in the summer of 2021 to assess the temporal and spatial variability of PFAS in the Rio Grande near Albuquerque, New Mexico and showed an order of magnitude increase of PFAS as it flows through the Albuquerque urban area. Discrete samples were collected at two different locations on the Rio Grande in addition to wastewater treatment plant (WWTP) effluent that discharges directly to the Rio Grande between the sampling locations. Short-term high-intensity precipitation events occurred during the study period and mobilized PFAS from urban runoff. Dissolved organic matter composed of tryptophan-like organic substances and refined fuel and fuel byproducts, characteristic of an urban signature, were also related to the precipitation events. The PFAS in discharge from the WWTP was consistent over a 24-h period with slight differences in some compounds. Wastewater presence on the Rio Grande downstream of the WWTP was evidenced by a gadolinium anomaly as well as increases in several other trace elements, total dissolved nitrogen, and fluorescence indicators, in addition to PFAS. PFAS varied depending on source contribution, where urban runoff was associated with PFOA, PFOS, and PFBA, whereas PFHxA and PFPeA were associated with wastewater effluent. In addition, passive polar organic chemical integrative samplers (POCIS) using hydrophilic-lipid balance (HLB) sorption media were deployed for a month at two locations on the Rio Grande to assess longer term PFAS concentrations. The POCIS results show some compounds (PFPeA and PFHpA) were greater than the average concentration from discrete samples, whereas other compounds (PFHxA, PFOA, PFDA, and PFNA) were lower in the POCIS, and PFOS was very similar between the two. The POCIS did not detect PFBA, which may be related to the HLB media not performing well for short chain PFAS compounds. The results show promise for integrative samplers utilizing sorbent media. More detailed investigation of the spatial and temporal variability of water chemistry on the Rio Grande as it flows through Albuquerque could provide information applicable to urban areas worldwide.

New Mexico↗

Factors contributing to pesticide contamination in riverine systems: The role of wastewater and landscape sources

Wastewater treatment plant (WWTP) discharges can be a source of organic contaminants, including pesticides, to rivers. An integrated model was developed for the Potomac River watershed (PRW) to determine the amount of accumulated wastewater percentage of streamflow (ACCWW) and calculate predicted environmental concentrations (PECs) for 14 pesticides in non-tidal National Hydrography Dataset Plus Version 2.1 stream segments. Predicted environmental concentrations were compared to measured environmental concentrations (MECs) from 32 stream sites that represented a range of ACCWW and land use to evaluate model performance and to assess possible non-WWTP loading sources. Statistical agreement between PECs and MECs was strongest for insecticides, followed by fungicides and herbicides. Principal component analysis utilizing optical fluorescence and ancillary water quality data identified wastewater and urban runoff sources. Pesticides that indicated relatively larger sources from WWTPs included dinotefuran, fipronil, carbendazim, thiabendazole, and prometon whereas imidacloprid, azoxystrobin, propiconazole, tebuconazole, and diuron were more related to urban runoff. In addition, PECs generally comprised a low proportion of MECs, which indicates possible dominant loading sources beyond WWTP discharges. Cumulative potential toxicity was higher for sites with greater ACCWW and/or located in developed areas. Imidacloprid, fipronil, and carbendazim accounted for the largest portion of predicted potential toxicity across sites. The chronic aquatic life toxicity benchmarks for freshwater invertebrates were exceeded for 82 % of the imidacloprid detections ( n = 28) and 47 % of the fipronil detections ( n = 19). These results highlight the ecological implications of pesticide contamination from WWTP discharges and also the potential legacy effects from accumulated soil and groundwater sources. Pesticide management strategies that mitigate both current and historical impacts may improve the health of aquatic ecosystems.

Potomac River watershed↗

Field techniques for fluorescence measurements targeting dissolved organic matter, hydrocarbons, and wastewater in environmental waters: Principles and guidelines for instrument selection, operation and maintenance, quality assurance, and data reporting

The use of field deployable fluorescence sensors by the U.S. Geological Survey has become increasingly common for a wide variety of surface water and groundwater investigations. This report addresses field deployable fluorometers that measure the fluorescence response of various substances in water exposed to incident light generated by the sensor. An introduction to the basic principles of field measurements of fluorescence is provided, as well as technical background information on sensors that target dissolved organic matter, wastewater, and hydrocarbons, including sensor selection, operating principles, key features, and design elements. General deployment, operation and maintenance protocols, quality-assurance techniques, and suggestions for data reporting are presented to facilitate and standardize the collection and accurate communication of data collected by the U.S. Geological Survey across studies, sites, and sensor types. Sensor performance issues and common interferences are also described. An appendix is included to describe sensor calibration criteria and procedures, reporting units, and specific approaches to correct for interferences for fluorescence of dissolved organic matter sensors.

Techniques and Methods↗

Wetland management strategy to reduce mercury export in water and bioaccumulation in fish

Wetland environments provide numerous ecosystem services but also facilitate methylmercury (MeHg) production and bioaccumulation. We developed a wetland‐management technique to reduce MeHg concentrations in wetland fish and water. We physically modified seasonal wetlands by constructing open‐ and deep‐water treatment cells at the downstream end of seasonal wetlands to promote naturally occurring MeHg‐removal processes. We assessed the effectiveness of reducing mercury (Hg) concentrations in surface water and western mosquitofish that were caged at specific locations within 4 control and 4 treatment wetlands. Methylmercury concentrations in wetland water were successfully decreased within treatment cells during only the third year of study; however, treatment cells were not effective for reducing total Hg concentrations. Furthermore, treatment cells were not effective for reducing total Hg concentrations in wetland fish. Mercury concentrations in fish were not correlated with total Hg concentrations in filtered, particulate, or whole water; and the slope of the correlation with water MeHg concentrations differed between months. Fish total Hg concentrations were weakly correlated with water MeHg concentrations in April when fish were introduced into cages but were not correlated in May when fish were retrieved from cages. Fish total Hg concentrations were greater in treatment wetlands than in control wetlands the year after the treatment wetlands’ construction but declined by the second year. During the third year, fish total Hg concentrations increased in both control and treatment wetlands after an unexpected regional flooding event. Overall, we found limited support for the use of open‐ and deep‐water treatment cells at the downstream end of wetlands to reduce MeHg concentrations in water but not fish. We suggest that additional evaluation over a longer period of time is necessary.

Environmental Toxicology and Chemistry↗

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↗

Procedures for using the Horiba Scientific Aqualog ® fluorometer to measure absorbance and fluorescence from dissolved organic matter

Advances in spectroscopic techniques have led to an increase in the use of optical measurements (absorbance and fluorescence) to assess dissolved organic matter composition and infer sources and processing. Although optical measurements are easy to make, they can be affected by many variables rendering them less comparable, including by inconsistencies in sample collection (for example, filter pore size, preservation), the application of corrections for interferences (for example, inner-filtering corrections), differences in holding times, and instrument drift (for example, lamp intensity). A documented, standardized procedure to address these variables ensures that the optical (absorbance and fluorescence) measurements collected by U.S. Geological Survey researchers are useful and widely comparable. Rigorous and quantifiable quality assurance and quality control are essential for making these data comparable, particularly because there is no published guideline for the measurement of dissolved organic matter absorbance and fluorescence, and especially because there is no National Institute of Standards and Technology standard for dissolved organic matter. Validation and quality-control samples are analyzed on a monthly basis to determine laboratory and instrument precision and daily (that is, each day samples are run) to ensure repeatability. Data are not considered acceptable unless they meet laboratory criteria: All standards should be within 10 percent of the target value, laboratory replicates should be within 5 percent relative percent difference, and laboratory blanks (that is, laboratory reagent-grade water) should be less than one-tenth of the long-term method detection limit. Finally, for data to be useful, they must be accessible to users in a format that can be easily analyzed and interpreted. The Organic Matter Research Laboratory staff has developed a processing routine that extracts a subset of the data, which is made available to the public through the USGS National Water Quality Information System ( http://nwis.waterdata.usgs.gov/usa/nwis/qwdata ), and organizes the full datasets (that is, complete absorbance spectra and fluorescence excitation-emission matrices) in different forms that allow for these data to be analyzed using multi-parameter and multi-way statistical approaches.

Open-File Report↗

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↗

Alternate wetting and drying decreases methylmercury in flooded rice (Oryza sativa) systems

In flooded soils, including those found in rice ( Oryza sativa L.) fields, microbes convert inorganic Hg to more toxic methylmercury (MeHg). Methylmercury is accumulated in rice grain, potentially affecting health. Methylmercury in rice field surface water can bioaccumulate in wildlife. We evaluated how introducing aerobic periods into an otherwise continuously flooded rice growing season affects MeHg dynamics. Conventional continuously flooded (CF) rice field water management was compared with alternate wetting and drying, where irrigation was stopped twice during the growing season, allowing soil to dry to 35% volumetric moisture content, at which point plots were reflooded (AWD-35). Methylmercury studies began at harvest in Year 3 and throughout Year 4 of a 4-yr replicated field experiment. Bulk soil, water, and plant samples were analyzed for MeHg and total Hg (THg), and iron (Fe) speciation was measured in soil samples. Rice grain yield over 4 yr did not differ between treatments. Soil chemistry responded quickly to AWD-35 dry-downs, showing significant oxidation of Fe(II) accompanied by a significant reduction of MeHg concentration (76% reduction at harvest) compared with CF. Surface water MeHg decreased by 68 and 39% in the growing and fallow seasons, respectively, suggesting that the effects of AWD-35 management can last through to the fallow season. The AWD-35 treatment reduced rice grain MeHg and THg by 60 and 32%, respectively. These results suggest that the more aerobic conditions caused by AWD-35 limited the activity of Hg(II)-methylating microbes and may be an effective way to reduce MeHg concentrations in rice ecosystems.

Soil Science Society of America Journal↗

Methylmercury dynamics in Upper Sacramento Valley rice fields with low background soil mercury levels

Few studies have considered how methylmercury (MeHg, a toxic form of Hg produced in anaerobic soils) production in rice ( Oryza sativa L.) fields can affect water quality, and little is known about MeHg dynamics in rice fields. Surface water MeHg and total Hg (THg) imports, exports, and storage were studied in two commercial rice fields in the Sacramento Valley, California, where soil THg was low (25 and 57 ng g −1 ). The median concentration of MeHg in drainage water exiting the fields was 0.17 ng g −1 (range: <0.007–2.1 ng g −1 ). Compared with irrigation water, drainage water had similar MeHg concentrations, and lower THg concentrations during the growing season. Significantly elevated drainage water MeHg and THg concentrations were observed in the fallow season compared with the growing season. An analysis of surface water loads indicates that fields were net importers of both MeHg (76–110 ng m −2 ) and THg (1947–7224 ng m −2 ) during the growing season, and net exporters of MeHg (35–200 ng m −2 ) and THg (248–6496 ng m −2 ) during the fallow season. At harvest, 190 to 700 ng MeHg m −2 and 1400 to 1700 ng THg m −2 were removed from fields in rice grain. Rice straw, which contained 120 to 180 ng MeHg m −2 and 7000–10,500 ng m −2 THg was incorporated into the soil. These results indicate that efforts to reduce MeHg and THg exports in rice drainage water should focus on the fallow season. Substantial amounts of MeHg and THg were stored in plants, and these pools should be considered in future studies.

Journal of Environmental Quality↗

The contribution of rice agriculture to methylmercury in surface waters: A review of data from the Sacramento Valley, California

Methylmercury (MeHg) is a bioaccumulative pollutant produced in and exported from flooded soils, including those used for rice ( Oriza sativa L.) production. Using unfiltered aqueous MeHg data from MeHg monitoring programs in the Sacramento River watershed from 1996 to 2007, we assessed the MeHg contribution from rice systems to the Sacramento River. Using a mixed-effects regression analysis, we compared MeHg concentrations in agricultural drainage water from rice-dominated regions (AgDrain) to MeHg concentrations in the Sacramento and Feather Rivers, both upstream and downstream of AgDrain inputs. We also calculated MeHg loads from AgDrains and the Sacramento and Feather Rivers. Seasonally, MeHg concentrations were higher during November through May than during June through October, but the differences varied by location. Relative to upstream, November through May AgDrain least-squares mean MeHg concentration (0.18 ng L −1 , range 0.15–0.23 ng L −1 ) was 2.3-fold higher, while June through October AgDrain mean concentration (0.097 ng L −1 , range 0.6–1.6 ng L −1 ) was not significantly different from upstream. June through October AgDrain MeHg loads contributed 10.7 to 14.8% of the total Sacramento River MeHg load. Missing flow data prevented calculation of the percent contribution of AgDrains in November through May. At sites where calculation was possible, November through May loads made up 70 to 90% of the total annual load. Elevated flow and MeHg concentration in November through May both contribute to the majority of the AgDrain MeHg load occurring during this period. Methylmercury reduction efforts should target elevated November through May MeHg concentrations in AgDrains. However, our findings suggest that the contribution and environmental impact of rice is an order of magnitude lower than previous studies in the California Yolo Bypass.

California↗

Mercury in western North America: A synthesis of environmental contamination, fluxes, bioaccumulation, and risk to fish and wildlife

Western North America is a region defined by extreme gradients in geomorphology and climate, which support a diverse array of ecological communities and natural resources. The region also has extreme gradients in mercury (Hg) contamination due to a broad distribution of inorganic Hg sources. These diverse Hg sources and a varied landscape create a unique and complex mosaic of ecological risk from Hg impairment associated with differential methylmercury (MeHg) production and bioaccumulation. Understanding the landscape-scale variation in the magnitude and relative importance of processes associated with Hg transport, methylation, and MeHg bioaccumulation requires a multidisciplinary synthesis that transcends small-scale variability. The Western North America Mercury Synthesis compiled, analyzed, and interpreted spatial and temporal patterns and drivers of Hg and MeHg in air, soil, vegetation, sediments, fish, and wildlife across western North America. This collaboration evaluated the potential risk from Hg to fish, and wildlife health, human exposure, and examined resource management activities that influenced the risk of Hg contamination. This paper integrates the key information presented across the individual papers that comprise the synthesis. The compiled information indicates that Hg contamination is widespread, but heterogeneous, across western North America. The storage and transport of inorganic Hg across landscape gradients are largely regulated by climate and land-cover factors such as plant productivity and precipitation. Importantly, there was a striking lack of concordance between pools and sources of inorganic Hg, and MeHg in aquatic food webs. Additionally, water management had a widespread influence on MeHg bioaccumulation in aquatic ecosystems, whereas mining impacts where relatively localized. These results highlight the decoupling of inorganic Hg sources with MeHg production and bioaccumulation. Together the findings indicate that developing efforts to control MeHg production in the West may be particularly beneficial for reducing food web exposure instead of efforts to simply control inorganic Hg sources.

Science of the Total Environment↗