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Cascadia Margin cold seeps: Subduction zone fluids, gas hydrates, and chemosynthetic habitats

Priority Geographic Area: The outer continental shelf and upper continental slope from Canada/U.S. border offshore Washington State to the Mendocino Fracture Zone (Northern California), entirely within the U.S. Exclusive Economic Zone (EEZ), from the outermost shelf to at least 2000 m water depth (Figure 1). Description of Priority Area: Since 2015, over a thousand water column gas plumes originating at seafloor gas seeps have been discovered landward of the Cascadia deformation front (e.g., Embley et al., 2016; Johnson et al., 2015, 2019; Merle and Embley, 2016; NA-95 Cruise Report, 2018; Riedel et al., 2018), adding to those that had long been known on Hydrate Ridge (e.g., Heeschen et al., 2003; Tréhu et al., 2004). The recently-discovered seeps stretch from offshore Vancouver Island to the Mendocino Fracture Zone and from the outer shelf to ~2000 m water depth, occurring both landward and seaward of the nominal limit for gas hydrate stability zone on the upper continental slope (Figure 1). Hundreds of seeps likely remain undiscovered. Water column imaging is incomplete both within the target geographic area and farther seaward, between the 2000 m isobath and the deformation front, which is the subject of an imaging study described in a white paper by Watt et al. The recently-discovered Cascadia Margin cold seeps partially overlap an important active margin gas hydrate province (Spence et al., 2001; Tréhu et al., 2003, 2004), as well as an area where sediments on the North American plate are folded and faulted and affected by fluids generated in the subduction complex beneath the Cascadia forearc (e.g., Saffer and Tobin, 2011). Several Ocean Drilling Program expeditions have focused on hydrate systems offshore Vancouver and Oregon (e.g., Riedel et al., 2009; Tréhu et al., 2004) and on the connection between the shallow and deep hydrogeologic systems. Cabled observatories now continuously monitor physical, chemical, and venting processes on south Hydrate Ridge (OOI; e.g., Philip et al., 2016a) and offshore Vancouver Island (NEPTUNE; e.g. Römer et al., 2016). Outside of these well-studied gas hydrate areas, a subset of the recently-discovered Cascadia seeps, including some that we visited with R/V Falkor in 2019 (e.g., https://schmidtocean.org/cruise/methane-seeps-at-edge-of-hydrate-stability/), also likely emit methane associated with shallow subseafloor gas hydrate systems. Other seeps are delivering not only methane, but also deep-derived gases (Baumberger et al., 2018, 2020) to the seafloor. Many Cascadia Margin seeps have also been recognized at water depths too shallow (e.g., 175 m) to be connected to gas hydrate dynamics. These seeps are postulated to be emitting gas and fluids that originated deep in accretionary wedge before migrating up normal faults generated during forearc extension associated with large earthquakes (Johnson et al., 2019). Only a small fraction of the recently discovered U.S. Cascadia Margin water column gas plumes has so far been verified by ROVs (Hercules from E/V Nautilus in 2016 and 2018; SuBastian from R/V Falkor in 2018 and 2019) to correspond to seafloor seeps. Careful scientific mapping, investigation, and sampling at the seeps have also been limited (e.g., Baumberger et al., 2018, 2020; Merle and Embley, 2016; Seabrook et al., 2018; Greinert et al. 2019). This white paper focuses on expanding exploration of already-identified U.S. Cascadia Margin cold seeps through a multipronged and multidisciplinary discovery program that could be accomplished with a variety of NOAA assets. The goals of the proposed exploration activities are to develop high-resolution maps of seep fields from deep ocean vehicles; to verify (and sample) seafloor gas emissions at the locations of water column plumes for compositional and isotopic studies; to map, sample, and conduct analyses on chemosynthetic communities and deep-sea coral habitats near seep sites to document species distributions and habitats as a function of depth and latitude along the margin; to collect seep geologic samples that can constrain the timing of methane emissions through geochronology; and to record environmental data (e.g., CTD) near the seafloor and in the water column above the seeps. Seafloor mapping using shipboard systems (multibeam/backscatter) would be needed to characterize seafloor features near seep sites. Water column imaging (EK60/80 and/or multibeam WCD data) conducted before and after seafloor explorations would capture active methane plumes and constrain temporal variations in seep emissions (e.g., Kannberg et al., 2013; Philip et al., 2016a, 2016b), which are known to vary on time scales as rapid as tidal cycles on this margin (e.g., Römer et al., 2016). What are the characterization and data needs in this area? Check all that apply: __x_ Biology, Geology, Physical Oceanography, Chemistry ___ Marine Archaeology ___ Other Provide a list or brief description of the data needed within this area, from your perspective: 1. Water column backscatter to image active gas plumes 2. High-resolution multibeam bathymetry, seafloor backscatter, and shallow sub-bottom imaging 3. Visual characterization and ground truthing of potential seeps, including high-resolution mapping and photography from near-seafloor vehicles; collection of seep-associated species, corals, sediments, authigenic carbonates, gases, and seawater Describe relevance to national security, conservation, and/or the economy: The Cascadia margin seeps provide significant ecosystem services, including habitat for commercially important fishes and support for diversity along the continental margin. Methane seeps are also biological hotspots for krill, plankton, and crustaceans, which in turn sustain higher trophic levels (e.g., whales). Methane-derived authigenic carbonates serve as a hard substrate for deep-sea corals and sponges on millennial time scales. The studies proposed here will elucidate the relationship among seep environments, deep-sea corals, sponges, fisheries, and other organisms and provide new insight into subduction zone and hydrate-associated fluids in this important seismogenic zone. The studies address fishery management concerns and inform future conservation of sensitive species (e.g., deep-sea corals) and benthic habitats. From your perspective, what makes this area unique? The Cascadia Margin seeps are a critical component of the leaky margin that stretches from Baja California to the Aleutian Arc along the Pacific coastline of North America. Cold seeps have been intensely studied on the Gulf of Mexico and U.S. Atlantic passive margins with a focus on chemosynthetic communities, deep-sea corals, and leakage of microbially-generated and/or thermogenic hydrocarbons; however, the recently-discovered Cascadia Margin seeps, as well as active margin seep systems in general, remain more poorly characterized. Such seeps not only contribute to the ocean carbon cycle (e.g., Pohlman et al., 2011), thereby fueling the base of the food chain in these settings, but also emit subduction zone fluids that provide clues about processes within the seismogenic zone and the accretionary complex. The Cascadia seeps area allows both biological (e.g., benthic habitats, coral distributions) and physical processes (e.g., generation of subduction zone fluids) to be studied along both depth (perpendicular to the deformation front) and latitudinal gradients.

California, Oregon, Washington↗

Geochemical evolution of groundwater in the Mud Lake area, eastern Idaho, USA

Groundwater with elevated dissolved-solids concentrations—containing large concentrations of chloride, sodium, sulfate, and calcium—is present in the Mud Lake area of Eastern Idaho. The source of these solutes is unknown; however, an understanding of the geochemical sources and processes controlling their presence in groundwater in the Mud Lake area is needed to better understand the geochemical sources and processes controlling the water quality of groundwater at the Idaho National Laboratory. The geochemical sources and processes controlling the water quality of groundwater in the Mud Lake area were determined by investigating the geology, hydrology, land use, and groundwater geochemistry in the Mud Lake area, proposing sources for solutes, and testing the proposed sources through geochemical modeling with PHREEQC. Modeling indicated that sources of water to the eastern Snake River Plain aquifer were groundwater from the Beaverhead Mountains and the Camas Creek drainage basin; surface water from Medicine Lodge and Camas Creeks, Mud Lake, and irrigation water; and upward flow of geothermal water from beneath the aquifer. Mixing of groundwater with surface water or other groundwater occurred throughout the aquifer. Carbonate reactions, silicate weathering, and dissolution of evaporite minerals and fertilizer explain most of the changes in chemistry in the aquifer. Redox reactions, cation exchange, and evaporation were locally important. The source of large concentrations of chloride, sodium, sulfate, and calcium was evaporite deposits in the unsaturated zone associated with Pleistocene Lake Terreton. Large amounts of chloride, sodium, sulfate, and calcium are added to groundwater from irrigation water infiltrating through lake bed sediments containing evaporite deposits and the resultant dissolution of gypsum, halite, sylvite, and bischofite.

Idaho↗

Monitoring and modeling wetland chloride concentrations in relationship to oil and gas development

Extraction of oil and gas via unconventional methods is becoming an important aspect of energy production worldwide. Studying the effects of this development in countries where these technologies are being widely used may provide other countries, where development may be proposed, with some insight in terms of concerns associated with development. A fairly recent expansion of unconventional oil and gas development in North America provides such an opportunity. Rapid increases in energy development in North America have caught the attention of managers and scientists as a potential stressor for wildlife and their habitats. Of particular concern in the Northern Great Plains of the U.S. is the potential for chloride-rich produced water associated with unconventional oil and gas development to alter the water chemistry of wetlands. We describe a landscape scale modeling approach designed to examine the relationship between potential chloride contamination in wetlands and patterns of oil and gas development. We used a spatial Bayesian hierarchical modeling approach to assess multiple models explaining chloride concentrations in wetlands. These models included effects related to oil and gas wells (e.g. age of wells, number of wells) and surficial geology (e.g. glacial till, outwash). We found that the model containing the number of wells and the surficial geology surrounding a wetland best explained variation in chloride concentrations. Our spatial predictions showed regions of localized high chloride concentrations. Given the spatiotemporal variability of regional wetland water chemistry, we do not regard our results as predictions of contamination, but rather as a way to identify locations that may require more intensive sampling or further investigation. We suggest that an approach like the one outlined here could easily be extended to more of an adaptive monitoring approach to answer questions about chloride contamination risk that are of interest to managers.

Montana, North Dakota↗

Evaluating chemical extraction techniques for the determination of uranium oxidation state in reduced aquifer sediments

Extraction techniques utilizing high pH and (bi)carbonate concentrations were evaluated for their efficacy in determining the oxidation state of uranium (U) in reduced sediments collected from Rifle, CO. Differences in dissolved concentrations between oxic and anoxic extractions have been proposed as a means to quantify the U(VI) and U(IV) content of sediments. An additional step was added to anoxic extractions using a strong anion exchange resin to separate dissolved U(IV) and U(VI). X-ray spectroscopy showed that U(IV) in the sediments was present as polymerized precipitates similar to uraninite and/or less ordered U(IV), referred to as non-uraninite U(IV) species associated with biomass (NUSAB). Extractions of sediment containing both uraninite and NUSAB displayed higher dissolved uranium concentrations under oxic than anoxic conditions while extractions of sediment dominated by NUSAB resulted in identical dissolved U concentrations. Dissolved U(IV) was rapidly oxidized under anoxic conditions in all experiments. Uraninite reacted minimally under anoxic conditions but thermodynamic calculations show that its propensity to oxidize is sensitive to solution chemistry and sediment mineralogy. A universal method for quantification of U(IV) and U(VI) in sediments has not yet been developed but the chemical extractions, when combined with solid-phase characterization, have a narrow range of applicability for sediments without U(VI).

Colorado↗

Pesticide concentrations of surface water and suspended sediment in Yolo By-Pass and Cache Slough Complex, California, 2019–2021

Managed flow pulses in the north Sacramento-San Joaquin Delta are an adaptive management tool used in efforts to enhance food availability in delta smelt ( Hypomesus transpacificus ) habitat as part of the North Delta Food Subsidies Action. The California Department of Water Resources (DWR) monitors non-managed seasonal and local flow pulses and managed flow pulses from agricultural drainage or main stem Sacramento River water redirected through Yolo By-Pass. Augmented flow pulses are hypothesized to improve net positive flow during summer and fall in Yolo By-Pass and enhance plankton availability in delta smelt habitat in Cache Slough complex. However, flow pulses may also result in unintended negative effects of increased pesticides that are transported through Yolo By-Pass. Here, we evaluate pesticides in surface water and suspended sediment correlated with flow pulses in Yolo By-Pass during the 2019–21 calendar years. Surface-water and suspended-sediment samples were collected by DWR personnel. Water samples were analyzed at the U.S. Geological Survey Organic Chemistry Research Laboratory in Sacramento, California, for a suite of as many as 178 current-use pesticides and pesticide degradates using gas chromatography with mass spectrometry (GC/MS), gas chromatography with tandem mass spectrometry, and liquid chromatography with tandem mass spectrometry. Suspended sediments filtered from water samples were analyzed for a suite of as many as 173 current-use pesticides and pesticide degradates. There were 52 different current-use pesticides and pesticide degradates detected in water samples collected throughout the study. Concentrations ranged from below method detection limits to 4,070 nanograms per liter. Five different compounds in water samples were detected with concentrations above U.S. Environmental Protection Agency aquatic life benchmarks. In suspended-sediment samples collected throughout the study, eight different current-use pesticides and pesticide degradates were detected. Total pesticide concentrations were highest at surface-water sites in the northern end of Yolo By-Pass and decreased farther downstream during the same sampling events. Total pesticide concentrations generally were higher for most surface-water sites immediately before or during the managed flow pulse in 2019 versus after the flow pulse. Finally, mean total pesticide concentrations for each surface-water site generally were higher during all of 2019 than 2021, regardless of sampling period.

California↗

Vegetation of prairie potholes, North Dakota, in relation to quality of water and other environmental factors

Measurements of specific conductance provide an adequate indication of the average salinity of surface waters in natural ponds and lakes of the northern .prairie region. Yearly and seasonal variations in specific conductance were much greater in brackish and subsaline wetlands than in fresh-water areas. The principal vegetational types. Land-use practices of varying brackish to saline wetlands were sulfates and chlorides of sodium and magnesium. In less saline waters, carbonate and bicarbonate salts of calcium and potassium were of greater importance, but as salinity increased, the proportion of these compounds decreased rapidly. A major environmental factor controlling the establishment of marsh and aquatic vegetation is the permanence of surface water. Permanence is a measure of the extent to which surface water persists at a given site. Varying degrees of water permanence during the growing season led to the establishment of distinct vegetational types, which were differentiated primarily on the 'basis of community structure or life form of the dominant vegetation. Salinity of surface waters was closely correlated with differences in species composition of plant communities found in the principal vegetational types. Land-use practices of varying degrees of intensity also had a secondary influence on species composition. Since an unstable water chemistry is characteristic of most prairie ponds and lakes, it is more reliable to use the plant communities as indicators of average salinity than to use single measurements of specific conductance. Characteristic species of wetland vegetational types occupied the central deeper parts of pond and lake basins or occurred as concentric peripheral bands. The wetland vegetational types are wetland low-prairie, wet-meadow, shallow-marsh emergent, deep-marsh emergent, fen emergent, submerged and floating, natural drawdown, cropland drawdown, and cropland tillage vegetation. Combinations of species (plant associations) within these vegetational types were placed in one of six salinity categories designated as fresh, slightly brackish, moderately brackish, brackish, subsaline, and saline. Salt tolerance apparently varied greatly among the various marsh and aquatic plants since the num'ber of species represented in moderately brackish to saline communities decreased markedly with increased salinity of the surface water environment.

Professional Paper↗

A benthic-macroinvertebrate index of biotic integrity and assessment of conditions in selected streams in Chester County, Pennsylvania, 1998-2009

The Stream Conditions of Chester County Biological Monitoring Network (Network) was established by the U.S. Geological Survey and the Chester County Water Resources Authority in 1969. Chester County encompasses 760 square miles in southeastern Pennsylvania and has a rapidly expanding population. Land-use change has occurred in response to this continual growth, as open space, agricultural lands, and wooded lands have been converted to residential and commercial lands. In 1998, the Network was modified to include 18 fixed-location sites and 9 flexible-location sites. Sites were sampled annually in the fall (October-November) during base-flow conditions for water chemistry, instream habitat, and benthic macroinvertebrates. A new set of 9 flexible-location sites was selected each year. From 1998 to 2009, 213 samples were collected from the 18 fixed-location sites and 107 samples were collected from the 84 flexible-location sites. Eighteen flexible-location sites were sampled more than once over the 12-year period; 66 sites were sampled only once. Benthic-macroinvertebrate data from samples collected during 1998-2009 were used to establish the Chester County Index of Biotic Integrity (CC-IBI). The CC-IBI was based on the methods and metrics outlined in the Pennsylvania Department of Environmental Protection's "A Benthic Index of Biotic Integrity for Wadeable Freestone Streams in Pennsylvania." The resulting CC-IBI consists of scores for benthic-macroinvertebrate samples collected from sites in the Network that related to reference conditions in Chester County. Mean CC-IBI scores for 18 fixed-location sites ranged from 37.21 to 88.92. Thirty-nine percent of the 213 samples collected at the 18 fixed-location sites had a CC-IBI score less than 50; 33 percent, 50 to 70; 28 percent, greater than 70. CC-IBI scores from the 107 flexible-location samples ranged from 23.48 to 99.96. Twenty-five percent of the 107 samples collected at the flexible-location sites had a CC-IBI score less than 50; 33 percent, 50 to 70; and 42 percent, greater than 70. Factors that were found to affect CC-IBI scores are nutrient concentrations, habitat conditions, and percent of wooded and urban land use. A positive relation was determined between mean CC-IBI scores and mean total habitat scores for the 18 fixed-location sites. CC-IBI scores were most strongly affected by stream bank vegetative protection, embeddedness, riparian zone width, and sediment deposition. The highest CC-IBI scores were associated with sites that had greater than 28 percent wooded-wetland-water land use, less than 5 percent urban land use, and no municipal wastewater discharges within 10 miles upstream from the sampling site. The lowest CC-IBI scores were associated with sites where urban land use was greater than 15 percent or a municipal wastewater discharge was within 10 miles upstream from the sampling reach. The Mann Kendall test for trends was used to determine trends in CC-IBI scores and concentrations of nitrate, orthophosphate, and chloride for the 18 fixed-location sites. A positive trend in CC-IBI was determined for six sites, and a negative trend was determined for one site. Positive trends in nitrate concentrations were determined for 4 of the 18 fixed-location sites, and a negative trend in orthophosphate concentrations was determined for 1 of the 18 fixed-location sites. Positive trends in chloride concentrations were determined for 16 of the 18 fixed-location sites.

Pennsylvania↗

Water depth fluctuations and water chemistry in five ephemeral rock pools (tinajas), Clark County, Nevada, 2021–23

Southern Nevada is characterized by an arid climate with limited perennial water resources. In this environment, rock pools (tinajas) are both a habitat and drinking water source for wildlife. In this reconnaissance-level project, the U.S. Geological Survey studied the water depth and water chemistry at five tinajas in Clark County, Nevada. The tinaja sites in this study are representative of the dominant plunge pool morphology and the sandstone or carbonate bedrock substrates that characterize tinajas in the region. Continuous water depth measurements at four tinajas between December 2021 and December 2023 indicated that tinajas may contain water for weeks to months after being recharged but are not a permanent drinking water source for wildlife. Tinajas were driest between April and August 2022, before the beginning of the monsoon season. Chemical analysis of select nutrients, major ions, metals, and trace elements from five tinajas detected concentrations below limits established by the U.S. Environmental Protection Agency for aquatic life and drinking water.

Nevada↗

Wetlands serve as natural sources for improvement of stream ecosystem health in regions affected by acid deposition

For over 40 years, acid deposition has been recognized as a serious international environmental problem, but efforts to restore acidified streams and biota have had limited success. The need to better understand the effects of different sources of acidity on streams has become more pressing with the recent increases in surface water organic acids, or 'brownification' associated with climate change and decreased inorganic acid deposition. Here, we carried out a large scale multi-seasonal investigation in the Adirondacks, one of the most acid-impacted regions in the United States, to assess how acid stream producers respond to local and watershed influences and whether these influences can be used in acidification remediation. We explored the pathways of wetland control on aluminum chemistry and diatom taxonomic and functional composition. We demonstrate that streams with larger watershed wetlands have higher organic content, lower concentrations of acidic anions, and lower ratios of inorganic to organic monomeric aluminum, all beneficial for diatom biodiversity and guilds producing high biomass. Although brownification has been viewed as a form of pollution, our results indicate that it may be a stimulating force for biofilm producers with potentially positive consequences for higher trophic levels. Our research also reveals that the mechanism of watershed control of local stream diatom biodiversity through wetland export of organic matter is universal in running waters, operating not only in hard streams, as previously reported, but also in acid streams. Our findings that the negative impacts of acid deposition on Adirondack stream chemistry and biota can be mitigated by wetlands have important implications for biodiversity conservation and stream ecosystem management. Future acidification research should focus on the potential for wetlands to improve stream ecosystem health in acid-impacted regions and their direct use in stream restoration, for example, through stream rechanneling or wetland construction in appropriate hydrologic settings.

Global Change Biology↗

Investigation of water quality and aquatic-community structure in Village and Valley Creeks, City of Birmingham, Jefferson County, Alabama, 2000-01

The U.S. Geological Survey conducted a 16-month investigation of water quality, aquatic-community structure, bed sediment, and fish tissue in Village and Valley Creeks, two urban streams that drain areas of highly intensive residential, commercial, and industrial land use in Birmingham, Alabama. Water-quality data were collected between February 2000 and March 2001 at four sites on Village Creek, three sites on Valley Creek, and at two reference sites near Birmingham—Fivemile Creek and Little Cahaba River, both of which drain less-urbanized areas. Stream samples were analyzed for major ions, nutrients, fecal bacteria, trace and major elements, pesticides, and selected organic constituents. Bed-sediment and fish-tissue samples were analyzed for trace and major elements, pesticides, polychlorinated biphenyls, and additional organic compounds. Aquatic-community structure was evaluated by conducting one survey of the fish community and in-stream habitat and two surveys of the benthic-invertebrate community. Bed-sediment and fish-tissue samples, benthic-invertebrates, and habitat data were collected between June 2000 and October 2000 at six of the nine water-quality sites; fish communities were evaluated in April and May 2001 at the six sites where habitat and benthic-invertebrate data were collected. The occurrence and distribution of chemical constituents in the water column and bed sediment provided an initial assessment of water quality in the streams. The structure of the aquatic communities, the physical condition of the fish, and the chemical analyses of fish tissue provided an indication of the cumulative effects of water quality on the aquatic biota. Water chemistry was similar at all sites, characterized by strong calcium-bicarbonate component and magnesium components. Median concentrations of total nitrogen and total phosphorus were highest at the headwaters of Valley Creek and lowest at the reference site on Fivemile Creek. In Village Creek, median concentrations of nitrite and ammonia increased in a downstream direction. In Valley Creek, median concentrations of nitrate, nitrite, ammonia, organic nitrogen, suspended phosphorus, and orthophosphate decreased in a downstream direction. Median concentrations of Escherichia coli and fecal coliform bacteria were highest at the most upstream site of Valley Creek and lowest at the reference site on Fivemile Creek. Concentrations of enterococci exceeded the U.S. Environmental Protection Agency criterion in 80 percent of the samples; concentrations of Escherichia coli exceeded the criterion in 56 percent of the samples. Concentrations of bacteria at the downstream sites on Village and Valley Creeks were elevated during high flow rather than low flow, indicating the presence of nonpoint sources. Surface-water samples were analyzed for chemical compounds that are commonly found in wastewater and urban runoff. The median number of wastewater indicators was highest at the most upstream site on Valley Creek and lowest at the reference site on Fivemile Creek. Concentrations of total recoverable cadmium, copper, lead, and zinc in surface water exceeded acute and chronic aquatic life criteria in up to 24 percent of the samples that were analyzed for trace and major elements. High concentrations of trace and major elements in the water column were detected most frequently during high flow, indicating the presence of nonpoint sources. Of the 24 pesticides detected in surface water, 17 were herbicides and 7 were insecticides. Atrazine, simazine, and prometon were the most commonly detected herbicides; diazinon, chlorpyrifos, and carbaryl were the most commonly detected insecticides. Concentrations of atrazine, carbaryl, chlorpyrifos, diazinon, and malathion periodically exceeded criteria for the protection of aquatic life. Trace-element priority pollutants, pesticides, and other organic compounds were detected in higher concentrations in bed sediment at the Village and Valley Creek sites than at the reference site on Fivemile Creek. Bed-sediment concentrations of chromium, copper, lead, mercury, and silver were highest at the most upstream site on Valley Creek; and concentrations of cadmium, nickel, selenium, and zinc were highest at the second downstream site on Village Creek. Bed-sediment concentrations of arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, and zinc from the Village and Valley Creek sites exceeded median concentrations observed nationwide. Concentrations of cadmium, selenium, and zinc were highest in fish-liver tissue samples collected from the second downstream site on Village Creek — concentrations of copper and mercury in fish-liver samples were highest at the most downstream site on Village Creek. The highest total concentration of organic compounds detected in bed-sediment samples occurred at the most upstream site on Valley Creek and the lowest total concentration occurred at Fivemile Creek. In Village Creek, concentrations of 75 percent of the detected organic compounds increased in a downstream direction; in Valley Creek, concentrations of about 70 percent of the detected organic compounds decreased in a downstream direction. Concentrations of 10 organic compounds in bed-sediment samples, including chlordane and p,p'-DDE, exceeded levels considered harmful to aquatic organisms at sites on Village and Valley Creeks. Concentrations of dieldrin, chlordane, and polychlorinated biphenyls in fish-tissue samples exceeded National Academy of Science/National Academy of Engineering guidelines for the protection of fish-eating wildlife. Fish and benthic-invertebrate community structure differed between Village and Valley Creeks and the reference streams. Multiple lines of evidence, including the richness and density of benthic invertebrates as well as fish-community structure, indicate that the aquatic community in Village Creek is similar to that of Valley Creek, but that the integrity of the aquatic communities in both creeks is poor in comparison to that observed at the two reference sites. The abundance of mayflies and the number of EPT (Ephemeroptera, Plecoptera, Trichoptera) taxa (two well-known indicators of good water quality) were negatively correlated with industrial land use. The abundance of midges (an indicator of poor water quality) was positively correlated with industrial land use — and midge density was positively correlated with commercial land use, providing additional evidence that these streams have been negatively affected by urbanization in the basins. The percentage of mosquitofishes (a tolerant species) was positively correlated with commercial land use. In contrast, the numbers of fish species, fish families, and the percentage of sunfishes (intolerant species) were positively correlated with forested land use, indicating that the more diverse fish communities were found in basins with a higher percentage of forested land. The concentrations of 12 water-quality constituents (including several nitrogen species, chloride, copper, and molybdenum, and the detection frequency of wastewater indicators) and 18 organic compounds detected in bed sediment were positively correlated with industrial land use. Mercury and molybdenum concentrations detected in fish-liver tissue also were positively correlated with industrial land use. Bed-sediment and water-quality constituents that were found to have significant correlations with land use often were found to be correlated with many biological indicators, further supporting the link between increased urbanization and changes in aquatic-community structure. The water quality and aquatic-community structure in Village and Valley Creeks are degraded in comparison to streams flowing through less-urbanized areas. Low community richness and increased density of certain species within the fish and benthic-invertebrate communities indicate that degradation has occurred during an extended period of time. Decreased diversity in the aquatic communities and elevated concentrations of trace elements and organic contaminants in the water column, bed sediment, and fish tissues at Village and Valley Creeks are indicative of the effects of urbanization. The degree of degradation may be related to point and nonpoint sources of contamination originating within the basins. Industrial land use, in particular, was significantly correlated to elevated contaminant levels in the water column, in bed sediment, in fish tissue, and to the declining health of the benthic-invertebrate communities. The results of the 16-month study have long-range watershed management implications, demonstrating the association of urban development and stream degradation. These data can serve as a baseline from which to determine the effectiveness of stream-restoration programs.

Alabama↗

Multiple stressors mediate the effects of warming on leaf decomposition in a large regulated river

Predicting how increasing temperatures interact with other global change drivers to influence the structure and dynamics of Earth's ecosystems is a primary challenge in ecology. Our study made use of multiple simultaneous “natural experiments” to examine how rapid warming, declining nutrients, invasive consumers, and riparian invasive species management interact to influence leaf decomposition in a large and regulated river. Specifically, we compared the breakdown of cottonwood ( Populus fremontii ), willow ( Salix exigua ), and saltcedar ( Tamarix sp.) leaf litter in 2022 to a previous experiment from 1998 that occurred under much cooler water temperatures, and had higher water phosphorus concentrations, low numbers of invasive New Zealand mudsnails ( Potamopyrgus antipodarum ), and unaltered litter chemistry from the herbivory of saltcedar leaf beetles ( Diorhabda carinulata ). We found that the effects of up to 10°C warmer temperatures on leaf decomposition were mediated by the establishment and management of invasive species and declining water nutrient concentrations arising from upstream reservoir lowering. Such interactions led to accelerated breakdown of saltcedar, but relatively minor effects of warming on the rate of cottonwood and willow decomposition. Additionally, our results demonstrate the potential for favorable invasive species management outcomes in the terrestrial environment to produce unintended responses in adjacent freshwater ecosystems. As temperatures continue to rise, it is critical that future studies consider how warming interacts with multiple stressors and environmental factors to influence processes such as decomposition in freshwater ecosystems.

Arizona↗

Methods for measuring denitrification: Diverse approaches to a difficult problem

Denitrification, the reduction of the nitrogen (N) oxides, nitrate (NO 3 − ) and nitrite (NO 2 − ), to the gases nitric oxide (NO), nitrous oxide (N 2 O), and dinitrogen (N 2 ), is important to primary production, water quality, and the chemistry and physics of the atmosphere at ecosystem, landscape, regional, and global scales. Unfortunately, this process is very difficult to measure, and existing methods are problematic for different reasons in different places at different times. In this paper, we review the major approaches that have been taken to measure denitrification in terrestrial and aquatic environments and discuss the strengths, weaknesses, and future prospects for the different methods. Methodological approaches covered include (1) acetylene-based methods, (2) 15 N tracers, (3) direct N 2 quantification, (4) N 2 :Ar ratio quantification, (5) mass balance approaches, (6) stoichiometric approaches, (7) methods based on stable isotopes, (8) in situ gradients with atmospheric environmental tracers, and (9) molecular approaches. Our review makes it clear that the prospects for improved quantification of denitrification vary greatly in different environments and at different scales. While current methodology allows for the production of accurate estimates of denitrification at scales relevant to water and air quality and ecosystem fertility questions in some systems (e.g., aquatic sediments, well-defined aquifers), methodology for other systems, especially upland terrestrial areas, still needs development. Comparison of mass balance and stoichiometric approaches that constrain estimates of denitrification at large scales with point measurements (made using multiple methods), in multiple systems, is likely to propel more improvement in denitrification methods over the next few years.

Ecological Applications↗

Water quality and aquatic communities of upland wetlands, Cumberland Island National Seashore, Georgia, April 1999 to July 2000

Cumberland Island is the southernmost and largest barrier island along the coast of Georgia. The island contains about 2,500 acres of freshwater wetlands that are located in a variety of physical settings, have a wide range of hydroperiods, and are influenced to varying degrees by surface and ground water, rainwater, and seawater. In 1999-2000, the U.S. Geological Survey, in cooperation with the National Park Service, conducted a water-quality study of Cumberland Island National Seashore to document and interpret the quality of a representative subset of surface- and ground-water resources for management of the seashore's natural resources. As part of this study, historical ground-water, surface-water, and ecological studies conducted on Cumberland Island also were summarized. Surface-water samples from six wetland areas located in the upland area of Cumberland Island were collected quarterly from April 1999 to March 2000 and analyzed for major ions, nutrients, trace elements, and field water-quality constituents including specific conductance, pH, temperature, dissolved oxygen, alkalinity, tannin and lignin, and turbidity. In addition, water temperature and specific conductance were recorded continuously from two wetland areas located near the mean high-tide mark on the Atlantic Ocean beaches from April 1999 to July 2000. Fish and invertebrate communities from six wetlands were sampled during April and December 1999. The microbial quality of the near-shore Atlantic Ocean was assessed in seawater samples collected for 5 consecutive days in April 1999 at five beaches near campgrounds where most recreational water contact occurs. Ground-water samples were collected from the Upper Floridan aquifer in April 1999 and from the surficial aquifer in April 2000 at 11 permanent wells and 4 temporary wells (drive points), and were analyzed for major ions, nutrients, trace elements, and field water-quality constituents (conductivity, pH, temperature, dissolved oxygen, and alkalinity). Fecal-coliform bacteria concentrations were measured, but not detected, in samples collected from two domestic water-supply wells. During the 12-month period from April 1999 to March 2000 when water-quality and aquatic-community samples were collected, rainfall was 12.93 inches below the 30-year average rainfall. Constituent concentrations were highly variable among the different wetlands during the study period. Rainfall and tidal surges associated with tropical storms and hurricanes substantially influenced water quantity and quality, particularly in wetland areas directly influenced by tidal surges. Although surface waters on Cumberland Island are not used as sources of drinking water, exceedances of U.S. Environmental Protection Agency primary and secondary standards for drinking water were noted for comparative purposes. A nitrate concentration of 12 milligrams per liter in one sample from Whitney outflow was the only exceedance of a maximum contaminant level. Secondary standards were exceeded in 26 surface-water samples for the following constituents: pH (10 exceedances), chloride (8), sulfate (5), total dissolved solids (4), iron (2), fluoride (1), and manganese (1). The total-dissolved-solids concentrations and the relative abundance of major ions in surface-water samples collected from wetlands on Cumberland Island provide some insight into potential sources of water and influences on water quality. Major-ion chemistries of water samples from Whitney Lake, Willow Pond, and South End Pond 3 were sodium-chloride dominated, indicating direct influence from rainwater, salt aerosol, or inundation of marine waters. The remaining wetlands sampled had low total-dissolved-solids concentrations and mixed major-ion chemistries--North Cut Pond 2A was magnesium-sodium-chloride-sulfate dominated and Lake Retta and the two beach outflows were sodium-calcium-bicarbonate-chloride dominated. The higher percent calcium and bicarbonate in some wetlands sugg

Georgia↗

Environmental controls on water quality: Case studies from Battle Mountain mining district, north-central Nevada

The environmental controls on water quality were the focus of our study in a portion of the Battle Mountain mining district, north-central Nevada. Samples representing areas outside known mineralized areas, in undisturbed mineralized areas, and in mined areas were chemically and isotopically analyzed. The results are related to geologic, hydrologic, and climatic data. Streams in background areas outside the mineralized zones reflect normal weathering of volcanically derived rocks. The waters are generally dilute, slightly alkaline in pH, and very low in metals. As these streams flow into mineralized zones, their character changes. In undisturbed mineralized areas, discharge into streams of ground water through hydrologically conductive fractures can be traced with chemistry and, even more effectively, with sulfur isotopic composition of dissolved sulfate. Generally, these tracers are much more subtle than in those areas where mining has produced adits and mine-waste piles. The influence of drainage from these mining relicts on water quality is often dramatic, especially in unusually wet conditions. In one heavily mined area, we were able to show that the unusually wet weather in the winter and spring greatly degraded water quality. Addition of calcite to the acid, metalrich mine drainage raised the stream pH and nearly quantitatively removed the metals through coprecipitation and (or) adsorption onto oxyhydroxides. This paper is divided into four case studies used to demonstrate our results. Each addresses the role of geology, hydrology, mining activity and (or) local climate on water quality. Collectively, they provide a comprehensive look at the important factors affecting water quality in this portion of the Battle Mountain mining district.

Nevada↗

Evidence of envronmental change in Rankin basin, Central Florida Bay, Everglades National Park

Analyses of core GLBW601 RL1 collected in Rankin Basin, Florida Bay, Everglades National Park, in June 2001 indicate that significant environmental changes occurred at the site over the last two centuries. The core was collected at a site of documented seagrass die-off in 1987-1988. The purpose of this study was to document the long-term sequences of events leading up to the die-off event. Analyses have been conducted to examine (1) faunal changes in the ostracodes and mollusks, (2) biochemistry of the ostracode shells, (3) floral changes in the pollen assemblages, and (4) geochemical and elemental changes in the sediment. The faunal assemblage analyses provide information on the salinity and benthic habitat at the site. The biochemical and geochemical data provide information about the water chemistry and sedimentation rates. The floral assemblage provides data about the nearby terrestrial environment and the first occurrence of pollen of the Australian pine, Casuarina equisetifolia , serves as a biostratigraphic marker for the beginning of the 20th century. These data provide clues to the cause and effect of the seagrass die-off and changes in salinity patterns and also illustrate decadal-scale patterns of change. The analyses of GLBW601 RL1 show two important results. First, prior to 1900, Rankin Basin tended to be oligohaline to mesohaline on the basis of faunal data showing the assemblage to be similar to that of the lowest portions of a core from Taylor Creek. Second, prior to the documented seagrass die-off, the faunal assemblages indicate an increase in the amplitude of salinity fluctuations; a significant increase occurs in the mollusks Brachidontes exustus and Anomalocardia auberiana , two species that tolerate fluctuations in salinity.

Florida↗

Hydrologic and geochemical controls on pesticide and nutrient transport to two streams on the Delmarva Peninsula

Pesticides and nutrients move from application areas through ground water and surface runoff to streams on the Delmarva Peninsula. The relative importance of different transport media to the movement of these compounds in different watersheds is related to locally variable hydrologic and geochemical conditions among areas of regionally similar land use, geology, and soils. Consideration of such local variability is important to land-management efforts or future environmental investigations on the Peninsula. Chemical analyses of samples collected over a multiyear period from two streams on the Delmarva Peninsula were analyzed along with similar available analyses of ground water to document the occurrence of pesticides and nutrients, and illustrate important processes controlling their movement through watersheds to streams. The upper Pocomoke River and Chesterville Branch drain predominantly agricultural watersheds typical of the Delmarva Peninsula. Chesterville Branch drains a watershed of moderate relief, good drainage, and a permeable surficial aquifer that ranges in thickness from about 15 to 25 meters. The upper Pocomoke River Watershed, however, is extremely flat with poorly drained soils and abundant artificial drainage. Influences on the chemistry of water in each stream were determined from seasonal patterns in the concentrations of selected constituents from 1996 through 2001, and relations with streamflow. Nutrients and pesticides are detectable throughout the year in the upper Pocomoke River and Chesterville Branch. Water in both streams is typically dilute, slightly acidic, and well oxygenated, and nitrate and phosphorus concentrations generally exceed estimated natural levels. Pesticide concentrations are generally low, although concentrations of selected metabolites commonly exceed 1 microgram per liter, particularly in Chesterville Branch. Nitrate and metabolites of pesticide compounds are apparently transported to Chesterville Branch preferentially through ground water in the surficial aquifer, although selected pesticide parent compounds and less soluble nutrients move primarily in surface runoff. Conversely, the relative proportion of discharge from surficial and partially confined aquifers is the most important factor controlling the chemistry of water in the upper Pocomoke River. Surface runoff in the larger and predominantly flat upper Pocomoke River Watershed is apparently limited to particularly significant precipitation events. Transport of pesticides in surface runoff becomes important in both watersheds during such events. Instantaneous loads of pesticides in streams typically stabilize or continue to increase with increasing flow even after runoff begins, although in-stream concentrations may decrease due to dilution.

Scientific Investigations Report↗

CO 2 mitigation via accelerated limestone weathering

We evaluate accelerated weathering of limestone (AWL: CO 2 + CaCO 3 + H 2 O=> Ca 2+ + 2HCO 3 - ) as a low-tech, inexpensive, high-capacity, environmentally-friendly CO 2 capture and sequestration technology. With access to seawater and limestone being essential to this approach, significant limestone resources are close to most CO 2 -emitting power plants along the coastal US. Waste fines, representing more than 20% of current US crushed limestone production (>10 9 tonnes/yr), could be used as an inexpensive source of AWL carbonate. Under such circumstances CO 2 mitigation cost could be as low as $3-$4/tonne. More broadly, 10-20% of US point-source CO 2 emissions could be treated at $20-$30/tonne CO 2 . AWL end-solution disposal in the ocean would significantly reduce effects on ocean pH and carbonate chemistry relative to those caused by direct atmospheric or ocean CO 2 disposal. Indeed, the increase in ocean Ca 2+ and bicarbonate offered by AWL should enhance growth of corals and other calcifying marine organisms.

Conference Paper↗

Where the past meets the present: Connecting nitrogen from watersheds to streams through groundwater flowpaths

Groundwater discharge to streams is a nonpoint source of nitrogen (N) that confounds N mitigation efforts and represents a significant portion of the annual N loading to watersheds. However, we lack an understanding of where and how much groundwater N enters streams and watersheds. Nitrogen concentrations at the end of groundwater flowpaths are the culmination of biogeochemical and physical processes from the contributing land area where groundwater recharges, within the aquifer system, and in the near-stream riparian area where groundwater discharges to streams. Our research objectives were to quantify the spatial distribution of N concentrations at groundwater discharges throughout a mixed land-use watershed and to evaluate how relationships among contributing and riparian land cover, modeled aquifer characteristics, and groundwater discharge biogeochemistry explain the spatial variation in groundwater discharge N concentrations. We accomplished this by integrating high-resolution thermal infrared surveys to locate groundwater discharge, biogeochemical sampling of groundwater, and a particle tracking model that links groundwater discharge locations to their contributing area land cover. Groundwater N loading from groundwater discharges within the watershed varied substantially between and within streambank groundwater discharge features. Groundwater nitrate concentrations were spatially heterogeneous ranging from below 0.03–11.45 mg-N/L, varying up to 20-fold within meters. When combined with the particle tracking model results and land cover metrics, we found that groundwater discharge nitrate concentrations were best predicted by a linear mixed-effect model that explained over 60% of the variation in nitrate concentrations, including aquifer chemistry (dissolved oxygen, Cl − , SO 4 2− ), riparian area forested land cover, and modeled physical aquifer characteristics (discharge, Euclidean distance). Our work highlights the significant spatial variability in groundwater discharge nitrate concentrations within mixed land-use watersheds and the need to understand groundwater N processing across the many spatiotemporal scales within groundwater cycling.

Connecticut↗