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Iodine-129 in the eastern Snake River Plain aquifer at and near the Idaho National Laboratory, Idaho, 2021–22

Between the 1950s and 1980s, wastewater generated at the Idaho National Laboratory contained Iodine-129 ( 129 I); this wastewater was discharged directly into the eastern Snake River Plain (ESRP) aquifer through a deep disposal well, unlined infiltration ponds, or leaked from distribution systems below industrial facilities. During 2021–22, the U.S. Geological Survey, in cooperation with the U.S. Department of Energy and the Idaho Department of Environmental Quality Idaho National Laboratory Oversight Program, collected groundwater samples from 64 monitoring wells in the ESRP aquifer, 6 of which are part of a multilevel monitoring system, to determine the concentration of 129 I in the groundwater. These samples were analyzed by accelerator mass spectrometry as part of a long-term ongoing study to track trends and occurrences of this carcinogenic, long-lived radionuclide in the environment. Concentrations ranged from slightly above the locally determined background concentration of 5.4×10 −6 picocuries per liter, to just below the U.S. Environmental Protection Agency’s maximum contaminant level of 1 picocurie per liter. Discharge of wastewater containing 129 I has been discontinued to the aquifer, and long-term trends from a subset (n=15) of sampled wells show decreasing 129 I concentrations over the last three decades. Concentrations of 129 I in groundwater from monitoring wells near facilities at the Idaho National Laboratory are affected by episodic recharge from an ephemeral surface-water source and by the fracture-flow dominated hydrologic regime in the ESRP aquifer. The spatially focused sampling effort has also identified a low-level 129 I plume that affects long-term water quality near and downgradient from the Advanced Test Reactor Complex in the southwestern part of the facility that had not been clearly defined in previous sampling efforts, although the definition of the plume is somewhat limited by available data.

Idaho

Enhanced hydrologic monitoring and characterization of groundwater drainage features

Groundwater drains to the land surface, generating the baseflow of streams, lakes, and wetlands. The hydrologic resilience of baseflow during prolonged dry periods and after disturbance can be assessed with evolving remote sensing analysis paired with localized monitoring of groundwater drainage features and creative model calibration strategies.

Nature Water

Evaluating mass flow meter measurements from chambers for greenhouse gas emissions from orphan wells and other point sources

This study evaluates the performance of a rigid gas flux chamber equipped with a mass flow meter (MFM) for measuring gas emissions from leaking orphan wells and similar pressure-driven gas point sources. We conducted a series of laboratory and field experiments to evaluate the sensitivity, stability, and dynamic range of an MFM chamber system and found an optimal method for sealing the chamber to the ground to isolate the emission source. From these results, we estimate the effects of different soil gas permeabilities on measurements and identify the uncertainty of environmental processes that can impact measurements. Simulations of an MFM chamber are compared to those of a dynamic flux chamber to contrast the data derived with both methodologies and illustrate the potential for measuring high variability leaks with the MFM chamber. Using a low flow resistance MFM and a chamber well-sealed to the ground, it is possible to measure leaks down to 1.08 x 10 -3 cubic meters per hour (m 3 h −1 ) (refenced to 25°/1 atm), corresponding to 0.77 grams per hour (g h −1 ) methane or 2.11 g h −1 carbon dioxide, with a mean uncertainty of 0.89 % relative standard deviation. Environmental processes such as heated gas inside the chamber from solar gain, wind blowing across the chamber vent, and changing humidity in the chamber, can cause variation in MFM measurements. Over 11 d of continuous monitoring under varying weather conditions, the standard deviation of the environmentally sourced signals was found to be 7.40 x 10 -3 m 3 h −1 (equivalent to or 5.27 g h −1 methane or 14.45 g h −1 carbon dioxide). Strategies to obtain the highest quality data from MFM chambers include burying the edges of the chamber below the surface sufficiently deep to seal the chamber edges against gas flow and soaking the dirt with water to lower the chances of escaping gases, while monitoring the gas flow and adjusting the chamber seal to achieve a maximum flow rate.

Atmospheric Measurement Techniques

The Long Island Sound and Watershed Metadata map application

The Long Island Sound and its watershed encompass an area of about 17,000 square miles and include the Connecticut, Housatonic, and Thames Rivers, which all drain to the sound. Dozens of organizations from government agencies, nonprofits, and Tribal Nations have developed projects and monitoring programs to analyze and protect the water resources of the watershed and sound. The abundance of data and lack of an existing searchable index require a centralized metadata repository to allow users to find water resources data more efficiently. The U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency and the Long Island Sound Study, has created an interactive map application to visualize and search for metadata information across organizations working to monitor and protect the Long Island Sound.

Connecticut, Massachusetts, New Hampshire, New Yor

Borehole geophysical time-series logging to monitor passive ISCO treatment of residual chlorinated-ethenes in a confining bed, NAS Pensacola, Florida

In-situ chemical oxidation (ISCO) is a common method to remediate chlorinated ethene contaminants in groundwater. Monitoring the effectiveness of ISCO can be hindered because of insufficient observations to assess oxidant delivery. Advantageously, potassium permanganate, one type of oxidant, provides the opportunity to use its strong electrical signal as a surrogate to track oxidant delivery using time-series borehole geophysical methods, like electromagnetic (EM) induction logging. Here we report a passive ISCO (P-ISCO) experiment, using potassium permanganate cylinders emplaced in boreholes, at a chlorinated ethene contamination site, Naval Air Station Pensacola, Florida. The contaminants are found primarily at the base of a shallow sandy aquifer in contact with an underlying silty-clay confining bed. We used results of the time-series borehole logging collected between 2017 and 2022 in 4 monitoring wells to track oxidant delivery. The EM-induction logs from the monitoring wells showed an increase in EM response primarily along the contact, likely from pooling of the oxidant, during P-ISCO treatment in 2021. Interestingly, concurrent natural gamma-ray (NGR) logging showed a decrease in NGR response at 3 of the 4 wells possibly from the formation of manganese precipitates coating sediments. The coupling of time-series logging and well-chemistry data allowed for an improved assessment of passive ISCO treatment effectiveness.

Florida

Decadal shifts in groundwater age detected by environmental tracers across California, USA

Groundwater age offers important insight into recharge, storage, and contamination risk. Although models predict age changes can be driven by pumping and climate variability, direct observational evidence remains limited. Here, we analyzed paired environmental tracer suites (tritium, carbon-14, and tritiogenic helium-3) collected a decade apart from 268 wells across California to assess the prevalence of groundwater age transience. Travel-time distribution models and statistical tests indicated age transience at 29% of sites, occurring most often in agricultural regions, such as the San Joaquin Valley and Southern Coast Ranges, where large carbon-14 changes coincided with substantial nitrate and chloride shifts. Sites with tritiogenic helium-3 data showed more frequent age transience, underscoring the value of multi-tracer data sets. These results provide the first regional evidence of widespread groundwater age change and a method for detecting changing water balances with implications for groundwater sustainability and water quality.

California

Metal-rich lacustrine sediments from legacy mining perpetuate copper exposure to aquatic-riparian food webs

Historic copper mining left a legacy of metal-rich tailings resulting in ecological impacts along and within Torch Lake, an area of concern in the Keweenaw Peninsula, Michigan, USA. Given the toxicity of copper to invertebrates, this study assessed the influence of this legacy on present day nearshore aquatic and terrestrial ecosystems. We measured the metal (Co, Cu, Ni, Zn, Cd) and metalloid (As) concentrations in sediment, pore water, surface water, larval and adult insects, and two riparian spider taxa collected from Torch Lake and a nearby reference lake. Overall, elevated metal and metalloid concentrations, particularly Cu, were measured in all sediment samples and some surface and pore water samples collected from Torch Lake. For instance, Cu concentrations in the Torch Lake sediment were ∼200% higher than the reference lake and all measured concentrations exceeded predicted effects concentrations by at least ninefold. Within larval insect tissues, we observed 160% higher Cu concentrations than measured in the reference lake, and Cu was the only measured element above predicted effects concentrations in Torch Lake. Adult insects collected at both lakes had similar metal concentrations irrespective of exposure levels. Yet we found 100% higher copper concentrations in Torch Lake riparian spiders, demonstrating elevated exposure risk to insectivores across the aquatic-terrestrial boundary. Our results highlight that other metals in the mixture may not be as concerning to adjacent riparian ecosystems, but copper remains a contaminant of concern in Torch Lake 60 years after mining ceased.

Michigan

Fiber-optic distributed temperature sensing of hydrologic processes—Diverse deployments and new applications by the U.S. Geological Survey

Fiber-optic distributed temperature sensing instruments harness the temperature-dependent properties of glass to measure temperature continuously along optical fibers by using precise pulses of laser light. In the mid-2000s, this technology was refined for environmental monitoring purposes such as snowpack-air exchange, groundwater/surface-water exchange, and lake-water stratification. Fiber-optic distributed temperature sensing has revealed unprecedented details about preferential flow processes; however, the method is labor intensive and requires specific training, resulting in limited use by the broader water community. With the ongoing national implementation of the U.S. Geological Survey Next Generation Water Observing System, there has been renewed interest in harnessing the unique spatiotemporal monitoring capabilities of fiber-optic distributed temperature sensing. This fact sheet briefly describes this technology, highlights uses by the U.S. Geological Survey, and discusses current applications and future opportunities.

Fact Sheet

Forecast, monitor, adapt: A multi-agency strategy to protect people from postfire debris flows

In 2020, a wildfire burned across Glenwood Canyon in Colorado, USA. A history of postfire debris flows in the region and a hazard assessment for the burn area indicated that potentially life-threatening debris flows could be triggered by rainfall within months of a wildfire. As a result, four government agencies evaluated strategies to help mitigate hazards, including the loss of human life, that may be associated with debris-flow events. After the fire, 26 large debris flows occurred in the summer of 2021 and three sediment-laden flows occurred in the summer of 2023, but there were no major injuries or fatalities reported. We found that integrating hazard assessment/ forecasting, monitoring, and adaptation scenarios was a successful strategy for reducing postfire debris-flow risks to human life (including injuries and fatalities). Weather forecasts and estimates of debris-flow triggering rainfall thresholds, likelihood, and volume were used to anticipate the timing, location, and magnitude of debris-flow events. Rainfall monitoring and detailed recordkeeping of storms that triggered debris flows were used to validate and update debris-flow warning thresholds that varied with time following the wildfire. Although the governmental agencies working in this burn area had distinct and differing agency mandates, they were able to integrate information to reduce the risk of debris-flow events to human life.

Colorado

Investigation of drivers and sources of potential harmful algal blooms in Lake Anna, Virginia, 2023-24

Algal blooms in freshwater reservoirs are an increasing concern because of the risk to aquatic ecosystem health, recreational use, and water quality. Among the taxa that comprise an algal bloom, cyanobacteria are of particular concern due to the potential to produce toxic compounds which can cause acute and chronic illness in humans if ingested through contaminated water or shellfish. When toxins are above a toxin-specific threshold in the water column, the Commonwealth of Virginia categorizes the bloom as a harmful algal bloom (HAB), distinguishing it from an algal bloom without toxins present. Toxins are of particular concern in bodies of water which serve as major recreational areas, such as Lake Anna in central Virginia. Lake Anna is a 27 km-long and 47 km2 reservoir in central Virginia. Since the Commonwealth of Virginia revised the HAB monitoring framework in 2018, algal bloom advisories for potentially toxigenic blooms have been issued in the western, riverine zone of the reservoir. There were detections of microcystin and anatoxin production but no detections of cylindrospermopsin and saxitoxin production in Lake Anna; however, toxin concentrations were low, at values less than 0.65 µg/L. In 2023, the U.S. Geological Survey, in cooperation with Virginia Department of Environmental Quality, initiated a 19-month intensive and extensive study of western Lake Anna and its tributaries (North Anna River and Pamunkey Creek) to (1) characterize the algal community, biomass, and toxin production; (2) identify potential drivers leading to algal bloom initiation, persistence, and decline; and (3) assess the primary sources of the drivers contributing to algal blooms. Continuous and discrete monitoring of water quality within the lake, watershed inputs, meteorological conditions, and algal communities were monitored. Multiple modeling scenarios identified that the formation and persistence of algal blooms in Lake Anna are driven by interactions among chemical, macro- and micronutrient, and physical factors. Key drivers include total nitrogen, total phosphorus, water temperature, suspended sediment concentration, wind speed, copper, iron, molybdenum, nickel, sodium, and alkalinity. During this study, winter stormflow events delivered the highest loading of macro- and micronutrients from the tributaries to the lake. The lake is a sink for these nutrients in the water column or in the lake-bed sediments. During high-occupancy and recreation periods on the lake in the summer months, boating activity can promote internal loading by the resuspension of the lake-bed sediments, thereby increasing the nutrient availability for algal uptake. Thermal stratification and hypoxic conditions were observed, which can contribute to the passive release of nutrients into the water column, further facilitating algal bloom proliferation. These processes may create a positive feedback loop that supports the formation, persistence, and annual recurrence of algal blooms in the western region of Lake Anna. Continued water-quality monitoring of early warning indicators may improve the detection and forecasting of algal growth in the lake and help managers proactively manage water quality and algal growth.

EarthArXiv

Decadal trends and occurrence of geogenic constituents and mixtures in groundwater across the continental United States

Worldwide, about 50% of the population is served by groundwater-sourced drinking water. Numerous groundwater quality assessments have found that geogenic constituents are among the most common contaminants in drinking-water aquifers. Documenting changing groundwater quality is a crucial aspect of water availability assessments. We assess trends and occurrence of geogenic constituent concentrations in groundwater across the continental United States using 3 decades of data from the U.S. Geological Survey’s National Water Quality Network. Thousands of groundwater wells were grouped into agricultural, urban, or domestic supply network types. Although most networks and constituents had no statistically significant change in concentration, many had increasing concentration trends, elevated concentrations, or both. Lithium, sodium, radium, sulfate, and uranium had increasing trends in more than 10% of the study networks. Urban and domestic well networks had increasing lithium and sodium trends more often than agricultural networks. Manganese most commonly increased in domestic well networks; uranium more commonly increased in agricultural and urban networks. Elevated concentration mixtures were widespread, and mixture complexities appeared to increase over time. Our results indicate that more than 2.3 million domestic-well users may be affected by elevated concentrations of one or more geogenic constituents.

continental United States

3D semantic mapping of surface geological features

Semantic mapping in 3D is fundamental to a wide range of geoscientific studies and applications, including geomorphology, hazard assessment, and environmental monitoring. However, automatically segmenting geological features from large-scale photogrammetric datasets remains a significant challenge. We present a methodology to address this gap. Using overlapping images collected over environments of interest, Structure-from-Motion (SfM) produces georeferenced point clouds and estimates camera poses. Existing large vision models, such as Segment Anything Model, segment objects in the images, generating pixel-segmentation associations. To produce pixel-point associations, we project the points back onto the camera image planes. As objects are independently segmented across multiple images with different perspectives, we develop a segmentation mosaicking algorithm to build probabilistic point-segmentation associations that combines the pixel-segmentation associations and pixel-point associations. Our methodology is validated using both synthetic data generated by Kubric and real-world UAV-SfM data. The implementation is designed to be compatible with existing SfM software, including Agisoft and OpenDroneMap, for photogrammetry mapping in geoscience studies. As a case study, we apply our method to the semantic mapping of precariously balanced rocks (PBRs), which provide upper-bound constraints on historical ground motion shaking intensity. To support object-level identification of PBRs, we additionally integrated Grounding DINO, enabling text-prompted segmentation of features of interest within UAV imagery. This case study demonstrates the effectiveness of our method in generating a 3D semantic map of PBRs, enabling spatial distribution of PBR fragility for earthquake hazard analysis.

Computers & Geosciences

Evaluation of daily stream temperature predictions (1979-2021) across the contiguous United States using a spatiotemporal aware machine learning algorithm

Stream temperature controls a variety of physical and biological processes that affect ecosystems, human health, and economic activities. We used 42 years (1979–2021) of data to predict daily summary statistics of stream temperature across >50,000 stream reaches in the contiguous United States using a recurrent graph convolution network. We comprehensively documented the performance – both across all reaches and by stream type (e.g., reservoir or groundwater influence) – as a baseline for future improvement. The model showed reach-level RMSE of <2 °C with 90 % prediction intervals that contain 90.7 % of observations. We also assessed how the model captured variability in ecologically relevant metrics (e.g., R 2 for annual 7-day maximum = 0.76; R 2 for days exceeding 25 °C = 0.75). This model does not outperform state-of-the-art machine learning efforts (e.g., RMSE ≤1.5 °C) due to a limited input set but does provide the most spatially complete modeling to date to support water availability assessments.

contiguous United States

Substrate Enhancement Pilot Project—Monitoring summary and evaluation, Kootenai River, Idaho, 2012–22

To assess changes in substrate conditions and the efficacy of artificially placed substrates at select sites on the Kootenai River near Bonners Ferry, Idaho, the U.S. Geological Survey, in cooperation with the Kootenai Tribe of Idaho, completed repeat bathymetric, velocimetric, and underwater videography surveys. Collectively, three project sites throughout the Kootenai River make up the Substrate Enhancement Pilot Project (SEPP), an effort intended to improve spawning and egg incubation viability at locations identified to be aquatic habitat limited for the endangered Kootenai River white sturgeon (Acipenser transmontanus). Following the placement of coarse substrates at each site, bathymetric, velocimetric, and underwater videography data were collected from 2012 to 2022 to assess the role of deposition and erosion on maintaining suitable white sturgeon spawning and incubation substrates. Minimal erosion and deposition occurred at all Substrate Enhancement Pilot Project sites, according to interannual and intra-annual net volumetric changes between bathymetric surveys. Depending on the timing of bathymetric surveys relative to the annual peak streamflow conditions, isolated locations of deposition or erosion were observed at each site and the potential for deposition or erosion was supported by measured mean depth-averaged velocities. This study concluded that variability of deposition and scour were common at each site throughout the monitoring period and may be attributed to fluctuations in streamflow. Repeat bathymetric, underwater videography, and velocity mapping surveys were used to verify the interstitial spaces and surfaces of substrates at each SEPP site remained free of fine sediments for intervals longer than a year but were susceptible to deposition between high streamflow events.

Idaho

Characterization of the hydrogeologic framework, groundwater-flow system, geochemistry, and aquifer hydraulic properties of the shallow groundwater system in the Wilcox and Lorraine process areas of the Wilcox Oil Company Superfund site near Bristow, Oklahoma, 2022

The Wilcox Oil Company Superfund site (hereinafter referred to as “the site”) was formerly an oil refinery northeast of Bristow in Creek County, Oklahoma. Historical refinery operations contaminated the soil, surface water, streambed sediments, alluvium, and groundwater with refined and stored products at the site. The Wilcox and Lorraine process areas are where the highest concentrations of volatile organic compounds, semivolatile organic compounds, polycyclic aromatic hydrocarbons, and trace elements (including metals) (collectively hereinafter referred to as “contaminants”) were measured in a local shallow perched groundwater system within the alluvium (hereinafter referred to as the “alluvial aquifer”) at the site during previous site assessments. In order to understand the potential migration of contaminants through the soil and groundwater in these areas, the U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency, investigated aquifer characteristics of the alluvial aquifer in the Wilcox and Lorraine process areas of the site to (1) document hydraulic conductivity and other aquifer characteristics of the alluvial aquifer that govern contaminant fate and transport, (2) describe the geospatial extent and concentration of the contaminants in the alluvial aquifer in the Wilcox and Lorraine process areas, and (3) describe the geochemical controls pertaining to oxidation and reduction governing the fate and transport and the degradation potential of contaminants in the groundwater. Various data were compiled and collected to evaluate the aquifer characteristics at the site including the hydrogeologic framework, groundwater-flow system, geochemistry, and hydraulic properties of the aquifer. A total of 20 new (2022) groundwater monitoring wells were installed at the site to collect data used to supplement groundwater-level altitude and groundwater-quality data collected from older, existing groundwater monitoring wells and piezometers. Data compiled and collected for the study were used to evaluate the characteristics of the alluvial aquifer at the site. These aquifer characteristics are defined by the hydrogeologic framework, groundwater-flow system, geochemistry, and hydraulic properties of the aquifer.

Oklahoma

Seismic techniques and suggested instrumentation to monitor volcanoes

Introduction Changes in the pressure or location of magma can stress or break surrounding rocks and trigger flow of nearby waters and gases, causing seismic signals, such as discrete earthquakes and tremor. These phenomena are types of seismic unrest that commonly precede eruption and can be used to forecast volcanic activity. Mass movements at the surface, including avalanches, debris flows, and lahars, may also generate seismic signals that are specifically addressed in chapter H , this volume (Thelen and others, 2024). Our focus in this chapter is to determine the levels of instrumentation recommended to produce high-quality, well-constrained seismic observations important for early warning of impending eruptions, detecting changes in ongoing eruptions, and characterizing other hazardous volcanic events. There are emerging techniques and new types of instrumentation, such as distributed acoustic sensing or rotational seismometers, that we do not consider here. These types of instrumentation show promise for monitoring but still require maturation before being considered more generally in volcano monitoring. Most of the capabilities mentioned below are universal for all types of volcanic systems, although some are best applied to stratovolcanoes with an apical single vent. In some settings, such as calderas or shield volcanoes, we must broaden coverage to include multiple possible storage regions or vent locations. As an example, Thelen (2014) discretized the long rift zones of shield volcanoes in Hawaiʻi as a set of evenly spaced “vents.” In this construct, each vent comes with recommendations, and several thousand network configurations were simulated to assess the effect on network quality levels and to determine the most efficient network design. The same process could be applied in a caldera setting or a volcanic field, where an evenly spaced grid of potential vents is considered. Localized recommendations for each unique system are beyond the scope of this report and left up to local experts to assess based on the conditions, restrictions, and requirements of each volcano.

Scientific Investigations Report

Environmental setting and water-quality issues in the lower Tennessee River basin

The goals of the National Water-Quality Assessment Program are to describe current water-quality conditions for a large part of the Nation's water resources, identify water-quality changes over time, and identify the primary natural and human factors that affect water quality. The lower Tennessee River Basin is one of 59 river basins selected for study. The water-quality assessment of the lower Tennessee River Basin study unit began in 1997. The lower Tennessee River Basin study unit encompasses an area of about 19,500 square miles and extends from Chattanooga, Tennessee, to Paducah, Kentucky. The study unit had a population of about 1.5 million people in 1995. The study unit was subdivided into subunits with relatively homogeneous geology and physiography. Subdivision of the study unit creates a framework to assess the effects of natural and cultural settings on water quality. Nine subunits were delineated in the study unit; their boundaries generally coincide with level III and level IV ecoregion boundaries. The nine subunits are the Coastal Plain, Transition, Western Highland Rim, Outer Nashville Basin, Inner Nashville Basin, Eastern Highland Rim, Plateau Escarpment and Valleys, Cumberland Plateau, and Valley and Ridge.The lower Tennessee River Basin consists of predominantly forest (51 percent) and agricultural land (40 percent). Activities related to agricultural land use, therefore, are the primary cultural factors likely to have a widespread effect on surface- and ground-water quality in the study unit. Inputs of total nitrogen and phosphorus from agricultural activities in 1992 were about 161,000 and 37,900 tons, respectively. About 3.7 million pounds (active ingredient) of pesticides was applied to crops in the lower Tennessee River Basin in 1992. State water-quality agencies identified nutrient enrichment and pathogens as water-quality issues affecting both surface and ground water in the lower Tennessee River Basin. Water-quality data collected by State and Federal agencies between 1980 and 1996 were summarized to characterize surface- and ground-water quality of the subunits with respect to these issues. Median concentrations of nitrogen species generally were less than 1 milligram per liter in surface and ground water in all subunits, and were highest throughout the subunits that had the largest percentages of agricultural land use. Median phosphorus concentrations also were less than 1 milligram per liter in all subunits. Phosphatic limestones present in two subunits had a larger effect on phosphorus concentrations in surface and ground water than did the amount of agricultural land use in these subunits. Median counts of fecal coliform were higher in surface water than in ground water in all subunits. The highest median counts in surface water were in the Valley and Ridge (7,500 colonies per 100 milliliters) and the Outer Nashville Basin subunits (5,000 colonies per 100 milliliters). Highest median counts in ground water were in the Inner and Outer Nashville Basin subunit. Natural setting likely has an important effect with respect to fecal contamination of surface and ground water in the lower Tennessee River Basin.

Alabama, Georgia, Kentucky, Mississippi, Tennessee

Critical review of mercury methylation and methylmercury demethylation rate constants in aquatic sediments for biogeochemical modeling

Mercury is a toxin that causes neurological impairments in adults, is particularly harmful for fetuses and children, and is deadly in severe cases, making it a worldwide health concern. Methylmercury (MeHg) is the environmentally relevant form of mercury (Hg) because it biomagnifies along the food chain. Methylmercury is mainly produced in aquatic sediments via methylation of inorganic Hg (Hg(II)) and transformed back via demethylation. Because transformation rates determine MeHg concentrations, quantification of methylation and demethylation rates is needed to inform management of MeHg. Published rate constants for Hg(II) methylation ( 𝑘 𝑚 ) and MeHg demethylation ( 𝑘 𝑑 ) vary greatly, stemming partly from differences in experimental methods. We conducted a comprehensive review of rate laws, evaluated published rate constants, and performed biogeochemical simulations to assess variability in reported 𝑘 𝑚 and 𝑘 𝑑 . Based on selected studies employing the same pseudo-first-order rate law and similar experimental methods, we found that 𝑘 𝑚 = 0.04 ± 0.03 d −1 is a reasonable range for wetland sediments. Over a number of environments, maximum 𝑘 𝑑 was smaller at sites without Hg source ( 𝑘 𝑑 = 0.5 d −1 ) than at sites with identified Hg source ( 𝑘 𝑑 = 1.8 d −1 ). Larger variability and higher uncertainty in 𝑘 𝑑 compared to 𝑘 𝑚 highlight the need for more research on MeHg demethylation rates. This critical review: (a) aids the design of future experimental studies of 𝑘 𝑚 and 𝑘 𝑑 ; (b) provides guidance for comparing rate constants from different studies; (c) presents a biogeochemical reaction model to assess rate constants; and (d) informs selection of 𝑘 𝑚 and 𝑘 𝑑 values from the literature for use in model simulations.

Critical Reviews in Environmental Science and Tech