USGS ScienceSearch

Geology topics

Luke C. Loken

Publications and source records attributed to Luke C. Loken.

At least 19 recordsLinked to original sources

Per- and polyfluoroalkyl substances in surface water and sediment in Great Lakes tributaries and relations with watershed attributes

Per- and polyfluoroalkyl substances (PFAS) are chemicals of emerging concern that potentially pose risks to human and environmental health. In May–Oct 2018, sediment and passively collected surface water samples were collected from 62 tributary sites of the Laurentian Great Lakes with site catchments spanning various land cover types. Discrete samples of sediment collected manually and time-integrated surface water samples collected with polar organic chemical integrative samplers (POCIS) were analyzed for 23 and 34 PFAS, respectively. Concentrations of individual PFAS in sediment and surface water varied immensely among sites from below detection to 20,800 ng kg −1 and 247 ng L −1 , respectively. Of all target compounds, PFOS was the most frequently detected in sediment (56 of 62 sites) and had the highest median concentration (132 ng kg −1 ). PFOA, PFHxS, PFOS, PFHpA, and PFNA (full chemical names are listed in online supplementary material Table S2) were detected in all 60 surface water sites, with median estimated concentrations of 5.9, 5.2, 4.6, 3.7, and 1.3 ng L −1 , respectively. Compounds with 8–13 fluorinated carbons comprised a larger proportion of sediment PFAS than compounds with 4–7 fluorinated carbons, whereas compounds with 4–7 fluorinated carbons comprised a greater proportion of PFAS in surface waters. Watershed attributes, including urban land cover, airports per catchment area, and wastewater treatment plants flow percentage were significantly ( p < 0.05) and positively related with PFAS sum concentrations in sediment and (or) surface water. Collectively, these results, albeit with some uncertainty in the estimated concentrations, highlight the relation PFAS occurrence has with human activities and documents widespread low-level PFAS contamination across the Great Lakes basin.

Great Lakes

Prioritizing chemicals of emerging concern in the Great Lakes Basin using covariance of chemical concentrations and diverse biological responses from a variety of species

The Great Lakes Restoration Initiative aims to protect and restore the nation’s largest freshwater resource, in part, by furthering our understanding of the effects of contaminants of emerging concern (CECs) and chemical mixtures on aquatic and terrestrial organisms. To address this goal, an interagency team conducted field studies at sites along the Maumee River in Ohio, USA, in 2016–2017, monitoring CEC levels along with diverse in vitro and in vivo biological effects in ecologically relevant species (fathead minnows, tree swallows, and golden clams). The objective of the present work was to prioritize the CECs in these studies for further monitoring and assessment by determining if there are patterns in chemical–bioeffect relations across data sets, species, and response types that indicate relatively high or low hazard to aquatic life from CEC exposure. Of the 748 monitored chemicals, 425 were detected and were analyzed for covariance with bioeffects. All 748 chemicals were placed into 10 bins based on their frequencies of monitoring, detection, and covariance with bioeffects across studies and species. We describe how chemicals can be prioritized across bins to aid monitoring and assessment efforts. Our approach using effects-based monitoring data is especially useful for prioritizing chemicals with little or no traditional toxicity testing data. Similar evidence-based prioritizations will allow agencies to more efficiently allocate limited resources to improve the ability to protect aquatic and terrestrial organisms from adverse impacts due to contaminant exposure.

Ohio

Potential for biological effects of per- and polyfluoroalkyl substances in Great Lakes tributaries and associations with land cover and wastewater effluent

Surface water concentrations of per- and polyfluoroalkyl substances (PFAS) and potential for resulting biological effects were estimated in a study using polar organic chemical integrative samplers (POCIS) from 60 tributary sites within 20 watersheds in the Great Lakes Basin in 2018. Sites represented a range of urban to agricultural, forested, and wetland land uses and included a gradient of wastewater treatment effluent from zero to 44% of annual streamflow. Several sites also had airport influence. Twenty-one of 32 targeted PFAS compounds were detected in POCIS samplers, of which, 16 had available POCIS sampling rates, enabling time-weighted water concentration estimates and comparison with available effects data. Estimated water concentrations were compared with published water quality guidelines (available for nine PFAS), effect concentrations reported in primary literature within the ECOTOX Knowledgebase for apical endpoints (10 PFAS) and nonapical endpoints (10 PFAS), and in vitro high-throughput screening data from the U.S. Environmental Protection Agency Toxicity Forecaster (ToxCast; 14 PFAS). Based on a conservative evaluation approach that was also weighted for persistence and limitations in available toxicological information, five individual PFAS, including perfluorooctanesulfonic acid, perfluorohexanesulfonic acid, perfluorobutanesulfonic acid, perfluorooctanoic acid, and perfluorononanoic acid were identified as warranting additional investigation. Possible increased potency of PFAS mixtures over individual chemical effects, estimated by summation of exposure-activity ratios (EARs) for chemicals that influence common ToxCast assays and specified gene targets, indicated that EAR values increased up to 5.6-fold over individual chemicals, with up to 14 chemicals contributing to mixture effect predictions. Potential for biological effects from PFAS, as estimated by summed exposure-activity ratios, were correlated with urban land use and the proportion of streamflow contributed by wastewater effluent.

Great Lakes tributaries

Changes in phosphorus concentration and flux from 2011 to 2023 in major U.S. tributaries to the Laurentian Great Lakes

Reducing phosphorus (P) flux to the Great Lakes is critical for improving water quality and controlling eutrophication. We used 13 water years (2011–2023) of U.S. Geological Survey data from 24 major U.S. tributaries (representing 47% of the U.S. Great Lakes watershed area) to evaluate temporal changes in orthophosphate (PO 4 -P) and total P (TP) using Weighted Regressions on Time, Discharge, and Season. We assessed actual and flow-normalized P concentrations and fluxes. Between 2011 and 2023, P concentrations and fluxes declined in many tributaries, although the extent and significance of these declines varied. Decreases were more common and statistically likely for TP than PO 4 -P, and several high-loading watersheds had modest or non-significant changes. Flow-normalized PO 4 -P:TP flux ratios increased in over half the tributaries, suggesting that even where P reductions occurred, reductions in the more bioavailable P fraction were proportionally smaller. Actual P fluxes were strongly correlated with streamflow, and year-to-year variability in actual fluxes was, on average, three times greater than variability related to trends in flow-normalized fluxes. This underscores the role of hydrology in modulating P export and highlights how changing precipitation and runoff patterns can obscure or counteract management progress. Spring accounted for the largest share of annual P flux in most tributaries, though many showed declining spring contributions. Our basin-wide analysis reveals that while management efforts may have yielded progress in reducing TP in many watersheds, additional strategies would be needed to address PO 4 -P reductions and account for changing hydrology, especially in high-contributing watersheds.

Journal of Great Lakes Research

Global methane emissions from rivers and streams

Methane (CH 4 ) is a potent greenhouse gas and its concentrations have tripled in the atmosphere since the industrial revolution. There is evidence that global warming has increased CH 4 emissions from freshwater ecosystems 1 , 2 , providing positive feedback to the global climate. Yet for rivers and streams, the controls and the magnitude of CH 4 emissions remain highly uncertain 3 , 4 . Here we report a spatially explicit global estimate of CH 4 emissions from running waters, accounting for 27.9 (16.7–39.7) Tg CH 4 per year and roughly equal in magnitude to those of other freshwater systems 5 , 6 . Riverine CH 4 emissions are not strongly temperature dependent, with low average activation energy ( E M = 0.14 eV) compared with that of lakes and wetlands ( E M = 0.96 eV) 1 . By contrast, global patterns of emissions are characterized by large fluxes in high- and low-latitude settings as well as in human-dominated environments. These patterns are explained by edaphic and climate features that are linked to anoxia in and near fluvial habitats, including a high supply of organic matter and water saturation in hydrologically connected soils. Our results highlight the importance of land–water connections in regulating CH 4 supply to running waters, which is vulnerable not only to direct human modifications but also to several climate change responses on land.

Nature

GRiMeDB: The Global River Database Methane Database of concentrations and fluxes

Despite their small spatial extent, fluvial ecosystems play a significant role in processing and transporting carbon in aquatic networks, which results in substantial emission of methane ( CH 4 ) into the atmosphere. For this reason, considerable effort has been put into identifying patterns and drivers of CH 4 concentrations in streams and rivers and estimating fluxes to the atmosphere across broad spatial scales. However, progress toward these ends has been slow because of pronounced spatial and temporal variability of lotic CH 4 concentrations and fluxes and by limited data availability across diverse habitats and physicochemical conditions. To address these challenges, we present a comprehensive database of CH 4 concentrations and fluxes for fluvial ecosystems along with broadly relevant and concurrent physical and chemical data. The Global River Methane Database (GriMeDB; https://doi.org/10.6073/pasta/f48cdb77282598052349e969920356ef , Stanley et al., 2023) includes 24 024 records of CH 4 concentration and 8205 flux measurements from 5029 unique sites derived from publications, reports, data repositories, unpublished data sets, and other outlets that became available between 1973 and 2021. Flux observations are reported as diffusive, ebullitive, and total CH 4 fluxes, and GriMeDB also includes 17 655 and 8409 concurrent measurements of concentrations and 4444 and 1521 fluxes for carbon dioxide ( CO 2 ) and nitrous oxide ( N 2 O ), respectively. Most observations are date-specific (i.e., not site averages), and many are supported by data for 1 or more of 12 physicochemical variables and 6 site variables. Site variables include codes to characterize marginal channel types (e.g., springs, ditches) and/or the presence of human disturbance (e.g., point source inputs, upstream dams). Overall, observations in GRiMeDB encompass the broad range of the climatic, biological, and physical conditions that occur among world river basins, although some geographic gaps remain (arid regions, tropical regions, high-latitude and high-altitude systems). The global median CH 4 concentration (0.20 µmol L −1 ) and diffusive flux (0.44 mmol m -2 d -1 ) in GRiMeDB are lower than estimates from prior site-averaged compilations, although ranges (0 to 456 µmol L −1 and − 136 to 4057 mmol m -2 d -1 ) and standard deviations (10.69 and 86.4) are greater for this larger and more temporally resolved database. Available flux data are dominated by diffusive measurements despite the recognized importance of ebullitive and plant-mediated CH 4 fluxes. Nonetheless, GriMeDB provides a comprehensive and cohesive resource for examining relationships between CH 4 and environmental drivers, estimating the contribution of fluvial ecosystems to CH 4 emissions, and contextualizing site-based investigations.

Earth System Science Data

Assessment of conservation management practices on water quality and observed trends in the Plum Creek Basin, 2010–20

The U.S. Geological Survey and University of Wisconsin–Green Bay collected hydrologic and water-quality data to assess the effectiveness of agricultural conservation management practice (CMP) implementation at mainstem Plum Creek and west Plum Creek in northeastern Wisconsin. These two subbasins cover 88 percent of the Plum Creek Basin (Hydrologic Unit Code 12), which is a subbasin of the lower Fox River Basin. A published total maximum daily load report for the lower Fox River Basin rated Plum Creek as one of the greatest contributors of total suspended solids (TSS) and total phosphorus (TP) draining into the lower Fox River. To reduce TSS and TP exports from Plum Creek, additional cropland conservation practices and watercourse protections were applied between 2012 and 2020. To detect water-quality trends, data were collected during 2010 to 2020 at mainstem Plum Creek and 2013 to 2020 at west Plum Creek. The project used two methods to evaluate CMP effectiveness. The first method focused on evaluating water-quality changes between initial and post-CMP implementation periods during rain- or snowmelt-induced runoff events (hereafter referred to as “events”). In this approach random-forest models were developed to account for environmental factors which influence water quality. Model residuals from the two time periods were compared to determine the significance of water-quality changes associated with CMP implementation for mainstem and west Plum Creek Basins. The second method used a Weighted Regressions on Time, Discharge, and Season time-series approach to examine changes in water quality during the entire study period in mainstem Plum Creek. Results from both methods indicated there were minimal water-quality changes in TSS concentrations and flow-normalized delivery during runoff events during the 10-year period from 2010 to 2020; however, TP concentrations during low streamflow (less than 3 cubic feet per second [ft 3 /s]) may have decreased. The lack of observed improvement may be attributable to any of the following: variability in weather and hydrologic conditions, insufficient post-treatment data, additional cropland being converted to corn production, above average rainfall, streambank degradation, acute and legacy sources of phosphorus from farm fields, excessive/vulnerable manure applications and spills, and point-source discharges.

Wisconsin

Hydrodynamics structure plankton communities and interactions in a freshwater tidal estuary

Drivers of phytoplankton and zooplankton dynamics vary spatially and temporally in estuaries due to variation in hydrodynamic exchange and residence time, complicating efforts to understand controls on food web productivity. We conducted approximately monthly (2012–2019; n = 74) longitudinal sampling at 10 fixed stations along a freshwater tidal terminal channel in the San Francisco Estuary, California, characterized by seaward to landward gradients in water residence time, turbidity, nutrient concentrations, and plankton community composition. We used multivariate autoregressive state space (MARSS) models to quantify environmental (abiotic) and biotic controls on phytoplankton and mesozooplankton biomass. The importance of specific abiotic drivers (e.g., water temperature, turbidity, nutrients) and trophic interactions differed significantly among hydrodynamic exchange zones with different mean residence times. Abiotic drivers explained more variation in phytoplankton and zooplankton dynamics than a model including only trophic interactions, but individual phytoplankton–zooplankton interactions explained more variation than individual abiotic drivers. Interactions between zooplankton and phytoplankton were strongest in landward reaches with the longest residence times and the highest zooplankton biomass. Interactions between cryptophytes and both copepods and cladocerans were stronger than interactions between bacillariophytes (diatoms) and zooplankton taxa, despite contributing less biovolume in all but the most landward reaches. Our results demonstrate that trophic interactions and their relative strengths vary in a hydrodynamic context, contributing to food web heterogeneity within estuaries at spatial scales smaller than the freshwater to marine transition.

California

Pesticide prioritization by potential biological effects in tributaries of the Laurentian Great Lakes

Watersheds of the Great Lakes Basin (USA/Canada) are highly modified and impacted by human activities including pesticide use. Despite labeling restrictions intended to minimize risks to nontarget organisms, concerns remain that environmental exposures to pesticides may be occurring at levels negatively impacting nontarget organisms. We used a combination of organismal-level toxicity estimates (in vivo aquatic life benchmarks) and data from high-throughput screening (HTS) assays (in vitro benchmarks) to prioritize pesticides and sites of concern in streams at 16 tributaries to the Great Lakes Basin. In vivo or in vitro benchmark values were exceeded at 15 sites, 10 of which had exceedances throughout the year. Pesticides had the greatest potential biological impact at the site with the greatest proportion of agricultural land use in its basin (the Maumee River, Toledo, OH, USA), with 72 parent compounds or transformation products being detected, 47 of which exceeded at least one benchmark value. Our risk-based screening approach identified multiple pesticide parent compounds of concern in tributaries of the Great Lakes; these compounds included: eight herbicides (metolachlor, acetochlor, 2,4-dichlorophenoxyacetic acid, diuron, atrazine, alachlor, triclopyr, and simazine), three fungicides (chlorothalonil, propiconazole, and carbendazim), and four insecticides (diazinon, fipronil, imidacloprid, and clothianidin). We present methods for reducing the volume and complexity of potential biological effects data that result from combining contaminant surveillance with HTS (in vitro) and traditional (in vivo) toxicity estimates. Environ Toxicol Chem 2022;00:1–18. Published 2022. This article is a U.S. Government work and is in the public domain in the USA. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Great Lakes

Prioritizing pesticides of potential concern and identifying potential mixture effects in Great Lakes tributaries using passive samplers

To help meet the objectives of the Great Lakes Restoration Initiative with regard to increasing knowledge about toxic substances, 223 pesticides and pesticide transformation products were monitored in 15 Great Lakes tributaries using polar organic chemical integrative samplers. A screening-level assessment of their potential for biological effects was conducted by computing toxicity quotients (TQs) for chemicals with available US Environmental Protection Agency (USEPA) Aquatic Life Benchmark values. In addition, exposure activity ratios (EAR) were calculated using information from the USEPA ToxCast database. Between 16 and 81 chemicals were detected per site, with 97 unique compounds detected overall, for which 64 could be assessed using TQs or EARs. Ten chemicals exceeded TQ or EAR levels of concern at two or more sites. Chemicals exceeding thresholds included seven herbicides (2,4-dichlorophenoxyacetic acid, diuron, metolachlor, acetochlor, atrazine, simazine, and sulfentrazone), a transformation product (deisopropylatrazine), and two insecticides (fipronil and imidacloprid). Watersheds draining agricultural and urban areas had more detections and higher concentrations of pesticides compared with other land uses. Chemical mixtures analysis for ToxCast assays associated with common modes of action defined by gene targets and adverse outcome pathways (AOP) indicated potential activity on biological pathways related to a range of cellular processes, including xenobiotic metabolism, extracellular signaling, endocrine function, and protection against oxidative stress. Use of gene ontology databases and the AOP knowledgebase within the R-package ToxMixtures highlighted the utility of ToxCast data for identifying and evaluating potential biological effects and adverse outcomes of chemicals and mixtures. Results have provided a list of high-priority chemicals for future monitoring and potential biological effects warranting further evaluation in laboratory and field environments. Environ Toxicol Chem 2023;42:340–366. Published 2022. This article is a U.S. Government work and is in the public domain in the USA. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Great Lakes tributaries

Whole-ecosystem experiment illustrates short timescale hydrodynamic, light, and nutrient control of primary production in a terminal slough

Estuaries are among the most productive of aquatic ecosystems. Yet the collective understanding of patterns and drivers of primary production in estuaries is incomplete, in part due to complex hydrodynamics and multiple controlling factors that vary at a range of temporal and spatial scales. A whole-ecosystem experiment was conducted in a deep, pelagically dominated terminal channel of the Sacramento-San Joaquin Delta (California, USA) that seasonally appears to become nitrogen limited, to test whether adding calcium nitrate would stimulate primary productivity or increase phytoplankton density. Production did not respond consistently to fertilization, in part because nitrate and phytoplankton were dispersed away from the manipulated area within 1–3 days. Temporal and spatial patterns of gross primary production were more strongly related to stratification and light availability (i.e., turbidity) than nitrogen, highlighting the role of hydrodynamics in regulating system production. Similarly, chlorophyll was positively related not only to stratification but also to nitrogen—with a positive interaction—suggesting stratification may trigger nutrient limitation. The average rate of primary production (4.3 g O 2 m −2 d −1 ), metabolic N demand (0.023 mg N L −1 d −1 ), and ambient dissolved inorganic nitrogen concentration (0.03 mg N L −1 ) indicate that nitrogen can become limiting in time and space, especially during episodic stratification events when phytoplankton are isolated within the photic zone, or farther upstream where water clarity increases, dispersive flux decreases, and stratification is stronger and more frequent. The role of hydrodynamics in organizing habitat connectivity and regulating physical and chemical processes at multiple temporal and spatial scales is critical for determining resource availability and evaluating biogeochemical processes in estuaries.

California

Challenges in linking soil health to edge-of-field water quality across the Great Lakes basin

To better understand agricultural nutrient losses, we evaluated relationships between management (e.g., manure and tillage), soil health measurements, and resulting edge-of-field (EOF) surface water quality. This work was conducted before or early into conservation implementation at 14 Great Lakes Restoration Initiative EOF sites spanning Wisconsin, Michigan, Indiana, Ohio, and New York. Analyses of site characteristics (hydroclimate, management, catchment properties) along with 3 yr of soil health measurements (chemical, biological, and physical properties) showed EOF-nutrient export depended on both site and soil properties. A pattern emerged whereby sites not receiving manure and sites with manure defined opposite ends of several gradients for soil and water data. Sites receiving manure had increased microbial activity, organic matter (3.2 vs. 2.7%), and soil test phosphorus (P) (2.8 times more) relative to sites without manure. Suspended sediments (SS), total P (TP), and total nitrogen (TN) in EOF surface runoff varied over three to five orders. Multivariate analysis among sites showed covariant linkages between soil nutrients, soil C, microbial properties, and nutrients in EOF water. There were positive univariate relationships between water-extractable soil P and annual EOF-water concentrations and yields of orthophosphate, TP, TN, and SS ( p < .01). Some soil physical properties (e.g., bulk density and infiltration) also covaried among sites but were not consistently related to runoff index or water yield variables. Given the observed among-site variability, we were not able to isolate desirable soil health signals on EOF surface water quality.

Journal of Environmental Quality

Risk-based prioritization of organic chemicals and locations of ecological concern in sediment from Great Lakes tributaries

With improved analytical techniques, environmental monitoring studies are increasingly able to report the occurrence of tens or hundreds of chemicals per site, making it difficult to identify the most relevant chemicals from a biological standpoint. For this study, organic chemical occurrence was examined, individually and as mixtures, in the context of potential biological effects. Sediment was collected at 71 Great Lakes tributary sites and analyzed for 87 chemicals. Multiple risk-based lines of evidence were used to prioritize chemicals and locations, including comparing sediment concentrations and estimated porewater concentrations to established whole-organism benchmarks (i.e., sediment and water quality criteria and screening values) and to high-throughput toxicity screening data from the U.S. Environmental Protection Agency's ToxCast database, estimating additive effects of chemical mixtures on common ToxCast endpoints, and estimating toxic equivalencies for mixtures of alkylphenols and polycyclic aromatic hydrocarbons (PAHs). This multiple-lines-of-evidence approach enabled the screening of more chemicals, mitigated the uncertainties of individual approaches, and strengthened common conclusions. Collectively, at least one benchmark/screening value was exceeded for 54 of the 87 chemicals, with exceedances observed at all 71 of the monitoring sites. Chemicals with the greatest potential for biological effects, both individually and as mixture components, were bisphenol A, 4-nonylphenol, indole, carbazole, and several polycyclic aromatic hydrocarbons (PAHs). Potential adverse outcomes based on ToxCast gene targets and putative adverse outcome pathways relevant to individual chemicals and chemical mixtures included tumors, skewed sex ratios, reproductive dysfunction, hepatic steatosis, and early mortality, among others. Results provide a screening level prioritization of chemicals with the greatest potential for adverse biological effects and an indication of sites where they are most likely to occur.

Illinois, Indiana, Michigan, Minnesota, New York,

Dispersion and stratification dynamics in the upper Sacramento River deep water ship channel

Hydrodynamics control the movement of water and material within and among habitats, where time-scales of mixing can exert bottom-up regulatory effects on aquatic ecosystems through their influence on primary production. The San Francisco Estuary (estuary) is a low-productivity ecosystem, which is in part responsible for constraining higher trophic levels, including fishes. Many research and habitat-restoration efforts trying to increase primary production have been conducted, including, as described here, a whole-ecosystem nutrient addition experiment where calcium nitrate was applied in the Sacramento River Deep Water Ship Channel (DWSC) to see if phytoplankton production could be increased and exported out of the DWSC. As an integral part of this experiment, we investigated the physical mechanisms that control mixing, and how these mechanisms affect the strength and duration of thermal stratification, which we revealed as critical for controlling phytoplankton dynamics in the relatively turbid upper DWSC. Analysis of a suite of mixing mechanisms and time-scales show that both tidal currents and wind control mixing rates and stratification dynamics in the DWSC. Longitudinal and vertical dispersion increased during periods of high wind, during which wind speed influenced dispersion more than tidal currents. Thermal stratification developed most days, which slowed vertical mixing but was rapidly broken down by wind-induced mixing. Stratification rarely persisted for longer than 24 hours, limiting phytoplankton production in the study area. The interaction between physical mechanisms that control mixing rates, mediate stratification dynamics, and ultimately limit primary production in the DWSC may be useful in informing habitat restoration elsewhere in the Delta and in other turbid aquatic environments.

California

Assessment of multiple ecosystem metabolism methods in an estuary

Ecosystem metabolism is a key ecological attribute and easy to describe, but quantifying metabolism in estuaries is challenging. Properly scaling measurements through time and space requires consideration of hydrodynamics and mixing water from heterogeneous sources, making any estimation uncertain. Here, we compared three methods for modeling ecosystem metabolism in a portion of the Sacramento-San Joaquin Delta. Metabolism estimates based on laboratory incubations, continuous in situ buoys, and an oxygen isotope approach all indicated the system was net heterotrophic, and calculated rates were comparable in magnitude when averaged over the 2-month study. Daily metabolic rates based on in situ buoys were the most variable, likely due to horizontal and vertical advection and poor portrayal of the dissolved oxygen budget. After temporally averaging in situ buoy estimates or smoothing the dissolved oxygen time series for tidal effects, rates were more comparable to the other methods, which may be necessary to account for tidal advection and unbalanced contributions from subhabitats within the metabolic footprint. Incubation-based rates represent the finest temporal and spatial scale and only account for pelagic processes, which may explain why incubation-based rates were lower than the other two methods. The oxygen isotope method provided temporally and spatially integrated rates that were bracketed by the other two methods and may be a valuable tool in systems matching the model requirements. Because uncertainty arises in each method from a number of assumptions and scaling calculations, the resolution of metabolic rates in estuaries is likely coarser and more variable than in other aquatic ecosystems.

California

Limited nitrate retention capacity in the Upper Mississippi River

The Mississippi River and other large rivers have the potential to regulate nitrogen export from terrestrial landscapes, and thus mitigate eutrophication in downstream aquatic ecosystems. In large rivers, human-constructed impoundments and connected backwaters may facilitate nitrogen removal; however, the capacity of these features is poorly quantified and incompletely incorporated into model frameworks. Using a high-resolution and spatially intensive sampling technique, we assessed the contribution of individual navigation pools, as well as impounded open waters and backwater wetlands within them, to overall nitrate retention by mapping the entire length (1370 km) of the Upper Mississippi River (UMR) main channel. Based on this single spatial survey of water chemistry, the river appeared to act primarily as a passive nitrate transporter, retaining only 12.5% of the incoming load, most of which occurred in the upper 150 km of the river, which includes the largest and only naturally impounded reach of the river. Although reservoirs typically are nitrogen sinks, our data indicate that UMR dams do not impede river flows to the extent necessary to promote substantial changes in water residence times and subsequent nitrogen removal. Backwaters routinely had lower nitrate concentrations than the main channel, but their limited hydrologic connectivity to the through-flowing river channel constrained their influence on downstream export. As a whole, the UMR did not remove a substantial proportion of its nitrate load despite optimal N removal conditions, numerous impoundments, and the presence of extensive backwater habitats. These results suggest that efforts to reduce delivery of nitrogen to the Gulf of Mexico should emphasize mitigation strategies that target upland nutrient sources rather than relying on removal within the Mississippi River.

Upper Mississippi River

Spatial early warning signals in a lake manipulation

Rapid changes in state have been documented for many of Earth's ecosystems. Despite a growing toolbox of methods for detecting declining resilience or early warning indicators (EWIs) of ecosystem transitions, these methods have rarely been evaluated in whole-ecosystem trials using reference ecosystems. In this study, we experimentally tested EWIs of cyanobacteria blooms based on changes in the spatial structure of a lake. We induced a cyanobacteria bloom by adding nutrients to an experimental lake and mapped fine-resolution spatial patterning of cyanobacteria using a mobile sensor platform. Prior to the bloom, we detected theoretically predicted spatial EWIs based on variance and spatial autocorrelation, as well as a new index based on the extreme values. Changes in EWIs were not discernible in an unenriched reference lake. Despite the fluid environment of a lake where spatial heterogeneity driven by biological processes may be overwhelmed by physical mixing, spatial EWIs detected an approaching bloom suggesting the utility of spatial metrics for signaling ecological thresholds.

Ecosphere

Spatial variability of CO2 concentrations and biogeochemistry in the Lower Columbia River

Carbon dioxide (CO 2 ) emissions from rivers and other inland waters are thought to be a major component of regional and global carbon cycling. In large managed rivers such as the Columbia River, contemporary ecosystem changes such as damming, nutrient enrichment, and increased water residence times may lead to reduced CO 2 concentrations (and emissions) due to increased primary production, as has been shown in another large North American river (Upper Mississippi). In this work, spatial patterns of water quality, including dissolved CO 2 concentrations, were assessed in the Lower Columbia River (LCR) and major tributaries using underway measurements from a small research vessel during July 2016. We observed near-equilibrium CO 2 conditions and overall weak supersaturation of CO 2 in the main channel (average 133.8% saturation) and tributaries. We observed only weak correlations between CO 2 saturation, chlorophyll a fluorescence, and turbidity, thus not strongly supporting our hypothesis of primary productivity controls. In general, the LCR was clear (low turbidity, mean = 1.48 FNU) and had low chlorophyll fluorescence (mean = 0.177 RFU) during the sampling period. As a whole, the LCR was homogeneous with respect to biogeochemical conditions and showed low spatial variability at >100 km scales. Overall, we find that the LCR is likely a weak summertime source of CO 2 to the atmosphere, in line with findings from other altered rivers such as the Upper Mississippi.

Columbia River