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Proactive aquatic ecotoxicological assessment of room-temperature ionic liquids

Aquatic environments are being contaminated with a myriad of anthropogenic chemicals, a problem likely to continue due to both unintentional and intentional releases. To protect valuable natural resources, novel chemicals should be shown to be environmentally safe prior to use and potential release into the environment. Such proactive assessment is currently being applied to room-temperature ionic liquids (ILs). Because most ILs are water-soluble, their effects are likely to manifest in aquatic ecosystems. Information on the impacts of ILs on numerous aquatic organisms, focused primarily on acute LC50 and EC50 endpoints, is now available, and trends in toxicity are emerging. Cation structure tends to influence IL toxicity more so than anion structure, and within a cation class, the length of alkyl chain substituents is positively correlated with toxicity. While the effects of ILs on several aquatic organisms have been studied, the challenge for aquatic toxicology is now to predict the effects of ILs in complex natural environments that often include diverse mixtures of organisms, abiotic conditions, and additional stressors. To make robust predictions about ILs will require coupling of ecologically realistic laboratory and field experiments with standard toxicity bioassays and models. Such assessments would likely discourage the development of especially toxic ILs while shifting focus to those that are more environmentally benign. Understanding the broader ecological effects of emerging chemicals, incorporating that information into predictive models, and conveying the conclusions to those who develop, regulate, and use those chemicals, should help avoid future environmental degradation.

Current Organic Chemistry

Using biological responses to monitor freshwater post-spill conditions over 3 years in Blacktail Creek, North Dakota, USA

A pipeline carrying unconventional oil and gas (OG) wastewater spilled approximately 11 million liters of wastewater into Blacktail Creek, North Dakota, USA. Flow of the mix of stream water and wastewater down the channel resulted in storage of contaminants in the hyporheic zone and along the banks, providing a long-term source of wastewater constituents to the stream. A multi-level investigation was used to assess the potential effects of oil and brine spills on aquatic life. In this study, we used a combination of experiments using a native fish species, Fathead Minnow ( Pimephales promelas ), field sampling of the microbial community structure, and measures of estrogenicity. The fish investigation included in situ experiments and experiments with collected site water. Estrogenicity was measured in collected site water samples, and microbial community analyses were conducted on collected sediments. During the initial post-spill investigation, February 2015, performing in situ fish bioassays was impossible because of ice conditions. However, microbial community (e.g., the presence of members of the Halomonadaceae, a family that is indicative of elevated salinity) and estrogenicity differences were compared to reference sites and point to early biological effects of the spill. We noted water column effects on in situ fish survival 6 months post-spill during June 2015. At that time, total dissolved ammonium (sum of ammonium and ammonia, TAN) was 4.41 mg NH 4 /L with an associated NH 3 of 1.09 mg/L, a concentration greater than the water quality criteria established to protect aquatic life. Biological measurements in the sediment defined early and long-lasting effects of the spill on aquatic resources. The microbial community structure was affected during all sampling events. Therefore, sediment may act as a sink for constituents spilled and as such provide an indication of continued and cumulative effects post-spill. However, lack of later water column effects may reflect pulse hyporheic flow of ammonia from shallow ground water. Combining fish toxicological, microbial community structure and estrogenicity information provides a complete ecological investigation that defines potential influences of contaminants at organismal, population, and community levels. In general, in situ bioassays have implications for the individual survival and changes at the population level, microbial community structure defines potential changes at the community level, and estrogenicity measurements define changes at the individual and molecular level. By understanding effects at these various levels of biological organization, natural resource managers can interpret how a course of action, especially for remediation/restoration, might affect a larger group of organisms in the system. The current work also reviews potential effects of additional constituents defined during chemistry investigations on aquatic resources.

North Dakota

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

National Research Program of the Water Resources Division, U.S. Geological Survey: Fiscal Year 1988

The National Research Program (NRP) of the US Geological Survey 's Water Resources Division (WRD) had its beginnings in the late 1950 's when ' core research ' was added as a line item to the Congressional budget. Since that time, the NRP has grown to encompass a broad spectrum of scientific investigations. The sciences of hydrology, mathematics, chemistry, physics, ecology, biology, geology, and engineering are used to gain a fundamental understanding of the processes that affect the availability, movement, and quality of the Nation 's water resources. The NRP is located principally in Reston, VA, Denver, CO, and Menlo Park , CA. The NRP is subdivided into six disciplines as follows: (1) Ecology; (2) Geomorphology and Sediment Transport; (3) Groundwater Chemistry; (4) Groundwater Hydrology; (5) Surface Water Chemistry; and (6) Surface Water Hydrology. The report provides current information about the NRP on an annual basis. Organized by the six research disciplines, the volume contains a summary of the problem, objective, approach, and progress for each project that was active during fiscal year 1988.

Open-File Report

Planetary science decadal survey planetary mission concept study report: Ceres: Exploration of Ceres’ habitability

Dwarf planet Ceres is a compelling target as an evolved ocean world with, at least, regional brine reservoirs and potentially ongoing geological activity. As the most water-rich body in the inner solar system (in relative abundance), it is a representative of the population of planetesimals that brought volatiles and organics to the inner solar system. Situated in the Main Belt of asteroids, Ceres is accessible enough for a sample return with the resources of a typical medium-class (New Frontiers) NASA mission. Under the Discovery program, Dawn explored Ceres from 2015 to 2018. The extensive dataset revealed the presence of liquid, brine-driven activity, organic matter, and a rich salt chemistry. With this evidence, the overarching goals of the mission concept presented herein are to quantify Ceres’ current habitability potential and origin.

Cooperator Report

Dissolved pesticide and organic carbon concentrations detected in surface waters, northern Central Valley, California, 2001-2002

Field and laboratory studies were conducted to determine the effects of pesticide mixtures on Chinook salmon under various environmental conditions in surface waters of the northern Central Valley of California. This project was a collaborative effort between the U.S. Geological Survey (USGS) and the University of California. The project focused on understanding the environmental factors that influence the toxicity of pesticides to juvenile salmon and their prey. During the periods January through March 2001 and January through May 2002, water samples were collected at eight surface water sites in the northern Central Valley of California and analyzed by the USGS for dissolved pesticide and dissolved organic carbon concentrations. Water samples were also collected by the USGS at the same sites for aquatic toxicity testing by the Aquatic Toxicity Laboratory at the University of California Davis; however, presentation of the results of these toxicity tests is beyond the scope of this report. Samples were collected to characterize dissolved pesticide and dissolved organic carbon concentrations, and aquatic toxicity, associated with winter storm runoff concurrent with winter run Chinook salmon out-migration. Sites were selected that represented the primary habitat of juvenile Chinook salmon and included major tributaries within the Sacramento and San Joaquin River Basins and the Sacramento?San Joaquin Delta. Water samples were collected daily for a period of seven days during two winter storm events in each year. Additional samples were collected weekly during January through April or May in both years. Concentrations of 31 currently used pesticides were measured in filtered water samples using solid-phase extraction and gas chromatography-mass spectrometry at the U.S. Geological Survey's organic chemistry laboratory in Sacramento, California. Dissolved organic carbon concentrations were analyzed in filtered water samples using a Shimadzu TOC-5000A total organic carbon analyzer.

California

The H4IIE cell bioassay as an indicator of dioxin-like chemicals in wildlife and the environment

The H4IIE cell bioassay has proven utility as a screening tool for planar halogenated hydrocarbons (PHHs) and structurally similar chemicals accumulated in organisms from the wild. This bioassay has additional applications in hazard assessment of PHH exposed populations. In this review, the toxicological principles, current protocols, performance criteria, and field applications for the assay are described. The H4IIE cell bioassay has several advantages over the analytical measurement of PHHs in environmental samples, but conclusions from studies can be strengthened when both bioassay and analytical chemistry data are presented together. Often, the bioassay results concur with biological effects in organisms and support direct measures of PHHs. For biomonitoring purposes and prioritization of PHH-contaminated environments, the H4IIE bioassay may be faster and less expensive than analytical measurements. The H4IIE cell bioassay can be used in combination with other biomarkers such as in vivo measurements of CYP1A1 induction to help pinpoint the sources and identities of dioxin-like chemicals. The number of studies that measure H4IIE-derived TCDD-EQs continues to increase, resulting in subtle improvements over time. Further experiments are required to determine if TCDD-EQs derived from mammalian cells are adequate predictors of toxicity to non-mammalian species. The H4IIE cell bioassay has been used in over 300 published studies, and its combination of speed, simplicity, and ability to integrate the effects of complex containment mixtures makes it a valuable addition to hazard assessment and biomonitoring studies.

Critical Reviews in Toxicology

National Research Program of the U.S. Geological Survey, Water Resources Division fiscal year 1994

This report provides current information about the National Research Program (NRP) of the U.S. Geological Survey's Water Resources Division (WRD) during fiscal year 1994. Organized by NRP's six research disciplines ecology, geomorphology and sediment transport, ground-water chemistry, ground-water hydrology, surface-water chemistry, and surface-water hydrology the volume contains a summary of the problem, objective, approach, and progress for each project that was active during fiscal year 1994. It also contains bibliographic information that, because of the long-term nature of the program, covers a 5-year period.

Open-File Report

Restoration handbook for sagebrush steppe ecosystems with emphasis on greater sage-grouse habitat—Part 3. Site level restoration decisions

Sagebrush steppe ecosystems in the United States currently (2016) occur on only about one-half of their historical land area because of changes in land use, urban growth, and degradation of land, including invasions of non-native plants. The existence of many animal species depends on the existence of sagebrush steppe habitat. The greater sage-grouse ( Centrocercus urophasianus ) depends on large landscapes of intact habitat of sagebrush and perennial grasses for their existence. In addition, other sagebrush-obligate animals have similar requirements and restoration of landscapes for greater sage-grouse also will benefit these animals. Once sagebrush lands are degraded, they may require restoration actions to make those lands viable habitat for supporting sagebrush-obligate animals, livestock, and wild horses, and to provide ecosystem services for humans now and for future generations. When a decision is made on where restoration treatments should be applied, there are a number of site-specific decisions managers face before selecting the appropriate type of restoration. This site-level decision tool for restoration of sagebrush steppe ecosystems is organized in nine steps. Step 1 describes the process of defining site-level restoration objectives. Step 2 describes the ecological site characteristics of the restoration site. This covers soil chemistry and texture, soil moisture and temperature regimes, and the vegetation communities the site is capable of supporting. Step 3 compares the current vegetation to the plant communities associated with the site State and Transition models. Step 4 takes the manager through the process of current land uses and past disturbances that may influence restoration success. Step 5 is a brief discussion of how weather before and after treatments may impact restoration success. Step 6 addresses restoration treatment types and their potential positive and negative impacts on the ecosystem and on habitats, especially for greater sage-grouse. We discuss when passive restoration options may be sufficient and when active restoration may be necessary to achieve restoration objectives. Step 7 addresses decisions regarding post-restoration livestock grazing management. Step 8 addresses monitoring of the restoration; we discuss important aspects associated with implementation monitoring as well as effectiveness monitoring. Step 9 takes the information learned from monitoring to determine how restoration actions in the future might be adapted to improve restoration success.

Circular

Groundwater resources of the Devils Postpile National Monument—Current conditions and future vulnerabilities

This study presents an extensive database on groundwater conditions in and around Devils Postpile National Monument. The database contains chemical analyses of springs and the monument water-supply well, including major-ion chemistry, trace element chemistry, and the first information on a list of organic compounds known as emerging contaminants. Diurnal, seasonal, and annual variations in groundwater discharge and chemistry are evaluated from data collected at five main monitoring sites, where streams carry the aggregate flow from entire groups of springs. These springs drain the Mammoth Mountain area and, during the fall months, contribute a significant fraction of the San Joaquin River flow within the monument. The period of this study, from fall 2012 to fall 2015, includes some of the driest years on record, though the seasonal variability observed in 2013 might have been near normal. The spring-fed streams generally flowed at rates well below those observed during a sequence of wet years in the late 1990s. However, persistence of flow and reasonably stable water chemistry through the recent dry years are indicative of a sizeable groundwater system that should provide a reliable resource during similar droughts in the future. Only a few emerging contaminants were detected at trace levels below 1 microgram per liter (μg/L), suggesting that local human visitation is not degrading groundwater quality. No indication of salt from the ski area on the north side of Mammoth Mountain could be found in any of the groundwaters. Chemical data instead show that natural mineral water, such as that discharged from local soda springs, is the main source of anomalous chloride in the monument supply well and in the San Joaquin River. The results of the study are used to develop a set of recommendations for future monitoring to enable detection of deleterious impacts to groundwater quality and quantity

California

Understanding ocean acidification impacts on organismal to ecological scales

Ocean acidification (OA) research seeks to understand how marine ecosystems and global elemental cycles will respond to changes in seawater carbonate chemistry in combination with other environmental perturbations such as warming, eutrophication, and deoxygenation. Here, we discuss the effectiveness and limitations of current research approaches used to address this goal. A diverse combination of approaches is essential to decipher the consequences of OA to marine organisms, communities, and ecosystems. Consequently, the benefits and limitations of each approach must be considered carefully. Major research challenges involve experimentally addressing the effects of OA in the context of large natural variability in seawater carbonate system parameters and other interactive variables, integrating the results from different research approaches, and scaling results across different temporal and spatial scales.

Oceanography

Status and understanding of groundwater quality in the central-eastside San Joaquin Basin, 2006: California GAMA Priority Basin Project

Groundwater quality in the approximately 1,695-square-mile Central Eastside San Joaquin Basin (Central Eastside) study unit was investigated as part of the Priority Basin Project (PBP) of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA PBP was developed in response to the California Groundwater Quality Monitoring Act of 2001, and is being conducted by the California State Water Resources Control Board in collaboration with the U.S. Geological Survey and the Lawrence Livermore National Laboratory. The GAMA Central Eastside study unit was designed to provide a spatially unbiased assessment of untreated-groundwater quality, as well as a statistically consistent basis for comparing water quality throughout California. During March through June 2006, samples were collected from 78 wells in Stanislaus and Merced Counties, 58 of which were selected using a spatially distributed, randomized grid-based method to provide statistical representation of the study unit (grid wells), and 20 of which were sampled to evaluate changes in water chemistry along groundwater-flow paths (understanding wells). Water-quality data from the California Department of Public Health (CDPH) database also were used for the assessment. An assessment of the current status of the groundwater quality included collecting samples from wells for analysis of anthropogenic constituents such as volatile organic compounds (VOCs) and pesticides, as well as naturally occurring constituents such as major ions and trace elements. The assessment of status is intended to characterize the quality of untreated-groundwater resources within the primary aquifer system, not the treated drinking water delivered to consumers by water purveyors. The primary aquifer system (hereinafter, primary aquifer) is defined as that part of the aquifer corresponding to the perforation interval of wells listed in the CDPH database for the Central Eastside study unit. The quality of groundwater in shallower or deeper water-bearing zones may differ from that in the primary aquifer; shallower groundwater may be more vulnerable to surficial contamination. The primary aquifer is represented by the grid wells, of which 90 percent had depths to the tops of their perforations of about 80 to 330 feet and depths to bottom of about 100 to 670 feet. Relative-concentrations (sample concentration divided by benchmark concentration) were used as the primary metric for assessing the status of water quality for those constituents that have Federal and (or) California human health or aesthetic benchmarks. A relative-concentration greater than (>) 1.0 indicates a concentration above a benchmark, and less than or equal to (≤) 1.0 indicates a concentration equal to or below a benchmark. For organic and special interest constituents, relative-concentrations were classified as high (>1.0), moderate (≤1.0 and >0.1), or low (≤0.1). For inorganic constituents, relative-concentrations were classified as high (>1.0), moderate (≤1.0 and >0.5), or low (≤0.5). The threshold between low and moderate classifications was lower for organic and special interest constituents than for inorganic constituents because organic constituents generally are less prevalent and have smaller relative-concentrations than inorganic constituents. Grid-based and spatially-weighted approaches, the latter incorporating data from all CDPH wells, were used to evaluate the proportion of the primary aquifer (aquifer-scale proportions) with high, moderate, or low relative-concentrations. For individual constituents or classes of constituents, the aquifer-scale high proportion is the percentage of the area of the study unit having high relative-concentrations within the depth-zones of the primary aquifer. Aquifer-scale moderate and low proportions are defined similarly. Spatially-weighted aquifer-scale high proportions nearly always fell within the 90-percent confidence interval of grid-based aquifer-scale high proportions, indicating that the grid-based approach yielded statistically equivalent results to the spatially-weighted approach incorporating CDPH data. The status assessment for inorganic constituents showed that inorganic constituents (one or more) were high, relative to human-health benchmarks, in 18.0 percent of the primary aquifer, moderate in 44.0 percent, and low in 38.0 percent. Of inorganic constituents with human-health benchmarks, arsenic, vanadium, and nitrate were detected at high relative-concentrations in 15.6 percent, 3.6 percent, and 2.1 percent, respectively, of the primary aquifer. Of inorganic constituents with secondary maximum contaminant levels (SMCL), manganese, iron, and TDS were detected at high relative-concentrations in 4.5 percent, 2.2 percent, and 1.7 percent, respectively, of the primary aquifer. The status assessment for organic constituents showed that organic constituents (one or more) were high, relative to human-health benchmarks, in a smaller proportion of the primary aquifer (1.2 percent) than inorganic constituents (18.0 percent). Organic constituents had moderate relative-concentrations in 14.3 percent, and had low relative-concentrations or were not detected in 84.5 percent, of the primary aquifer. The proportion of the primary aquifer with high relative-concentrations of organic constituents reflected high proportions of the discontinued soil fumigant 1,2-dibromo-3-chlororopane (DBCP; 1.0 percent) and the solvent tetrachloroethene (PCE; 0.2 percent). Most of the organic and special interest constituents detected in groundwater in the Central Eastside study unit have human-health benchmarks. Of the 205 organic and special interest constituents analyzed for, 36 constituents were detected. Of these constituents, 32 were detected only at low relative-concentrations. Four constituents, chloroform, carbon tetrachloride, DBCP, and perchlorate, were detected at moderate relative-concentrations in grid wells. Nine organic and special-interest constituents were detected frequently (detected in greater than 10 percent of samples): the trihalomethanes chloroform, bromoform, bromodichloromethane, and dibromochloromethane; the solvent PCE; the herbicides atrazine, simazine, and metolachlor, and special-interest constituent perchlorate. An assessment of understanding of the groundwater quality included sampling of understanding wells, some of which were perforated in shallower or deeper portions of the aquifer system than the primary aquifer, and analysis of correlations of groundwater quality with land use, depth, age classification, and other potential explanatory factors. The understanding assessment indicated that the concentrations of many constituents were related to depth and groundwater age. However, concentrations of individual constituents or constituent classes also were sometimes related to geochemical conditions, lateral position in the flow system, or land use. High and moderate relative-concentrations of uranium, nitrate, and total dissolved solids (TDS) were detected in some wells where the tops of perforations are within the upper 200 feet of the aquifer system. In wells with the depth to the top of perforations below this depth, concentrations were low. A similar pattern occurred for the sum of herbicide concentrations. These vertical water-chemistry patterns are consistent with the hydrogeologic setting, in which return flows from agricultural and urban land use are the major source of recharge, and withdrawals for irrigation and urban supply are the major source of discharge, resulting in substantial vertical components of groundwater flow. The decrease in concentrations of many constituents with depth reflects in part that groundwater gets older with depth. Tritium, helium-isotopes, and carbon-14 data were used to classify the predominant age of groundwater samples into three categories: modern (water that has entered the aquifer in the last 50 years), pre-modern (water that entered the aquifer more than 50 years, up to tens of thousands of years, ago), and mixed (mixtures of waters with modern and pre-modern ages). Uranium, nitrate, and herbicide concentrations were significantly higher in groundwater having modern- and mixed-ages than pre-modern ages, indicating that these constituents may be affected by anthropogenic activities in the last 50 years. Other patterns in the distribution of nitrate, uranium, and TDS are evident. Isotopic and geochemical data are consistent with partial denitrification of nitrate in some reducing groundwaters in the western and deeper parts of the flow system. Uranium and TDS concentrations increase from east to west across the valley, along the direction of regional lateral groundwater flow. High and moderate relative-concentrations of arsenic can be attributed to reductive dissolution of manganese or iron oxides, or to desorption by high pH waters. Arsenic concentrations also increased with increasing depth and groundwater age. High to moderate relative-concentrations of vanadium primarily are related to high pH under oxic conditions. The frequency of detections of DBCP was greater in areas with orchard-vineyard land use >40 percent and at depths <200 feet. THMs and solvents were correlated positively with percent urban land use. Herbicide concentrations were correlated negatively with percent natural land use. Perchlorate concentrations were significantly greater in waters having modern and mixed ages than waters having pre-modern ages and were significantly and positively correlated with two land uses—percent orchard/vineyard land use and percent urban land use.

California

How could a freshwater swamp produce a chemical signature characteristic of a saltmarsh?

Reduction–oxidation (redox) reaction conditions, which are of great importance for the soil chemistry of coastal marshes, can be temporally dynamic. We present a transect of cores from northwest Florida wherein radical postdepositional changes in the redox regime has created atypical geochemical profiles at the bottom of the sedimentary column. The stratigraphy is consistent along the transect, consisting of, from the bottom upward, carbonate bedrock, a gray clay, an organic mud section, a dense clay layer, and an upper organic mud unit representing the current saltwater marsh. However, the geochemical signature of the lower organic mud unit suggests pervasive redox reactions, although the interval has been identified as representing a freshwater marsh, an unlikely environment for such conditions. Analyses indicate that this discrepancy results from postdepositional diagenesis driven by millennial-scale environmental parameters. Rising sea level that led to the deposition of the capping clay layer, created anaerobic conditions in the freshwater swamp interval, and isolated it hydrologically from the rest of the sediment column. The subsequent infiltration of marine water into this organic material led to sulfate reduction, the buildup of H 2 S and FeS, and anoxic conditions. Continued sulfidation eventually resulted in euxinic conditions, as evidenced by elevated levels of Fe, S, and especially Mo, the diagnostic marker of euxinia. Because this chemical transformation occurred long after the original deposition the geochemical signature does not reflect soil chemistry at the time of deposition and cannot be used to infer syn-depositional environmental conditions, emphasizing the importance of recognizing diagenetic processes in paleoenvironmental studies.

Florida

Water-resources activities of the U.S. Geological Survey in New Mexico, fiscal year 1992

Awareness of our environment in general, and water resources in particular, has brought increased interest in and support of hydrologic data collection and research. The quantity, quality, and distribution of water are extremely important to the future well-being of New Mexico. The State's surface-water resources are minimal and highly variable due to climate and to regulation and diversion; ground-water resources are subject to development that exceeds natural recharge and to potential contamination by land use. Issues related to global climate change, disposal of hazardous wastes, toxic substances in water, water rights, and ground-water contamination are evolving areas of greater public concern. At the same time there is a continuing need for a better understanding of various hydrologic systems and processes in order to manage these limited water resources for maximum benefit to present and future generations. The U.S. Geological Survey has collected and disseminated information on the water resources of New Mexico for more than a century. The Survey began to collect records of streamflow in New Mexico in December 1888 when the first discharge measurements were made on the Rio Grande near the present gaging station at Embudo. This site, called the "birthplace of systematic stream gaging," was chosen to be the training center for the first hydrographers of the Irrigation Survey, a bureau within the original Geological Survey. Since that time, in cooperation with Federal, State, local, and tribal agencies, we have monitored streams at hundreds of sites throughout the State and have a current network of more than 200 streamflow-gaging stations. Through the Cooperative Program, we also have established sites where ground-water levels are monitored to document changes in ground-water storage or where surface-water and groundwater samples are collected to determine water chemistry, and we have undertaken investigative studies to define the availability, quality, and distribution of water resources. Information from the data program and results of investigative studies are made available to water-resources managers, regulators, and the public to be used for the effective management of the State's water resources. This report provides a brief summary of the activities of the New Mexico District for FY (fiscal year) 1992, including our mission, organization, sources of funding, and descriptions of current projects. This report serves to document not only the content of the program, but also the diversity and complexity of that program. Cooperation among water-resources agencies will be essential in effectively dealing with water-related issues facing New Mexico. We look forward to the challenge of addressing these issues by continuing to provide factual hydrologic data and technically sound areal appraisals and interpretive studies.

New Mexico

Multiple stressor effects in relation to declining amphibian populations

Original research discusses the protocols and approaches to studying the effects of multiple environmental stressors on amphibian populations and gives new perspectives on this complicated subject. This new publication integrates a variety of stressors that can act in concert and may ultimately cause a decline in amphibian populations. Sixteen peer-reviewed papers cover: Toxicity Assessment examines methods, which range from long-established laboratory approaches for evaluating adverse chemical effects to amphibians, to methods that link chemicals in surface waters, sediments, and soils with adverse effects observed among amphibians in the field. Field and Laboratory Studies illustrates studies in the evaluation of multiple stressor effects that may lead to declining amphibian populations. A range of laboratory and field studies of chemicals, such as herbicides, insecticides, chlorinated organic compounds, metals, and complex mixtures are also included. Causal Analysis demonstrates the range of tools currently available for evaluating "cause-effect" relationships between environmental stressors and declining amphibian populations. Audience: This new publication is a must-have for scientists and resource management professionals from diverse fields, including ecotoxicology, chemistry, ecology, field biology, conservation biology, and natural resource management.

Special Technical Report

Diversity of diatoms, benthic macroinvertebrates, and fish varies in response to different environmental correlates in Arctic rivers across North America

Climate change poses a significant threat to Arctic freshwater biodiversity, but impacts depend upon the strength of organism response to climate‐related drivers. Currently, there is insufficient knowledge about Arctic freshwater biodiversity patterns to guide assessment, prediction, and management of biodiversity change. As part of the Circumpolar Biodiversity Monitoring Program's first freshwater assessment, we evaluated diversity of diatoms, benthic macroinvertebrates, and fish in North American Arctic rivers. Alpha diversity was assessed in relation to temperature, water chemistry, bedrock geology, and glaciation history to identify important environmental correlates. Biotic composition was compared among groups to evaluate response to environmental gradients. Macroinvertebrate α‐diversity declined strongly with increasing latitude from 48°N to 82°N, whereas diatom and fish diversity peaked around 70°N without a clear latitudinal decline. Macroinvertebrate diversity was significantly positively related to air temperature. Diatom diversity was related to bedrock geology and temperature, whereas fish diversity was related to glaciation history. Fish and macroinvertebrate assemblages differed between sites in western Canada, where invertebrate composition was more variable, and Alaska, where fish composition was more variable. In sites with both diatom and macroinvertebrate data, diatom composition was distinct in Alaska, where richness was highest in former glacial refugia. Macroinvertebrate composition was distinct in lowest‐latitude eastern and high‐latitude western Canadian sites where temperature was highest. Temperature, precipitation, geology, calcium, and substrate size were important environmental correlates for diatoms and macroinvertebrates, although the relative importance of each correlate differed. Diatom taxa were most strongly associated with water chemistry, whereas benthic invertebrate composition related most strongly to precipitation and temperature. This large‐scale study provides the most substantial integration and analysis of river diatom, macroinvertebrate, and fish data from the North American Arctic to date. Findings suggest that macroinvertebrates will show the strongest response to climate‐related shifts in temperature, whereas diatoms and fish are more likely to respond to climate‐induced shifts in nutrients and hydraulic connectivity. However, significant gaps in data coverage limited our ability to reliably evaluate spatial patterns and detect change. These gaps could be reduced by improving collaborative efforts between the U.S.A. and Canada to harmonise future monitoring.

Arctic

Summer runoff generation in foothill catchments of the Colorado Front Range

Climatic shifts, disturbances, and land-use change can alter hydrologic flowpaths, water quality, and water supply to downstream communities. Prior research investigating streamflow generation processes in mountainous areas has largely focused on high-elevation alpine and subalpine catchments; less is known about these processes in lower-elevation foothills and montane catchments. In these lower-elevation ecoregions, precipitation shifts seasonally from snow to rain, which can result in differing seasonal flowpaths. We analyzed stream water for electrical conductivity, SiO 2 , Ca, Mg, Na, Cl, SO 4 , K, and dissolved organic carbon on both a weekly and storm event basis from April to August 2018 in three small (<10 km 2 ) foothill catchments, and one larger (63.2 km 2 ) catchment extending from the foothills to the subalpine ecoregions, in the Colorado Front Range. Using two end-member hydrograph separations and concentration-runoff relationships, we inferred the dominant catchment-scale flowpaths of precipitation to the streams. We selected catchments with varying land use to investigate the relationship between these characteristics and hydrologic flowpaths. We observed that concentrations of lithogenic constituents generally increased and dissolved organic carbon decreased as seasonal runoff decreased in the three foothill catchments, reflecting a transition from shallow subsurface flowpaths to deeper subsurface flowpaths. Elevated SO 4 and Cl concentrations during low-flow periods in two of our catchments suggest that historical or current anthropogenic activities, such as mining, application of road salt, and/or near-stream septic systems, affect local stream and groundwater chemistry. In a foothill catchment with anthropogenic and geologic impervious surfaces, streamflow during storm responses was sourced from faster, surficial flowpaths compared to a less disturbed neighboring catchment, highlighting the influence of anthropogenic land-use on runoff generation. This study provides insight into the fundamental hydrology of foothill catchments and how they may function in the future with human development, precipitation shifts and disturbances.

Colorado

Biomarker similarities between the saline lacustrine Eocene Green River and the Paleoproterozoic Barney Creek Formations

The Paleoproterozoic Barney Creek Formation, which is currently interpreted as a restricted, deep marine paleoenvironment, plays a disproportionate role in our understanding of Proterozoic ocean chemistry and the rise of complex life. The Barney Creek Formation hosts several unusual biomarker features, specifically its methylhopane and carotenoid signatures. Herein, we demonstrate that the saline lacustrine Eocene Green River Formation shares a similar distribution of methylhopanes and carotenoids, which is characteristic of saline lacustrine organic matter more generally. These distinct methylhopane and carotenoid patterns are not observed together in marine organic matter of any geologic age. These results imply a saline lacustrine depositional environment for the Barney Creek Formation, which agrees with earlier but now abandoned depositional models of this formation. As a result, models of Proterozoic ocean chemistry and emergence of complex life that rely on a marine Barney Creek Formation should be re-examined. Alternatively, if Paleoproterozoic marine biomarker signatures resemble those of younger saline lacustrine systems, then this must be recognized to accurately interpret geologic biomarker and paleoenvironmental records.

Colorado, Utah