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Geochemistry of inorganic nitrogen in waters released from coal-bed natural gas production wells in the Powder River Basin, Wyoming

Water originating from coal-bed natural gas (CBNG) production wells typically contains ammonium and is often disposed via discharge to ephemeral channels. A study conducted in the Powder River Basin, Wyoming, documented downstream changes in CBNG water composition, emphasizing nitrogen-cycling processes and the fate of ammonium. Dissolved ammonium concentrations from 19 CBNG discharge points ranged from 95 to 527 μM. Within specific channels, ammonium concentrations decreased with transport distance, with subsequent increases in nitrite and nitrate concentrations. Removal efficiency, or uptake, of total dissolved inorganic nitrogen (DIN) varied between channel types. DIN uptake was greater in the gentle-sloped, vegetated channel as compared to the incised, steep, and sparsely vegetated channel and was highly correlated with diel patterns of incident light and dissolved oxygen concentration. In a larger main channel with multiple discharge inputs ( n = 13), DIN concentrations were >300 μM, with pH > 8.5, after 5 km of transport. Ammonium represented 25−30% of the large-channel DIN, and ammonium concentrations remained relatively constant with time, with only a weak diel pattern evident. In July 2003, the average daily large-channel DIN load was 23 kg N day −1 entering the Powder River, an amount which substantially increased the total Powder River DIN load after the channel confluence. These results suggest that CBNG discharge may be an important source of DIN to western watersheds, at least at certain times of the year, and that net oxidation and/or removal is dependent upon the extent of contact with sediment and biomass, type of drainage channel, and time of day.

Wyoming

Metolachlor and alachlor breakdown product formation patterns in aquatic field mesocosms

The transformation of metolachlor [2-chloro- N -(2-ethyl-6-methylphenyl)- N -(2-methoxy-1-methylethyl)acetamide] and alachlor [2-chloro- N -(2,6-diethylphenyl)- N -(methoxymethyl)acetamide] in aquatic systems was investigated using outdoor tank mesocosms. Metolachlor and alachlor levels and their ethane sulfonic acid (ESA) and oxanillic acid breakdown products were monitored over time under five experimental treatments (each in quadruplicate). Background water conditions were identical in all treatments with each treatment differing based on the level and type(s) of herbicide present. Treatments included a no-herbicide control, 10 μg/L metolachlor, 25 μg/L metolachlor, 25 μg/L alachlor, and 25 μg/L alachlor plus 25 μg/L metolachlor in combination. The experiment was initiated by adding herbicide(s) to the units to the target concentrations; herbicide and breakdown product levels and other chemical parameters were then monitored for 85 days. In general, metolachlor half-lives were longer than alachlor half-lives under all treatments, although the differences were not statistically significant. Metolachlor half-lives (±95% confidence limits) ranged from 33.0 d (±14.1 d) to 46.2 d (±40.0 d), whereas alachlor half-lives ranged from 18.7 d (±3.5 d) to 21.0 d (±6.5 d) for different treatments. Formation patterns of ESA were similar in all treatments, whereas oxanillic acid formation differed for the two herbicides. Alachlor oxanillic acid was produced in larger quantities than metolachlor oxanillic acid and either ESA under equivalent conditions. Our results suggest that the transformation pathways for alachlor and metolachlor in aquatic systems are similar and resemble the acetochlor pathway in soils proposed by Feng ( Pestic. Biochem. Physiol . 1991 , 34 , 136); however, the oxanillic acid branch of the pathway is favored for alachlor as compared with metolachlor.

Environmental Science & Technology

Centurial persistence of forever chemicals at military fire training sites

Drinking water contamination by per- and polyfluoroalkyl substances (PFAS) is widespread near more than 300 United States (U.S.) military bases that used aqueous film-forming foams (AFFF) for fire training and firefighting activities. Much of the PFAS at these sites consist of precursors that can transform into terminal compounds of known health concern but are omitted from standard analytical methods. Here, we estimate the expected duration and contribution of precursor biotransformation to groundwater PFAS contamination at an AFFF-contaminated military base on Cape Cod, Massachusetts, United States, by optimizing a geochemical box model using measured PFAS concentrations from a multidecadal time series of groundwater and a soil survey in the source zone. A toolbox of analytical techniques used to reconstruct the mass budget of PFAS showed that precursors accounted for 46 ± 8% of the extractable organofluorine (a proxy for total PFAS) across years. Terminal PFAS still exceed regulatory limits by 2000-fold decades after AFFF use ceased. Measurements and numerical modeling show that sulfonamido precursors are retained in the vadose zone and their slow biotransformation into perfluoroalkyl sulfonates (half-life > 66 yr) sustains groundwater concentrations of perfluorobutane sulfonate (PFBS) and perfluorohexane sulfonate (PFHxS). The estimated PFAS reservoir in the vadose zone and modeled flux into groundwater suggest PFAS contamination above regulatory guidelines will persist for centuries without remediation.

Massachusetts

The role of the Everglades Mangrove Ecotone Region (EMER) in regulating nutrient cycling and wetland productivity in South Florida

The authors summarize the main findings of the Florida Coastal Everglades Long-Term Ecological Research (FCE-LTER) program in the EMER, within the context of the Comprehensive Everglades Restoration Plan (CERP), to understand how regional processes, mediated by water flow, control population and ecosystem dynamics across the EMER landscape. Tree canopies with maximum height <3 m cover 49% of the EMER, particularly in the SE region. These scrub/dwarf mangroves are the result of a combination of low soil phosphorus (P < 59 μg P g dw −1 ) in the calcareous marl substrate and long hydroperiod. Phosphorus limits the EMER and its freshwater watersheds due to the lack of terrigenous sediment input and the phosphorus-limited nature of the freshwater Everglades. Reduced freshwater delivery over the past 50 years, combined with Everglades compartmentalization and a 10 cm rise in coastal sea level, has led to the landward transgression (∼1.5 km in 54 years) of the mangrove ecotone. Seasonal variation in freshwater input strongly controls the temporal variation of nitrogen and P exports (99%) from the Everglades to Florida Bay. Rapid changes in nutrient availability and vegetation distribution during the last 50 years show that future ecosystem restoration actions and land use decisions can exert a major influence, similar to sea level rise over the short term, on nutrient cycling and wetland productivity in the EMER.

Florida

Regional patterns in the isotopic composition of natural and anthropogenic nitrate in groundwater, High Plains, U.S.A.

Mobilization of natural nitrate (NO 3 - ) deposits in the subsoil by irrigation water in arid and semiarid regions has the potential to produce large groundwater NO 3 - concentrations. The use of isotopes to distinguish between natural and anthropogenic NO 3 - sources in these settings could be complicated by the wide range in δ 15 N values of natural NO 3 - . An ∼10 000 year record of paleorecharge from the regionally extensive High Plains aquifer indicates that δ 15 N values for NO 3 - derived from natural sources ranged from 1.3 to 12.3‰ and increased systematically from the northern to the southern High Plains. This collective range in δ 15 N values spans the range that might be interpreted as evidence for fertilizer and animal-waste sources of NO 3 - ; however, the δ 15 N values for NO 3 - in modern recharge ( less than 50 years) under irrigated fields were, for the most part, distinctly different from those of paleorecharge when viewed in the overall regional context. An inverse relation was observed between the δ 15 N[NO 3 - ] values and the NO 3 - /Cl - ratios in paleorecharge that is qualitatively consistent with fractionating losses of N increasing from north to south in the High Plains. N and O isotope data for NO 3 - are consistent with both NH 3 volatilization and denitrification, having contributed to fractionating losses of N prior to recharge. The relative importance of different isotope fractionating processes may be influenced by regional climate patterns as well as by local variation in soils, vegetation, topography, and moisture conditions.

Environmental Science & Technology

Contaminant exposure and transport from three potential reuse waters within a single watershed

Global demand for safe and sustainable water supplies necessitates a better understanding of contaminant exposures in potential reuse waters. In this study, we compared exposures and load contributions to surface water from the discharge of three reuse waters (wastewater effluent, urban stormwater, and agricultural runoff). Results document substantial and varying organic-chemical contribution to surface water from effluent discharges (e.g., disinfection byproducts [DBP], prescription pharmaceuticals, industrial/household chemicals), urban stormwater (e.g., polycyclic aromatic hydrocarbons, pesticides, nonprescription pharmaceuticals), and agricultural runoff (e.g., pesticides). Excluding DBPs, episodic storm-event organic concentrations and loads from urban stormwater were comparable to and often exceeded those of daily wastewater-effluent discharges. We also assessed if wastewater-effluent irrigation to corn resulted in measurable effects on organic-chemical concentrations in rain-induced agricultural runoff and harvested feedstock. Overall, the target-organic load of 491 g from wastewater-effluent irrigation to the study corn field during the 2019 growing season did not produce substantial dissolved organic-contaminant contributions in subsequent rain-induced runoff events. Out of the 140 detected organics in source wastewater-effluent irrigation, only imidacloprid and estrone had concentrations that resulted in observable differences between rain-induced agricultural runoff from the effluent-irrigated and nonirrigated corn fields. Analyses of pharmaceuticals and per-/polyfluoroalkyl substances in at-harvest corn-plant samples detected two prescription antibiotics, norfloxacin and ciprofloxacin, at concentrations of 36 and 70 ng/g, respectively, in effluent-irrigated corn-plant samples; no contaminants were detected in noneffluent irrigated corn-plant samples.

Oklahoma

Association of toxin-producing Clostridium botulinum with the macroalga Cladophora in the Great Lakes

Avian botulism, a paralytic disease of birds, often occurs on a yearly cycle and is increasingly becoming more common in the Great Lakes. Outbreaks are caused by bird ingestion of neurotoxins produced by Clostridium botulinum, a spore-forming, gram-positive, anaerobe. The nuisance, macrophytic, green alga Cladophora (Chlorophyta; mostly Cladophora glomerata L.) is a potential habitat for the growth of C. botulinum. A high incidence of botulism in shoreline birds at Sleeping Bear Dunes National Lakeshore (SLBE) in Lake Michigan coincides with increasingly massive accumulations of Cladophora in nearshore waters. In this study, free-floating algal mats were collected from SLBE and other shorelines of the Great Lakes between June and October 2011. The abundance of C. botulinum in algal mats was quantified and the type of botulism neurotoxin (bont) genes associated with this organism were determined by using most-probable-number PCR (MPN-PCR) and five distinct bont gene-specific primers (A, B, C, E, and F). The MPN-PCR results showed that 16 of 22 (73%) algal mats from the SLBE and 23 of 31(74%) algal mats from other shorelines of the Great Lakes contained the bont type E (bont/E) gene. C. botulinum was present up to 15 000 MPN per gram dried algae based on gene copies of bont/E. In addition, genes for bont/A and bont/B, which are commonly associated with human diseases, were detected in a few algal samples. Moreover, C. botulinum was present as vegetative cells rather than as dormant spores in Cladophora mats. Mouse toxin assays done using supernatants from enrichment of Cladophora containing high densities of C. botulinum (>1000 MPN/g dried algae) showed that Cladophora-borne C. botulinum were toxin-producing species (BoNT/E). Our results indicate that Cladophora provides a habitat for C. botulinum, warranting additional studies to better understand the relationship between this bacterium and the alga, and how this interaction potentially contributes to botulism outbreaks in birds.

Great Lakes

Sorption of selected organic compounds from water to a peat soil and its humic-acid and humin fractions: Potential sources of the sorption nonlinearity

The sorption isotherms of ethylene dibromide (EDB), diuron (DUN), and 3,5-dichlorophenol (DCP) from water on the humic acid and humin fractions of a peat soil and on the humic-acid of a muck soil have been measured. The data were compared with those of the solutes with the whole peat from which the humic-acid (HA) and humin (HM) fractions were derived and on which the sorption of the solutes exhibited varying extents of nonlinear capacities at low relative concentrations (C(e)/S(w)). The HA fraction as prepared by the density-fractionated method is relatively pure and presumably free of high- surface-area carbonaceous material (HSACM) that is considered to be responsible for the observed nonlinear sorption for nonpolar solutes (e.g., EDB) on the peat; conversely, the base-insoluble HM fraction as prepared is presumed to be enriched with HSACM, as manifested by the greatly higher BET- (N2) surface area than that of the whole peat. The sorption of EDB on HA exhibits no visible nonlinear effect, whereas the sorption on HM shows an enhanced nonlinearity over that on the whole peat. The sorption of polar DUN and DCP on HA and HM display nonlinear effects comparable with those on the whole peat; the effects are much more significant than those with nonpolar EDB. These results conform to the hypothesis that adsorption onto a small amount of strongly adsorbing HSACM is largely responsible for the nonlinear sorption of nonpolar solutes on soils and that additional specific interactions with the active groups of soil organic matter are responsible for the generally higher nonlinear sorption of the polar solutes.

Environmental Science & Technology

Trophodynamics of per- and polyfluoroalkyl substances in the food web of a large Atlantic slope river

Per- and polyfluoroalkyl substances (PFASs) have attracted scientific and regulatory attention due to their persistence, bioaccumulative potential, toxicity, and global distribution. We determined the accumulation and trophic transfer of 14 PFASs (5 short-chain and 9 long-chain) within the food web of the Yadkin-Pee Dee River of North Carolina and South Carolina, US. Food web components and pathways were determined by stable isotope analyses of producers, consumers, and organic matter. Analyses of water, sediment, organic matter, and aquatic biota revealed that PFASs were prevalent in all food web compartments. Biofilm, an aggregation of bacteria, fungi, algae, and protozoans and a basal resource for the aquatic food web, showed high PFAS accumulation (in 10 of 14 compounds), particularly for perfluorooctanoic acid, with the greatest mean concentration of 463.73 ng/g. The food web compartment with the most detections and greatest concentrations of PFASs was aquatic insects; all 14 PFASs were detected in individual aquatic insect samples (range of <limit of detection [<LOD] to 1670.10 ng/g of wet weight [WW]). These findings may suggest a trophic link between biofilm PFASs and aquatic insect PFASs. Individual fish tissue samples ranged from <LOD to 797.00 ng/g of WW, where perfluorooctanesulfonate (PFOS) was the dominant PFAS among all samples (64%). The ova of an imperiled fish, the robust redhorse ( Moxostoma robustum ), had concentrations of 10 PFASs (range of <LOD to 482.88 ng/g of WW) and the highest PFOS concentration (482.88 ng/g of WW), indicating a likely maternal transfer. The trophic magnification factors (TMFs) calculated in this study showed that various taxa accumulated PFAS compounds differently. PFBS, a short-chain PFAS compound that would presumably exhibit lesser TMFs, had nine values among our compartments and organisms >1.0 (range of 0.57 to 2.33); it is possible that an unmeasured PFBS precursor may be accumulating in biota and metabolizing to PFBS, leading to a higher than expected TMFs for this compound. Our findings demonstrate the prevalence of PFASs in a freshwater food web with potential implications for ecological and human health.

North Carolina, South Carolina

Expanded target-chemical analysis reveals extensive mixed-organic-contaminant exposure in USA streams

Surface water from 38 streams nationwide was assessed using 14 target-organic methods (719 compounds). Designed-bioactive anthropogenic contaminants (biocides, pharmaceuticals) comprised 57% of 406 organics detected at least once. The 10 most-frequently detected anthropogenic-organics included eight pesticides (desulfinylfipronil, AMPA, chlorpyrifos, dieldrin, metolachlor, atrazine, CIAT, glyphosate) and two pharmaceuticals (caffeine, metformin) with detection frequencies ranging 66–84% of all sites. Detected contaminant concentrations varied from less than 1 ng L –1 to greater than 10 μg L –1 , with 77 and 278 having median detected concentrations greater than 100 ng L –1 and 10 ng L –1 , respectively. Cumulative detections and concentrations ranged 4–161 compounds (median 70) and 8.5–102 847 ng L –1 , respectively, and correlated significantly with wastewater discharge, watershed development, and toxic release inventory metrics. Log 10 concentrations of widely monitored HHCB, triclosan, and carbamazepine explained 71–82% of the variability in the total number of compounds detected (linear regression; p -values: < 0.001–0.012), providing a statistical inference tool for unmonitored contaminants. Due to multiple modes of action, high bioactivity, biorecalcitrance, and direct environment application (pesticides), designed-bioactive organics (median 41 per site at μg L –1 cumulative concentrations) in developed watersheds present aquatic health concerns, given their acknowledged potential for sublethal effects to sensitive species and lifecycle stages at low ng L –1 .

Environmental Science & Technology

Characterization and copper binding of humic and nonhumic organic matter isolated from the South Platte River: Evidence for the presence of nitrogenous binding site

Humic substances typically constitute 40−60% of the dissolved organic matter (DOM) in surface waters. However, little information is available regarding the metal binding properties of the nonhumic hydrophilic portion of the DOM. In this study, humic and nonhumic DOM samples were isolated from the South Platte River (Colorado, DOC = 2.6 mg·L - 1 , SUVA 254 = 2.4 L/mg·m) using a two-column array of XAD-8 and XAD-4 resins. The three major isolated fractions of DOM, which accounted for 57% of the bulk DOM, were characterized using a variety of analytical tools. Proton and copper binding properties were studied for each fraction. The main objective of this work was to compare the structural and chemical characteristics of the isolated fractions and test models describing DOM reactivity toward metal ions. The characterization work showed significant structural differences between the three isolated fractions of DOM. The hydrophobic acid fraction (i.e., humic substances isolated from the XAD-8 resin) gave the largest C/H, C/O, and C/N ratios and aromatic carbon content among the three isolated fractions. The transphilic acid (TPHA) fraction (“transphilic” meaning fraction of intermediate polarity isolated from the XAD-4 resin) was found to incorporate the highest proportion of polysaccharides, whereas the transphilic neutral (TPHN) fraction was almost entirely proteinaceous. The gradual increase of the charge with pH for the three DOM fractions is most likely caused by a large distribution of proton affinity constants for the carboxylic groups, as well as a second type of group more generally considered to be phenolic. In the case of the DOM fraction enriched in proteinaceous material (i.e., TPHN fraction), the results showed that the amino groups are responsible for the charge reversal. For low copper concentrations, nitrogen-containing functional groups similar to those of amino acids are likely to be involved in complexation, in agreement with previously published data.

Colorado

Use case development for earth monitoring, analysis, and prediction (EarthMAP)—A road map for future integrated predictive science at the U.S. Geological Survey

Executive Summary The U.S. Geological Survey (USGS) 21st-century science strategy 2020–30 promotes a bureau-wide strategy to develop and deliver an integrated, predictive science capability that works at the scales and timelines needed to inform societally relevant resource management and protection and public safety and environmental health decisions (U.S. Geological Survey, 2021). This is the overarching goal of the USGS Earth Monitoring, Analysis, and Prediction (EarthMAP) vision, which consists of three components: (1) integrated data and information, (2) integrated predictive science, and (3) actionable information—all designed and delivered to respond to user needs. To launch this vision and help shape the design and implementation of integrated predictive science, the USGS Regional Offices each developed a set of use cases (hereafter Use Cases)—short descriptions of potential science applications that could clearly address high priority decision-making needs of our stakeholders and that align with an integrated science focus. Use Cases are not actionable science planning documents, nor stand-alone scholarly works, but should be considered as innovative, next-generation science ideas that can be considered as potential components of science plans still under development. The goal of Use Case development was to (1) identify and characterize existing USGS scientific capacities and expertise that can support science goals and products, (2) identify opportunities to leverage current capacities for next-generation science, and (3) foster engagement across the entire Bureau to further refine the USGS strategy for EarthMAP and integrated predictive science. The Use Case development effort documented in this report was coordinated by the Use Case Development Team (UCDT), consisting of representatives from each region. The UCDT undertook five tasks: (1) develop a unified approach to engage bureau scientists consistently across all regions in aspirational thinking about what can be accomplished; (2) work with the regions and their Science Centers to generate an initial set of Use Cases, authored directly by scientists; (3) characterize, summarize, and document the initial set of Use Case submissions from authors to illuminate bureau-level demand for integrated science; (4) compare existing and needed capacities from the Use Case descriptions with preliminary results of the EarthMAP Capacity Assessment (Keisman and others, 2021); and (5) describe lessons learned from the Use Case development process and provide recommendations to inform future efforts to generate integrated science activities. This report outlines the approach the UCDT developed to solicit Use Cases from the regions and summarizes the high-level qualitative findings from this first-round effort. The UCDT received 36 Use Cases from the regions and identified potential points of convergence and commonalities considered useful in making connections among the participating scientists. The Southwest (SW) Region and the Rocky Mountain (RM) Region asked scientists to give special consideration to Use Cases with applicability to the Colorado River Basin, and seven of the Use Cases specifically named that geographic area as a focus. Coastal hazards and coastal resilience were identified in Use Cases from the Alaska (AK), Northeast (NE), and Southeast (SE) Regions. Aspects of wildfire and post-wildfire response were part of Uses Cases from AK, RM, and SW Regions. The greatest convergence of Use Case themes was related to conservation of public lands and waters, which is a powerful linkage lending strength to future collaborative efforts. The most common type of stakeholder decisions that would be informed by the Use Case science applications were related to adaptation, mitigation, and response (for example, how to increase the resilience of coastal communities to climate-related stressors and how to prevent or respond to harmful algal blooms). Other common types of decisions included water and land management decisions (including operational water management decisions such as reservoir operations and land use planning in the sagebrush biome), decisions about how to manage and conserve habitats and species, and risk management decisions (such as managing the post-wildfire flood risks). These decision types are not exclusive because many Use Cases cross categories. Use Case authors identified existing and needed science and technology capabilities required for Use Case implementation, which were then aligned to capabilities assessed in the EarthMAP Capacity Assessment (Keisman and others, 2021). Strong alignment was found for data and information integration approaches, modeling and prediction approaches, and capabilities related to delivery of actionable information. A majority of Use Cases indicated insufficient current capacity for needed data collection methods, data integration, and modeling and prediction approaches, whereas only 25 percent indicated insufficient capacity for actionable information delivery. Overall, many Use Case capacity demand gaps could potentially be met by existing bureau-wide capacity. In addition, nearly half of the Use Cases could potentially be implemented within 3 years if funding, capabilities, and personnel impediments were removed and science priorities were realigned. Several challenges emerged during the Use Case development process. The first challenge was developing an approach that was flexible enough to accommodate regional differences in planning and implementation, while also ensuring enough guidance to promote meaningful summary analyses. The UCDT encountered a strong demand for continuous communication and education to improve overall understanding of the integrated predictive science strategy. Another challenge was managing expectations about EarthMAP activities as a design effort that was not aligned to an immediate funding opportunity. Connecting the Use Cases to stakeholder needs without the opportunity for direct stakeholder engagement was also challenging. The last notable challenge was in obtaining consistent interpretation and characterization of the qualitative data housed in the narrative descriptions of Use Cases, written in different styles. Overall, the 36 Use Cases can serve as components of a road map for advancing integrated monitoring and predictive science throughout the USGS by revealing opportunities to (1) encourage cross-region initiatives that address shared interests in common themes by integrating similar Use Cases and through direct involvement of stakeholders in identifying needs and designing effective responses, (2) leverage the Use Cases to target investments that are aligned with the Bureau and Department of the Interior (DOI) priorities, (3) connect Use Cases and the results of the companion EarthMAP Capacity Assessment (Keisman and others, 2021) to identify potential priorities for capacity building investments, and (4) raise awareness of common integrated and interdisciplinary science interests within and across the regions through Use Case and Capacity Assessment summary outreach activities.

Open-File Report

Fishway Entrance Palisade

This technical report summarizes the work that was conducted by the University of Massachusetts Amherst and the United States Geological Survey (USGS), along with other project partners, on the Fishway Entrance Palisade (EP), a projected funded through the Department of Energy’s (DOE) funding opportunity titled ‘Innovative Solutions for Fish Passage at Hydropower Dams’ (DE‐FOA‐0001662). The period of performance ranged from September 1, 2018 through September 30, 2021. The EP is a novel fish passage engineering technology designed to provide more favorable entry conditions for fish and to reduce costs relative to conventional fishway auxiliary water systems (AWS). The EP project has four primary components. First, the Northeast United States Auxiliary Water Systems Database was created (Northeast Fishway Auxiliary Water Systems Database Section). The database, developed with material provided by the U.S. Fish and Wildlife Service, contains information on fishway type (e.g., lift, Denil, pool and weir) and Auxiliary Water System (AWS) details (e.g., water conveyance method, diffuser type) for 60 hydroelectric sites in the region. Findings indicate that nearly 4 out of every 10 fishway in the region is a fish lift and approximately 1 out of every 4 is a Denil ladder. The remainder are a mix of vertical slot fishways, pool and weirs, and Ice Harbor fishways. Furthermore, over half of all AWS systems use floor diffusers to discharge the auxiliary (or attraction) water into the entrance of a fishway, whereas only 14% use wall diffusers. Second, limited experiments on a conventional AWS with live, actively migrating fish were conducted at the USGS Easter Ecological Science Center (EESC) S.O. Conte Research Laboratory (Conventional Auxiliary Water System Experiments Section). This study determined how water velocity through a wall diffuser, without turning vanes or timber baffles to distribute the flow, affects the behavior and passage of adult American shad, a conservative surrogate species for migratory fish on the East Coast. Two gross diffuser velocity treatments were examined, 0.5 ft/s and 1.0 ft/s. These wall diffuser velocities represented current (0.5 ft/s) and past (1.0 ft/s) design criteria guidelines set forth by the USFWS North Atlantic-Appalachian Region (Rojas 2020; USFWS 2019). Six trials with a total of 151 American Shad were conducted in June of 2019 for the two treatments. No differences in American shad passage efficiency were discovered between the two treatments, while approximately 3 in every 4 attempts were successful at passing the diffuser. While these results may appear to indicate that the generally accepted gross wall diffuser velocity criteria for American shad of 0.5 ft/s could be safely increased to 1.0 ft/s, further analysis is warranted. Furthermore, it is unknown how other migratory and resident fish species that traverse these structures would be impacted by such a change. Studying the wall diffuser hydraulics led to an important AWS observation. Without turning vanes or timber baffles in this study, doubling the diffuser area was insufficient at producing the type of flow field change one may expect by halving the gross diffuser velocity. Instead, the flow fields throughout each treatments study area were similar, which led to similar results in shad performance. This not only highlights the importance of installing flow guidance devices like turning vanes, but also to the importance of properly maintaining them, which can be costly. Third, more expansive experiments on the novel EP were conducted in the spring of 2019 and 2021 (Fishway Entrance Palisade Experiments). The goal of this study was to determine how adult American shad responded to a variety of conditions at a full-scale EP. A total of six treatments were examined by changing the average auxiliary channel velocity between 1.0 and 5.0 ft/s in intervals of 1.0 ft/s and by inserting/removing an entrance gate at the opening of the fishway. Thirty trials with a total of 1,273 shad were conducted over the two years. In all treatments, at least ~7 out of every 10 fish successfully passed the EP diffuser and swam into the entrance channel within the 3.5-hour long trial, highlighting the general effectiveness of the novel AWS technology. In both study years, lower velocities through the EP diffuser led to increased shad performance, though performance peaked for the 2 ft/s velocity treatment. This treatment condition represents an approximate six-fold increase in gross diffuser velocity relative to conventional auxiliary water systems, which in turn presents opportunities for cost savings (e.g., reduction in diffuser size). Shad performance, in general, was worse in 2019 than in 2021, potentially due to the different run timing when our trials were conducted (2019 trials occurred near the end of the migration season, unlike in 2021). Treatments in 2019 had approximately a 20% reduction in entrance efficiency by the trial end, including a 16.7% drop for the 3 ft/s velocity treatment in 2019 relative to 2021 (the only carryover treatment between years). Lastly, adding an entrance gate caused a significant delay to entry. The time to 25% entry raised ~20 minutes from the near instantaneous 25% entry that was reported for the other treatments conducted in the same year (2021). Though by the end of the 3.5-hour trial, the overall entrance efficiency nearly matched those of the other 2021 treatments. The fourth and final component of the EP project was an economic analysis that focused on the cost of attraction and environmental flows (Modeling Power Generation Losses Due to Environmental and Fish Passage Attraction Flows at a Run-Of-River Hydroelectric Operation in the Northeast). The study assessed the economic impact of meeting environmental flow requirements at a representative hydroelectric facility and fish lift in the Northeast. An initial finding of the study was that there is a paucity of published data on the costs of meeting attraction and environmental flows. This is due, in part, to the proprietary nature of this data. To explore the costs associated with these flows, three types of environmental flows were assessed: upstream fishway attraction flows, downstream fishway attraction flows, and habitat maintenance minimum flows. A physics-based model was developed and calibrated with three years of hourly generation and flow data as inputs. Gage flow inputs were adjusted and used to calculate power generated. To address hydrologic variability, the model was executed to simulate 30 years of historical flows. Results indicate that both interannual and seasonal climatic factors impact the costs of meeting environmental flow requirements. Generation potential is most strongly curtailed during dry years in terms of maximizing the capacity factor (the percent of time a plant generates at capacity). Dry years, and especially dry summers, have the most significant costs associated with mitigation flows. Of the three types of flows, habitat flows are most costly in terms of power production, followed by upstream attraction flows. Downstream attraction flows are least costly. This finding is the likely result of differences in both flow rates and duration of the seasonal requirement for each flow. Overall, environmental flows represented a 2-12% loss in annual generation, but losses during a dry summer can reach over 20%.

Final Technical Report

Perchlorate in pleistocene and holocene groundwater in North-Central New Mexico

Groundwater from remote parts of the Middle Rio Grande Basin in north-central New Mexico has perchlorate (ClO 4 - ) concentrations of 0.12−1.8 μg/L. Because the water samples are mostly preanthropogenic in age (0−28 000 years) and there are no industrial sources in the study area, a natural source of the ClO 4 - is likely. Most of the samples have Br - , Cl - , and SO 4 2 - concentrations that are similar to those of modern bulk atmospheric deposition with evapotranspiration (ET) factors of about 7−40. Most of the ET values for Pleistocene recharge were nearly twice that for Holocene recharge. The NO 3 - /Cl - and ClO 4 - /Cl - ratios are more variable than those of Br - /Cl - or SO 4 2 - /Cl - . Samples thought to have recharged under the most arid conditions in the Holocene have relatively high NO 3 - /Cl - ratios and low δ 15 N values (+1 per mil (‰)) similar to those of modern bulk atmospheric N deposition. The δ 18 O values of the NO 3 - (−4 to 0 ‰) indicate that atmospheric NO 3 - was not transmitted directly to the groundwater but may have been cycled in the soils before infiltrating. Samples with nearly atmospheric NO 3 - /Cl - ratios have relatively high ClO 4 - concentrations (1.0−1.8 μg/L) with a nearly constant ClO 4 - /Cl - mole ratio of (1.4 ± 0.1) × 10 - 4 , which would be consistent with an average ClO 4 - concentration of 0.093 ± 0.005 μg/L in bulk atmospheric deposition during the late Holocene in north-central NM. Samples thought to have recharged under wetter conditions have higher δ 15 N values (+3 to +8 ‰), lower NO 3 - /Cl - ratios, and lower ClO 4 - /Cl - ratios than the ones most likely to preserve an atmospheric signal. Processes in the soils that may have depleted atmospherically derived NO 3 - also may have depleted ClO 4 - to varying degrees prior to recharge. If these interpretations are correct, then ClO 4 - concentrations of atmospheric origin as high as 4 μg/L are possible in preanthropogenic groundwater in parts of the Southwest where ET approaches a factor of 40. Higher ClO 4 - concentrations in uncontaminated groundwater could occur in recharge beneath arid areas where ET is greater than 40, where long-term accumulations of atmospheric salts are leached suddenly from dry soils, or where other (nonatmospheric) natural sources of ClO 4 - exist.

Environmental Science & Technology

Effects of dissolved carbonate on arsenate adsorption and surface speciation at the hematite-water interface

Effects of dissolved carbonate on arsenate [As(V)] reactivity and surface speciation at the hematite−water interface were studied as a function of pH and two different partial pressures of carbon dioxide gas [ P CO 2 = 10 - 3.5 atm and ∼0; CO 2 -free argon (Ar)] using adsorption kinetics, pseudo-equilibrium adsorption/titration experiments, extended X-ray absorption fine structure spectroscopic (EXAFS) analyses, and surface complexation modeling. Different adsorbed carbonate concentrations, due to the two different atmospheric systems, resulted in an enhanced and/or suppressed extent of As(V) adsorption. As(V) adsorption kinetics [4 g L - 1 , [As(V)] 0 = 1.5 mM and I = 0.01 M NaCl] showed carbonate-enhanced As(V) uptake in the air-equilibrated systems at pH 4 and 6 and at pH 8 after 3 h of reaction. Suppressed As(V) adsorption was observed in the air-equilibrated system in the early stages of the reaction at pH 8. In the pseudo-equilibrium adsorption experiments [1 g L - 1 , [As(V)] 0 = 0.5 mM and I = 0.01 M NaCl], in which each pH value was held constant by a pH-stat apparatus, effects of dissolved carbonate on As(V) uptake were almost negligible at equilibrium, but titrant (0.1 M HCl) consumption was greater in the air-equilibrated systems ( P CO 2 = 10 - 3.5 atm) than in the CO 2 -free argon system at pH 4−7.75. The EXAFS analyses indicated that As(V) tetrahedral molecules were coordinated on iron octahedral via bidentate mononuclear (≈2.8 Å) and bidentate binuclear (≈3.3 Å) bonding at pH 4.5−8 and loading levels of 0.46−3.10 μM m - 2 . Using the results of the pseudo-equilibrium adsorption data and the XAS analyses, the pH-dependent As(V) adsorption under the P CO 2 = 10 - 3.5 atm and the CO 2 -free argon system was modeled using surface complexation modeling, and the results are consistent with the formation of nonprotonated bidentate surface species at the hematite surfaces. The results also suggest that the acid titrant consumption was strongly affected by changes to electrical double-layer potentials caused by the adsorption of carbonate in the air-equilibrated system. Overall results suggest that the effects of dissolved carbonate on As(V) adsorption were influenced by the reaction conditions [e.g., available surface sites, initial As(V) concentrations, and reaction times]. Quantifying the effects of adsorbed carbonate may be important in predicting As(V) transport processes in groundwater, where iron oxide-coated aquifer materials are exposed to seasonally fluctuating partial pressures of CO 2 (g).

Environmental Science & Technology

Sources and characteristics of organic matter in the Clackamas River, Oregon, related to the formation of disinfection by-products in treated drinking water

This study characterized the amount and quality of organic matter in the Clackamas River, Oregon, to gain an understanding of sources that contribute to the formation of chlorinated and brominated disinfection by-products (DBPs), focusing on regulated DBPs in treated drinking water from two direct-filtration treatment plants that together serve approximately 100,000 customers. The central hypothesis guiding this study was that natural organic matter leaching out of the forested watershed, in-stream growth of benthic algae, and phytoplankton blooms in the reservoirs contribute different and varying proportions of organic carbon to the river. Differences in the amount and composition of carbon derived from each source affects the types and concentrations of DBP precursors entering the treatment plants and, as a result, yield varying DBP concentrations and species in finished water. The two classes of DBPs analyzed in this study-trihalomethanes (THMs) and haloacetic acids (HAAs)-form from precursors within the dissolved and particulate pools of organic matter present in source water. The five principal objectives of the study were to (1) describe the seasonal quantity and character of organic matter in the Clackamas River; (2) relate the amount and composition of organic matter to the formation of DBPs; (3) evaluate sources of DBP precursors in the watershed; (4) assess the use of optical measurements, including in-situ fluorescence, for estimating dissolved organic carbon (DOC) concentrations and DBP formation; and (5) assess the removal of DBP precursors during treatment by conducting treatability "jar-test" experiments at one of the treatment plants. Data collection consisted of (1) monthly sampling of source and finished water at two drinking-water treatment plants; (2) event-based sampling in the mainstem, tributaries, and North Fork Reservoir; and (3) in-situ continuous monitoring of fluorescent dissolved organic matter (FDOM), turbidity, chlorophyll- a , and other constituents to continuously track source-water conditions in near real-time. Treatability tests were conducted during the four event-based surveys to determine the effectiveness of coagulant and powdered activated carbon (PAC) on the removal of DBP precursors. Sample analyses included DOC, total particulate carbon (TPC), total and dissolved nutrients, absorbance and fluorescence spectroscopy, and, for regulated DBPs, concentrations of THMs and HAAs in finished water and laboratory-based THM and HAA formation potentials (THMFP and HAAFP, respectively) for source water and selected locations throughout the watershed. The results of this study may not be typical given the record and near record amounts of precipitation that occurred during spring that produced streamflow much higher than average in 2010-11. Although there were algal blooms, lower concentrations of chlorophyll- a were observed in the water column during the study period compared to historical data. Concentrations of DBPs in finished (treated) water averaged 0.024 milligrams per liter (mg/L) for THMs and 0.022 mg/L for HAAs; maximum values were about 0.040 mg/L for both classes of DBPs. Although DBP concentrations were somewhat higher within the distribution system, none of the samples collected for this study or for the quarterly compliance monitoring by the water utilities exceeded levels permissible under existing U.S. Environmental Protection Agency (USEPA) regulations: 0.080 mg/L for THMs and 0.060 mg/L for HAAs. DOC concentrations were generally low in the Clackamas River, typically about 1.0-1.5 mg/L. Concentrations in the mainstem occasionally increased to nearly 2.5 mg/L during storms; DOC concentrations in tributaries were sometimes much higher (up to 7.8 mg/L). The continuous in-situ FDOM measurements indicated sharp rises in DOC concentrations in the mainstem following rainfall events; concentrations were relatively stable during summer base flow. Even though the first autumn storm mobilized appreciable quantities of carbon, higher concentrations of DBPs in finished water were observed 3-weeks later, after the ground was saturated from additional rainfall. The majority of the DOC in the lower Clackamas River appears to originate from the upper basin, suggesting terrestrial carbon was commonly the dominant source. Lower-basin tributaries typically contained the highest concentrations of DOC and DBP precursors and contributed substantially to the overall loads in the mainstem during storms. During low-flow periods, tributaries were not major sources of DOC or DBP precursors to the Clackamas River. Although the dissolved fraction of organic carbon contributed the majority of DBP precursors, at times the particulate fraction (inorganic sediment and organic particles including detritus and algal material) contributed a substantial fraction of DBP precursors. Considering just the main-stem sites, on average, 10 percent of THMFP and 32 percent of HAAFP were attributed to particulate carbon. This finding suggests water-treatment methods that remove particles prior to chlorination would reduce finished-water DBP concentrations to some degree. Overall, concentrations of THM and HAA precursors were closely linked to DOC concentrations; laboratory DBP formation potentials (DBPFPs) clearly showed that THMFP and HAAFP were greatest in the downstream tributaries that contained elevated carbon concentrations. However, carbon-normalized "specific" formation potentials for THMs and HAAs (STHMFP and SHAAFP, respectively) revealed changes in carbon character over time that affected the two types of DBP classes differently. HAA precursors were elevated in waters containing aromatic-rich soil-derived material arising from forested areas. In contrast, THM precursors were associated with carbon having a lower aromatic content; highest STHMFP occurred in autumn 2011 in the mainstem from North Fork Reservoir downstream to LO DWTP. This pattern suggests the potential for a link between THM precursors and algal-derived carbon. The highest STHMFP value was measured within North Fork Reservoir, indicating reservoir derived carbon may be important for this class of DBPs. Weak correlations between STHMFP and SHAAFP emphasize that precursor sources for these types of DBPs may be different. This highlights not only that different locations within the watershed produce carbon with different reactivity (specific DBPFP), but also that different management approaches for each class of DBP precursors could be required for control. Treatability tests conducted on source water during four basin-wide surveys demonstrated that an average of about 40 percent of DOC can be removed by coagulation. While the decrease in THMFP following coagulation was similar to DOC, the decrease in HAAFP was much greater (approximately 70 percent), indicating coagulation is particularly effective at removing HAA precursors'likely because of the aromatic nature of the carbon associated with HAA precursors. Several findings from this study have direct implications for managing drinking-water resources and for providing useful information that may help improve treatment-plant operations. For example, the use of in-situ fluorometers that measure FDOM provided an excellent proxy for DOC concentration in this system and revealed short-term, rapid changes in DOC concentration during storm events. In addition, the strong correlation between FDOM values measured in-situ and HAA5 concentrations in finished water may permit estimation of continuous HAA concentrations, as was done here. As part of this study, multiple in-situ FDOM sensors were deployed continuously and in real-time to characterize the composition of dissolved organic matter. Although the initial results were promising, additional research and engineering developments will be needed to demonstrate the full utility of these sensors for this purpose. In conclusion, although DBPFPs were strongly correlated to DOC concentration, some DBPs formed from particulate carbon, including terrestrial leaf material and algal material such as planktonic species of blue-green algae and sloughed filaments, stalks, and cells of benthic algae. Different precursor sources in the watershed were evident from the data, suggesting specific actions may be available to address some of these sources. In-situ measurements of FDOM proved to be an excellent proxy for DOC concentration as well as HAA formation during treatment, which suggests further development and refinement of these sensors have the potential to provide real-time information about complex watershed processes to operators at the drinking-water treatment plants. Follow-up studies could examine the relative roles that terrestrial and algal sources have on the DBP precursor pool to better understand how watershed-management activities may be affecting the transport of these compounds to Clackamas River drinking-water intakes. Given the low concentrations of algae in the water column during this study, additional surveys during more typical river conditions could provide a more complete understanding of how algae contribute DBP precursors. Further development of FDOM-sensor technology can improve our understanding of carbon dynamics in the river and how concentrations may be trending over time. This study was conducted in collaboration with Clackamas River Water and the City of Lake Oswego water utilities. Other research partners included Oregon Health and Science University in Hillsboro, Oregon, Alexin Laboratory in Tigard, Oregon, U.S. Geological Survey National Research Program Laboratory in Denver, Colorado, and the U.S. Geological Survey Water Science Centers in Portland, Oregon, and Sacramento, California. This project was supported with funding from Clackamas River Water, City of Lake Oswego, the U.S. Geological Survey, and the Water Research Foundation.

Oregon

Capacity assessment for Earth Monitoring, Analysis, and Prediction (EarthMAP) and future integrated monitoring and predictive science at the U.S. Geological Survey

Executive Summary Managers of our Nation’s resources face unprecedented challenges driven by the convergence of increasing, competing societal demands and a changing climate that affects the stability, vulnerability, and predictability of those resources. To help meet these challenges, the scientific community must take advantage of all available technologies, data, and integrative Earth systems modeling capacity to better inform resource and risk management decisions. This is the overarching goal of the U.S. Geological Survey (USGS) Earth Monitoring, Analysis, and Prediction (EarthMAP) vision: “By 2030, the USGS will deliver well integrated observations and predictions of the future state of natural systems—water, ecosystems, energy, minerals, hazards—at regional and national scales, working primarily with federal, state, and academic partners to develop and operate the capability” (U.S. Geological Survey, 2021). Providing more integrated Earth systems science and actionable information to decision makers, stakeholders, and the public requires a better understanding of the depth and distribution of existing capacity (capabilities, tools, and techniques) across the Bureau. Identifying existing capacity is also a critical first step toward gap analysis and targeted investments to increase capacity over time. The USGS formed a Capacity Assessment Team (CAT) and charged it with (1) conducting a Request for Information (RFI) to identify existing USGS expertise and activities supportive of integrated and predictive science to inform decision making, (2) developing a strategy and proof-of-concept for a continuously updated capacity assessment capability, and (3) identifying lessons learned to inform development of best practices for future capacity assessment efforts. The RFI took the form of a survey, with content guided by the science and technology needs identified in a USGS report titled “Grand Challenges for Integrated U.S. Geological Survey Science—A Workshop Report” (Jenni and others, 2017). The 44-question survey provided respondents the ability to rate their level of experience with a suite of priority disciplines, analysis and modeling approaches, technologies, and stakeholder engagement strategies and to enter optional narrative text for supporting context. An introductory portion focused on general science capacity assessment, followed by three sections targeting capabilities related to the foundational components of EarthMAP: (1) data and information integration, (2) integrated predictive science, and (3) actionable information. The survey results provided a high-level snapshot of USGS capacity in the targeted areas. Respondents (1,035 individuals) represented approximately 13 percent of the USGS across all mission areas and regions. Seventy-four percent of the respondents held a science-focused position title and the remainder had position titles in information technology, computer science, management, administrative, or other (contractors, volunteers, emeritus, and unknown). To provide greater insight into respondent capabilities and activities, information from the U.S. Department of the Interior and USGS enterprise information systems were used to further characterize topical expertise and organizational associations of survey respondents. To address the ongoing need to assess the Bureau’s capacity to address integrated predictive science priorities, the CAT developed a software-based proof-of-concept called the Integrated Science Assessment Information Database (iSAID) for assembling various information sources together toward making the full extent of USGS capabilities and scientific assets available for routine capacity assessment. This proof-of-concept is intended to serve as a catalyst for further development. The process of implementing the EarthMAP capacity assessment survey, analyzing survey responses, and developing the proof-of-concept resulted in lessons learned, findings, and recommendations. Example scenarios throughout the report demonstrate how capacity assessment data can inform science planning. Three overarching findings and recommendations are: (1) Finding: Capacity is limited in some critical disciplines, skills, and technology applications, but “sufficient” depends on the question and the need relative to availability at a given point in time. Recommendation: Develop an on-demand capacity assessment framework that enables rapid identification and evaluation of existing and available expertise to support decision needs as they arise. (2) Finding: Institutional barriers and lack of awareness constrain the ability of USGS staff to adopt new technologies, collaborate across administrative boundaries, and deliver actionable information to stakeholders in a timely manner. However, these barriers are not universally experienced. Recommendation: Pursue more targeted inquiries to clarify which institutional barriers are obstructing the adoption of new technologies and approaches or the sharing of expertise and equipment across organizational and regional boundaries. These inquiries should inform USGS leadership, mission areas, and regions whether policies can be revised or whether a lack of understanding is creating perceived obstacles. Highlight cases when staff have successfully adopted new technologies and approaches to advance EarthMAP priorities and provide actionable information in a timely manner to spread awareness of how perceived obstacles can be navigated and overcome when appropriate. (3) Finding: Examples of people and projects integrating across disciplines and scales and applying advanced approaches to meet complex stakeholder needs exist. Such examples provide transfer value across the spectrum from approach to decision making. Many projects, already underway, appear to meet elements of the EarthMAP vision, and the USGS has people who can provide leadership in multiple types of specific integrated science efforts. Recommendation: Use these findings as a starting point for near-term strategic planning for integrated science. Highlight, incentivize, and build on existing interdisciplinary predictive science and information delivery activities across the USGS to advance toward further realization of an EarthMAP capacity. The CAT efforts to develop and assess existing USGS capacity to advance the EarthMAP vision revealed a fundamental challenge for not only this effort but any effort to assess existing capacity: A considerable amount of thought, time, and effort is required to survey and assess capabilities and tools available to support a given need, yet best results are still likely to provide an incomplete assessment. To better meet the frequent need to assess capabilities, tools, products, and projects that address an expressed strategic priority, the CAT proposes the concept of an on-demand capacity assessment framework supported by a software package that dynamically pulls and integrates information from existing USGS information systems and public domain registries. Although existing USGS enterprise information systems currently lack the structure, cross-system consistency, interoperability, and stability to support a continuously updated capacity assessment capability, we identify reasonable near-term steps to improve the utility of information gathered on expertise and project capacity and to improve the consistency and completeness of information and the ability of USGS systems to share that information. The ability to search and characterize this information will make future assessments of capacity faster, more complete, more efficient, and more targeted. This approach would grow the Bureau’s capacity knowledge over time, iteratively improving the ability to access, leverage, and synthesize existing capabilities and assets as well as identify and fill critical gaps. The greatest promise for developing integrated science could lie in linking across existing projects and expertise to create a multi-project capacity for addressing large, complex environmental issues.

Open-File Report