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Tree swallows as indicators of per- and polyfluoroalkyl substance exposure and effects at select Department of Defense sites along the East Coast and at sites with different sources in the Upper Midwest, United States

Questions remain about the distribution of per- and polyfluoroalkyl substances (PFAS) in the environment, the sources and movement within and between ecosystems, and whether there are effects from such exposure. Information from the Upper Midwest and the mid-Atlantic regions of the United States, which have different PFAS sources, were investigated. Concentrations of Total 40 (sum of 40 PFAS), perfluorooctane sulfonate, perfluorohexane sulfonate, and Total 13 (sum of 13 PFAS) were consistently higher, by as much as a factor of 40, in tree swallow ( Tachycineta bicolor ) tissue samples (eggs, nestlings, and diet) at sites along the East Coast, where aqueous film-forming foams (AFFF) were extensively used when compared with East Coast reference sites. Sites in the Upper Midwest, with other PFAS sources, had qualitatively lower concentrations of PFAS than AFFF source sites. Perfluorooctane sulfonate was the only PFAS detected in all samples. Concentrations of most other PFAS, such as the carboxylates and fluorotelomers, did not differ between AFFF and reference sites. Perfluorohexane sulfonate, the second-most common constituent of some legacy AFFF formulations, was <1% of Total 40 at the reference sites in eggs and nestlings, but perfluorohexane sulfonate represented up to 9.7% (eggs) and 9.0% (nestlings) at AFFF-influenced sites. Despite differences in PFAS exposure, the daily probability of egg and nestling survival, as well as haptoglobin-like activity (PIT54) and total immunoglobulin Y, was similar across all sites. There were also no significant associations between these end points and concentrations of Total 40 or individual PFAS in eggs or nestlings.

East Coast, Upper Midwest↗

Temperature‐related responses of an invasive mussel and 2 unionid mussels to elevated carbon dioxide

Zebra mussels (Dreissena polymorpha) have exacerbated the decline of native freshwater mussels (Order Unionida) in North America since their arrival in the 1980s. Options for controlling invasive mussels, particularly in unionid mussel habitats, are limited. Previously, carbon dioxide (CO2) showed selective toxicity for zebra mussels, relative to unionids, when applied in cool water (12 °C). We first determined 96 h lethal concentrations of CO2 at 5 and 20 °C to zebra mussels and responses of juvenile plain pocketbook (Lampsilis cardium). Next, we compared the time to lethality for zebra mussels at 5, 12, and 20 °C during exposure to partial pressure of CO2 (PCO2) 110¬–120 atmospheres (atm; 1 atm = 101.325 kPa) and responses of juvenile plain pocketbook and fragile papershell (Leptodea fragilis). We found efficacious CO2 treatment regimens at each temperature that were minimally lethal to unionids. At 5 °C, plain pocketbook survived 96 h exposure to the highest PCO2 treatment (139 atm). At 20 °C, the 96 h LC10 (lethal concentration to 10% of animals) for plain pocketbook [173 atm PCO2, 95% confidence interval (CL) 147–198 atm] was higher than the LC99 for zebra mussels (118 atm PCO2, CL 109–127 atm). Lethal time to 99% mortality (LT99) of zebra mussels in 110 to 120 atm PCO2 ranged from 100 h at 20 °C to 300 h at 5 °C. Mean survival of juvenile unionids exceeded 85% in LT99 CO2 treatments at all temperatures. Short-term infusion of 100 to 200 atm PCO2 at a range of water temperatures could reduce biofouling by zebra mussels with limited adverse effects on unionid mussels.

Environmental Toxicology and Chemistry↗

Effects of wastewater disinfection on waterborne bacteria and viruses

Wastewater disinfection is practiced with the goal of reducing risks of human exposure to pathogenic microorganisms. In most circumstances, the efficacy of a wastewater disinfection process is regulated and monitored based on measurements of the responses of indicator bacteria. However, inactivation of indicator bacteria does not guarantee an acceptable degree of inactivation among other waterborne microorganisms (e.g., microbial pathogens). Undisinfected effluent samples from several municipal wastewater treatment facilities were collected for analysis. Facilities were selected to provide a broad spectrum of effluent quality, particularly as related to nitrogenous compounds. Samples were subjected to bench-scale chlorination and dechlorination and UV irradiation under conditions that allowed compliance with relevant discharge regulations and such that disinfectant exposures could be accurately quantified. Disinfected samples were subjected to a battery of assays to assess the immediate and long-term effects of wastewater disinfection on waterborne bacteria and viruses. In general, (viable) bacterial populations showed an immediate decline as a result of disinfectant exposure; however, incubation of disinfected samples under conditions that were designed to mimic the conditions in a receiving stream resulted in substantial recovery of the total bacterial community. The bacterial groups that are commonly used as indicators do not provide an accurate representation of the response of the bacterial community to disinfectant exposure and subsequent recovery in the environment. UV irradiation and chlorination/dechlorination both accomplished measurable inactivation of indigenous phage; however, the extent of inactivation was fairly modest under the conditions of disinfection used in this study. UV irradiation was consistently more effective as a virucide than chlorination/dechlorination under the conditions of application, based on measurements of virus (phage) diversity and concentration. Taken together, and when considered in conjunction with previously published research, the results of these experiments illustrate several important limitations of common disinfection processes as applied in the treatment of municipal wastewaters. In general, it is not clear that conventional disinfection processes, as commonly implemented, are effective for control of the risks of disease transmission, particularly those associated with viral pathogens. Microbial quality in receiving streams may not be substantially improved by the application of these disinfection processes; under some circumstances, an argument can be made that disinfection may actually yield a decrease in effluent and receiving water quality. Decisions regarding the need for effluent disinfection must account for site-specific characteristics, but it is not clear that disinfection of municipal wastewater effluents is necessary or beneficial for all facilities. When direct human contact or ingestion of municipal wastewater effluents is likely, disinfection may be necessary. Under these circumstances, UV irradiation appears to be superior to chlorination in terms of microbial quality and chemistry and toxicology. This advantage is particularly evident in effluents that contain appreciable quantities of ammonia-nitrogen or organic nitrogen.

Water Environment Research↗

Surface-water quality of the Skokomish, Nooksack, and Green-Duwamish rivers and Thornton Creek, Puget Sound Basin, Washington, 1995-98

Streamflow and surface-water-quality data were collected from November 1995 through April 1998 (water years 1996-98) from a surface-water network in the Puget Sound Basin study unit of the U.S. Geological Survey National Water-Quality Assessment program. Water samples collected monthly and during storm runoff events were analyzed for nutrients, major ions, organic carbon, and suspended sediment, and at selected sites, samples were analyzed for pesticides and volatile organic compounds. Eleven sites were established in three major watersheds--two in the Skokomish River Basin, three in the Nooksack River Basin, five in the Green-Duwamish River Basin, and one site in Thornton Creek Basin, a small tributary to Lake Washington. The Skokomish River near Potlatch, Nooksack River at Brennan, and Duwamish River at Tukwila are integrators of mixed land uses with the sampling sites locally influenced by forestry practices, agriculture, and urbanization, respectively. The remaining eight sites are indicators of relatively homogeneous land use/land cover in their basins. The site on the North Fork Skokomish River is an indicator site chosen to measure reference or background conditions in the study unit. In the Nooksack River Basin, the site on Fishtrap Creek is an indicator of agriculture, and the Nooksack River at North Cedarville is an indicator site of forestry practices in the upper watershed. In the Green-Duwamish River Basin, Springbrook Creek is an urban indicator, Big Soos Creek is an indicator of a rapidly developing suburban basin; Newaukum Creek is an indicator of agriculture; and the Green River above Twin Camp Creek is an indicator of forestry practices. Thornton Creek is an indicator of high-density urban residential and commercial development. Conditions during the first 18 months of sampling were dominated by above-normal precipitation. For the Seattle-Tacoma area, water year 1997 was the wettest of the 3 years during the sample-collection period. Nearly 52 inches fell (about 14 inches above average) and monthly precipitation was often 200 percent of normal. The wet years kept streamflows generally above normal and contributed to high concentrations of pesticides, nutrients, suspended sediment, and organic carbon in samples. On the basis of chemical concentrations, dissolved oxygen concentrations, and water temperature, the relative quality of water among the 11 study sites ranged from exceptionally high in the North Fork Skokomish and the Green to fair in Springbrook and Thornton. Water in the large rivers (Skokomish, Nooksack, Green-Duwamish) and in two of the small streams in the Puget Sound Lowlands (Big Soos and Newaukum) was characterized by dilute water chemistry with dissolved solids concentrations less than 130 milligrams per liter. Water in three other small streams in the Lowlands (Fishtrap, Springbrook, and Thornton) had dissolved solids concentrations as high as 320 milligrams per liter. Nutrient and pesticide concentrations mostly were higher in the small streams than in the large rivers. Suspended-sediment concentrations, however, were highest in the large rivers, with averages ranging from 85 to 443 milligrams per liter. During storm and flood events, suspended-sediment concentrations in samples from the Nooksack were as much as 2,800 milligrams per liter, and from the Skokomish, 1,500 milligrams per liter. Out of 86 pesticides and 86 volatile organic compounds analyzed, a total of 35 pesticides and 11 volatile organic compounds were detected at concentrations above laboratory reporting levels in samples collected from the four intensively studied sites, the lower Nooksack River, Duwamish River, Fishtrap Creek, and Thornton Creek. Herbicides were detected more frequently than insecticides. The herbicide prometon was detected in 66 percent of all 124 samples collected, followed by simazine (65 percent), atrazine (64 percent), and the insecticide diazinon (50 percent). The detected volatile organic compounds belonged to one of three general classes--fuel-related, the trihalomethanes, or solvents. Water-quality standards and criteria for drinking water or for the protection of aquatic life were nearly always met, except on occasion by concentrations of dissolved oxygen, iron, and manganese in samples from Springbrook and Fishtrap, and concentrations of diazinon in Thornton and Fishtrap. Concentrations of three other insecticides (carbaryl, chlorpyrifos, and lindane) also did not meet criteria protecting aquatic life in a few samples (from 1 to 5) from Thornton and Fishtrap and from the Duwamish River. Water-quality conditions at the sampling sites resulted from natural characteristics of the watersheds and from human activities. In the Nooksack and Skokomish, natural conditions were probably important contributors to the large suspended-sediment concentrations observed during high streamflow events. However, logging and road building in the basins might also have contributed to the suspended-sediment loads. In the forested study basins, the water chemistry was more dilute, based on dissolved solids and nutrient concentrations. The North Fork Skokomish (indicator site of background conditions) and the Green (indicator site of forestry and natural conditions) were characterized by high-quality water with low concentrations of dissolved solids, nutrients, and sediment and by standards or criteria that were nearly always met. Unlike the high-quality water at the background and forestry sites, natural conditions appear to have adversely affected the quality of water in Springbrook. High concentrations of iron and manganese and low dissolved-oxygen concentrations were possibly the result of ground-water discharge at this site. Of all the sites, nutrient concentrations were highest in the agricultural streams (Fishtrap and Newaukum) and next highest in the urban streams, indicating that human activities affect the water quality of these streams. Of the three large rivers integrating a mix of land uses, the lower Nooksack, in an agricultural setting, on average had the highest total nitrogen and phosphorus concentrations, followed by the Duwamish in an urban setting, and the Skokomish in a forestry-practices setting. In both urban and agricultural settings, pesticides affected water quality at the four sites sampled for organic compounds. However, more types of pesticides were found at the agricultural sites than at the urban sites. The most pesticides were detected in Fishtrap. Many of these were pesticides applied for agricultural purposes, but several were pesticides applied in urban settings, such as those used in maintaining rights-of-way. In urban Thornton Creek, however, high application rates and retail availability of pesticides likely resulted in generally higher concentrations, the detections of certain pesticides in many samples year round, and the number of times insecticide concentrations did not meet chronic criteria for the protection of freshwater aquatic life. The two sites located in urban areas also had more detections of volatile organic compounds and at a higher detection frequency than the two sites in agricultural areas. The most compounds were detected in Thornton, and in the highest concentrations. Conversely, the least number of compounds was detected in the lower Nooksack, with only 2 percent urban land upstream. Methyl tert -butyl ether, an automotive fuel additive, was detected in a few samples from Fishtrap. Many solvents, such as trichloroethene and tetrachloroethene, were detected only in samples from the urban sites on the Duwamish River and Thornton Creek. The only volatile organic compound with a distinctly agricultural signature was 1,2-dichloropropane, detected only in Fishtrap Creek samples.

Washington↗

Geologic history of sea water: An attempt to state the problem

Paleontology and biochemistry together may yield fairly definite information, eventually, about the paleochemistry of sea water and atmosphere. Several less conclusive lines of evidence now available suggest that the composition of both sea water and atmosphere may have varied somewhat during the past; but the geologic record indicates that these variations have probably been within relatively narrow limits. A primary problem is how conditions could have remained so nearly constant for so long. It is clear, even from inadequate data on the quantities and compositions of ancient sediments, that the more volatile materials—H 2 O, CO 2 , Cl, N, and S— are much too abundant in the present atmosphere, hydrosphere, and biosphere and in ancient sediments to be explained, like the commoner rock-forming oxides, as the products of rock weathering alone. If the earth were once entirely gaseous or molten, these “excess” volatiles may be residual from a primitive atmosphere. But if so, certain corollaries should follow about the quantity of water dissolved in the molten earth and the expected chemical effects of a highly acid, primitive ocean. These corollaries appear to be contradicted by the geologic record, and doubt is therefore cast on this hypothesis of a dense primitive atmosphere. It seems more probable that only a small fraction of the total “excess” volatiles was ever present at one time in the early atmosphere and ocean. Carbon plays a significant part in the chemistry of sea water and in the realm of living matter. The amount now buried as carbonates and organic carbon in sedimentary rocks is about 600 times as great as that in today's atmosphere, hydrosphere, and biosphere. If only 1/100 of this buried carbon were suddenly added to the present atmosphere and ocean, many species of marine organisms would probably be exterminated. Furthermore, unless CO 2 is being added continuously to the atmosphere-ocean system from some source other than rock weathering, the present rate of its subtraction by sedimentation would, in only a few million years, cause brucite to take the place of calcite as a common marine sediment. Apparently, the geologic record shows no evidence of such simultaneous extinctions of many species nor such deposits of brucite. Evidently the amount of CO 2 in the atmosphere and ocean has remained relatively constant throughout much of the geologic past. This calls for some source of gradual and continuous supply, over and above that from rock weathering and from the metamorphism of older sedimentary rocks. A clue to this source is afforded by the relative amounts of the different “excess” volatiles. These are similar to the relative amounts of the same materials in gases escaping from volcanoes, fumaroles, and hot springs and in gases occluded in igneous rocks. Conceivably, therefore, the hydrosphere and atmosphere may have come almost entirely from such plutonic gases. During the crystallization of magmas, volatiles such as H 2 O and CO 2 accumulate in the remaining melt and are largely expelled as part of the final fractions. Volcanic eruptions and lava flows have brought volatiles to the earth's surface throughout the geologic past; but intrusive rocks are probably a much more adequate source of the constituents of the atmosphere and hydrosphere. Judged by the thermal springs of the United States, hot springs (carrying only 1 per cent or less of juvenile matter) may be the principal channels by which the “excess” volatiles have escaped from cooling magmas below. This mechanism fails to account for a continuous supply of volatiles unless it also provides for a continuous generation of new, volatile-rich magmas. Possibly such local magmas form by a continuous process of selective fusion of subcrustal rocks, to a depth of several hundred kilometers below the more mobile areas of the crust. This would imply that the volume of the ocean has grown with time. On this point, geologic evidence permits differences of interpretation; the record admittedly does not prove, but it seems consistent with, an increasing growth of the continental masses and a progressive sinking of oceanic basins. Perhaps something like the following mechanism could account for a continuous escape of volatiles to the earth's surface and a relatively uniform composition of sea water through much of geologic time: (1) selective fusion of lower-melting fractions from deep-seated, nearly anhydrous rocks beneath the unstable continental margins and geosynclines; (2) rise of these selected fractions (as granitic and hydrous magmas) and their slow crystallization nearer the surface; (3) essentially continuous isostatic readjustment between the differentiating continental masses and adjacent ocean basins; and (4) renewed erosion and sedimentation, with resulting instability of continental margins and mountainous areas and a new round of selective fusion below.

Geological Society of America Bulletin↗

Groundwater, surface–water, and water-chemistry data, Black Mesa area, northeastern Arizona—2007-2008

The N aquifer is an extensive aquifer and the primary source of groundwater in the 5,400-square-mile Black Mesa area in northeastern Arizona. Availability of water is an important issue in northeastern Arizona because of continued water requirements for industrial and municipal use by a growing population and because of low precipitation in the arid climate of the Black Mesa area, which is typically about 6 to 14 inches per year. The U.S. Geological Survey water-monitoring program in the Black Mesa area began in 1971 and provides information about the long-term effects of groundwater withdrawals from the N aquifer for industrial and municipal uses. This report presents results of data collected as part of the monitoring program in the Black Mesa area from January 2007 to September 2008. The monitoring program includes measurements of (1) groundwater withdrawals, (2) groundwater levels, (3) spring discharge, (4) surface-water discharge, and (5) groundwater chemistry. In 2007, total groundwater withdrawals were 4,270 acre-feet, industrial withdrawals were 1,170 acre-ft, and municipal withdrawals were 3,100 acre-ft. Total withdrawals during 2007 were about 41 percent less than total withdrawals in 2005. From 2006 to 2007, however, total withdrawals increased by 4 percent, industrial withdrawals decreased by approximately 2 percent, and total municipal withdrawals increased by 7 percent. From 2007 to 2008, annually measured water levels in the Black Mesa area declined in 6 of 11 wells measured in the unconfined areas of the N aquifer, and the median change was -0.2 feet. Water levels declined in 9 of 18 wells measured in the confined area of the aquifer. The median change for the confined area of the aquifer was -0.2 feet. From the prestress period (prior to 1965) to 2008, the median water-level change for 33 wells in both the confined and unconfined area was -12.9 feet. Median water-level changes were -1.0 feet for 15 wells measured in the unconfined areas and -33.2 feet for 18 wells measured in the confined area. Spring flow was measured at two springs in 2008. Flow decreased at both Moenkopi School Spring and Pasture Canyon Spring from previous years. Flow fluctuated during the period of record, but a decreasing trend was apparent. Continuous records of surface-water discharge in the Black Mesa area were collected from streamflow-gaging stations at the following sites: Moenkopi Wash at Moenkopi 09401260 (1976 to 2007), Dinnebito Wash near Sand Springs 09401110 (1993 to 2007), Polacca Wash near Second Mesa 09400568 (1994 to 2007), and Pasture Canyon Springs 09401265 (August 2004 to 2007). Median winter flows (November through February) of each water year were used as an index of the amount of groundwater discharge at the above-named sites. For the period of record of each streamflow-gaging station, the median winter flows have generally remained constant, which suggests no change in groundwater. The period of record is too short to determine if there is a trend at Pasture Canyon Spring. In 2008, water samples collected from 6 wells and 2 springs in the Black Mesa area were analyzed for selected chemical constituents and the results compared with previous analyses. Concentrations of dissolved solids, chloride, and sulfate have varied at all 6 wells for the period of record, but neither increasing nor decreasing trends over time were found. Dissolved-solids, chloride, and sulfate concentrations increased at Moenkopi School Spring during the more than 12 years of record at that site. Concentrations of dissolved solids, chloride, and sulfate at Pasture Canyon Spring have not varied much since the early 1980s, and there is no trend in those data.

Arizona↗

Groundwater, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona— 2008–2009

The N aquifer is an extensive aquifer and the primary source of groundwater in the 5,400-square-mile Black Mesa area in northeastern Arizona. Availability of water is an important issue in northeastern Arizona because of continued water requirements for industrial and municipal use by a growing population and because of low precipitation in the arid climate of the Black Mesa area, which is typically about 6 to 14 inches per year. The U.S. Geological Survey water-monitoring program in the Black Mesa area began in 1971 and provides information about the long-term effects of groundwater withdrawals from the N aquifer for industrial and municipal uses. This report presents results of data collected as part of the monitoring program in the Black Mesa area from January 2008 to September 2009. The monitoring program includes measurements of (1) groundwater withdrawals, (2) groundwater levels, (3) spring discharge, (4) surface-water discharge, and (5) groundwater chemistry. In 2008, total groundwater withdrawals were 4,110 acre-feet, industrial withdrawals were 1,210 acre-ft, and municipal withdrawals were 2,900 acre-ft. Total withdrawals during 2008 were about 44 percent less than total withdrawals in 2005. From 2007 to 2008 total withdrawals decreased by 4 percent, industrial withdrawals increased by approximately 3 percent, but total municipal withdrawals decreased by 6 percent. From 2008 to 2009, annually measured water levels in the Black Mesa area declined in 8 of 15 wells that were available for comparison in the unconfined areas of the N aquifer, and the median change was -0.1 feet. Water levels declined in 11 of 18 wells measured in the confined area of the aquifer. The median change for the confined area of the aquifer was -0.2 feet. From the prestress period (prior to 1965) to 2009, the median water-level change for 34 wells in both the confined and unconfined area was -11.8 feet. Also, from the prestress period to 2009, the median water-level changes were -1.6 feet for 16 wells measured in the unconfined areas and -36.7 feet for 18 wells measured in the confined area. Spring flow was measured at three springs in 2009. Flow fluctuated during the period of record, but a decreasing trend was apparent at Moenkopi School Spring and Pasture Canyon Spring. Discharge at Burro spring has remained constant since it was first measured in 1998. Continuous records of surface-water discharge in the Black Mesa area were collected from streamflow-gaging stations at the following sites: Moenkopi Wash at Moenkopi 09401260 (1976 to 2008), Dinnebito Wash near Sand Springs 09401110 (1993 to 2008), Polacca Wash near Second Mesa 09400568 (1994 to 2008), and Pasture Canyon Springs 09401265 (August 2004 to 2008). Median winter flows (November through February) of each water year were used as an index of the amount of groundwater discharge at the above-named sites. For the period of record of each streamflow-gaging station, the median winter flows have generally remained constant, which suggests no change in groundwater discharge. In 2009, water samples collected from 6 wells and 3 springs in the Black Mesa area were analyzed for selected chemical constituents, and the results were compared with previous analyses. Concentrations of dissolved solids, chloride, and sulfate have varied at all 6 wells for the period of record, but neither increasing nor decreasing trends over time were found. Dissolved-solids, chloride, and sulfate concentrations increased at Moenkopi School Spring during the more than 12 years of record at that site. Concentrations of dissolved solids, chloride, and sulfate at Pasture Canyon Spring have not varied much since the early 1980s, and there is no trend in those data. Concentrations of dissolved solids, chloride, and sulfate at Burro Spring have varied for the period of record, but there is no trend in the data.

Arizona↗

Integrated geoscience studies in the Greater Yellowstone Area - Volcanic, tectonic, and hydrothermal processes in the Yellowstone geoecosystem

Yellowstone National Park, rimmed by a crescent of older mountainous terrain, has at its core the Quaternary Yellowstone Plateau, an undulating landscape shaped by forces of volcanism, tectonism, and later glaciation. Its spectacular hydrothermal systems cap this landscape. From 1997 through 2003, the United States Geological Survey Mineral Resources Program conducted a multidisciplinary project of Yellowstone National Park entitled Integrated Geoscience Studies of the Greater Yellowstone Area, building on a 130-year foundation of extensive field studies (including the Hayden survey of 1871, the Hague surveys of the 1880s through 1896, the studies of Iddings, Allen, and Day during the 1920s, and NASA-supported studies starting in the 1970s—now summarized in USGS Professional Paper 729 A through G) in this geologically dynamic terrain. The project applied a broad range of scientific disciplines and state-of-the-art technologies targeted to improve stewardship of the unique natural resources of Yellowstone and enable the National Park Service to effectively manage resources, protect park visitors from geologic hazards, and better educate the public on geologic processes and resources. This project combined a variety of data sets in characterizing the surficial and subsurface chemistry, mineralogy, geology, geophysics, and hydrothermal systems in various parts of the park. The sixteen chapters presented herein in USGS Professional Paper 1717, Integrated Geoscience Studies in the Greater Yellowstone Area—Volcanic, Tectonic, and Hydrothermal Processes in the Yellowstone Geoecosystem , can be divided into four major topical areas: (1) geologic studies, (2) Yellowstone Lake studies, (3) geochemical studies, and (4) geophysical studies. The geologic studies include a paper by Ken Pierce and others on the influence of the Yellowstone hotspot on landscape formation, the ecological effects of the hotspot, and the human experience and human geography of the greater Yellowstone ecosystem as influenced by the Yellowstone hotspot. Another paper by Paul Carrara describes the recent movement of a large landslide block dated by tree-ring analyses in the Tower Falls area. The section under Yellowstone Lake studies begins with a classic paper by J. David Love and others on ancestral Lake Yellowstone. Other papers in this section include results and interpretation of the high-resolution bathymetric, seismic reflection, and submersible studies by Lisa Morgan and others. Ken Pierce and others describe results from their studies of shorelines along Yellowstone Lake and their interpretation of inflation-deflation cycles, tilting, and faulting in the Yellowstone caldera. The influence of sublacustrine hydrothermal vent fluids on the geochemistry of Yellowstone Lake is described by Laurie Balistrieri and others. In Pat Shanks and others’ chapter, hydrothermal reactions, stable-isotope systematics, sinter deposition, and spire formation are related to the geochemistry of sublacustrine hydrothermal deposits in Yellowstone Lake. The geochemical studies section considers park-wide geochemical systems in Yellowstone National Park. In Bob Rye and Alfred Truesdell’s paper, the question of recharge to the deep thermal reservoir underlying the geysers and hot springs of Yellowstone National Park is discussed. Irving Friedman and Dan Norton report on the chloride flux emissions from Yellowstone in their paper questioning whether Yellowstone is losing its steam. Wildlife issues as addressed by examining trace-element and stable-isotope geochemistry are discussed in a chapter by Maurice Chaffee and others. In another chapter by Chaffee and others, natural and anthropogenic anomalies and their potential impact on the environment using geochemistry is reported. Pam Gemery-Hill and others present geochemical data for selected rivers, lake waters, hydrothermal vents, and subaerial geysers for the time interval of 1996–2004. The life cycle of gold deposits near the northeast corner of the park is discussed by Brad Van Gosen. Under the geophysical studies segment, Ray Kokaly and others use AVIRIS (Airborne Visible and Infrared Spectroscopy) data to map vegetation cover and microbial communities in Yellowstone National Park. Eric Livo and others report their results using AVIRIS data on hydrothermally altered rock and hot-spring deposits. In his final paper following a half century of scientific research, Irving Friedman presents data on monitoring changes in geothermal activity at Norris Geyser Basin using satellite telemetry. These papers summarize a near-decade-long effort by the USGS from the late 1990s to mid-2000s. In 2001, the USGS in cooperation with the National Park Service (Yellowstone National Park) and the University of Utah established the Yellowstone Volcano Observatory, the 5th volcano observatory in the United States.

Idaho, Montana, Wyoming↗

Treatability study to evaluate bioremediation of trichloroethene at Site K, former Twin Cities Army Ammunition Plant, Arden Hills, Minnesota, 2020–22

Executive Summary Chlorinated solvents, including trichloroethene (TCE) and other chlorinated volatile organic compounds (cVOCs), are widespread contaminants that can be treated by bioremediation approaches that enhance anaerobic reductive dechlorination. Reductive dechlorination can be enhanced either through the addition of an electron donor (biostimulation) or the addition of a known dechlorinating culture (bioaugmentation) along with an electron donor. Although bioremediation has been applied at many TCE-contaminated groundwater sites, application in source zones at sites where residual dense nonaqueous phase liquid (DNAPL) is present is more limited. In this study, laboratory and field treatability tests were completed to evaluate the potential application of anaerobic bioremediation for a shallow groundwater plume containing TCE in a perched alluvial aquifer at Site K, former Twin Cities Army Ammunition Plant, Arden Hills, Minnesota, which was on the National Priorities List as the New Brighton/Arden Hills Superfund site until 2019. In addition to the presence of residual DNAPL at the site, temporal variability in groundwater flow directions and input of oxygenated recharge were possible complicating factors for the application of enhanced anaerobic biodegradation in the shallow plume. The Site K plume extends beneath the footprint of Building 103, which was demolished in 2006, and soil excavations to a maximum depth of 6 feet (ft) below ground surface in 2014 were known to leave some deeper contaminated soil in place in the TCE source area. Groundwater treatment at the site, formalized as part of the 1997 Record of Decision, has been in operation since 1986 and consists of an extraction trench at the downgradient edge of the plume to collect groundwater, which is then pumped to an on-site air stripper. Groundwater concentrations in the plume have been relatively stable since treatment began, indicating a continued source of TCE in the aquifer. The desire for a destructive remedy that would enhance the removal of cVOCs in the aquifer at Site K and shorten the remediation timeframe led the U.S. Army to request that the U.S. Geological Survey conduct a groundwater treatability study to assess bioremediation. This report describes the U.S. Geological Survey bioremediation treatability study conducted during 2020–22, including pre-design site characterization to assist in formulating the bioremediation approach, laboratory experiments to support the design of the field pilot test, and implementation and 1-year performance monitoring results for the pilot test. Pre-design site characterization included the collection of soil cores for cVOC analysis and lithologic descriptions and the re-installment of three wells to obtain hydrologic measurements and initial groundwater chemistry. Relatively flat head gradients were measured at the site, and substantial decreases in water-level elevations occurred from spring to summer (May–July 2021). Continuous water-level monitoring indicated a rapid response to precipitation. Groundwater flow velocities were consistently less than 0.5 foot per day, and the pilot bioremediation test was therefore designed with short lateral distances (about 5 ft) between injection and individual monitoring points. Soil analyses confirmed that high volatile organic compound contamination was left in place in the source area. The highest concentrations were near or in clay at the base of the perched aquifer. Concentrations of cVOCs measured in the replaced wells were consistent with historical data and had a maximum TCE concentration of 57,700 micrograms per liter (μg/L), indicative of nearby residual DNAPL based on the general rule of observed concentrations exceeding 1 percent of solubility. The primary TCE daughter product detected was 1,2-cis-dichloroethene (cisDCE), which indicated limited reductive dechlorination in the plume. Groundwater in both the source and downgradient areas was relatively reducing during the pre-design characterization, particularly in the source area where methane concentrations greater than 400 μg/L were measured. Initial laboratory tests conducted using native aquifer microorganisms from the three replacement wells showed that anaerobic TCE biodegradation rates were low when biostimulated with the addition of sodium lactate as an electron donor, also known as a carbon donor, and resulted in the production of only cisDCE. Addition of a known dechlorinating culture, WBC-2, however, resulted in rapid biodegradation and production of ethene, verifying complete reductive dechlorination of TCE. Microcosms constructed with aquifer soil collected from the site were used to evaluate other electron donors besides lactate to support reductive dechlorination by WBC-2, including corn syrup as an alternative fast-release compound and whey, soy-based vegetable oil, and 3-D Microemulsion (Regenesis, San Clemente, California) as slow-release compounds. First-order rate constants for total organic chlorine removal in these WBC-2 amended microcosms were greatest with either lactate or vegetable oil as the donor, ranging between 0.061 and 0.047 per day or corresponding half-lives of 11–15 days. Testing of commercial products in other WBC-2-bioaugmented microcosms led to selection for the field pilot test of an emulsified vegetable oil product that also contained some sodium lactate as a fast-release donor. Delaying the addition of WBC-2 relative to the donor in the microcosms resulted in the most rapid overall biodegradation rates. The selected design for the pilot test utilized three separate test plots, each about 30-ft wide and 60-ft long: plots GS1 and GS2 in the source area of the plume and plot GS3 in the downgradient area of the plume near the excavation trench. Each test plot had one injection well, one monitoring well upgradient from the injection point, and 12 surrounding monitoring wells in a grid to capture variable groundwater flow directions. Donor injections, which included a bromide tracer, were completed in October 2021, immediately following baseline sampling, and the WBC-2 culture was injected about 40 days later, between November 30 and December 2, 2021. Performance monitoring conducted until December 2022 included hydrologic measurements and analyses of cVOCs, redox-sensitive constituents, dissolved organic carbon, bromide, volatile fatty acids, compound-specific carbon isotopes, and microbial communities. The biogeochemical data collected during the pilot tests in the three treatment plots showed that enhanced, complete reductive dechlorination of cVOCs in the groundwater was achieved in the GS1 and GS3 plots. In contrast, evidence of distribution of the injected amendments and subsequent biodegradation was limited in GS2, which was in an area of more heterogeneous soil lithology and low water table elevations. The molar composition of volatile organic compounds in the GS1 and GS3 plots was dominated by ethene in wells that were reached by the injected amendments by the end of the monitoring period. In the GS1 and GS3 plots, similar patterns were observed of cVOC concentrations decreasing to near detection levels, or below, at some wells sampled in July and October 2022, whereas ethene became dominant and indicated sustained complete reductive dechlorination. Baseline cVOC concentrations were more than a factor of 10 higher in the groundwater in the GS1 plot than in GS3, but no apparent inhibition of complete dechlorination occurred. As expected from the initial pre-design site data and the laboratory experiments, enhanced dissolution of residual DNAPL coupled to biodegradation was evident in the GS1 plot, where a marked increase in dichloroethene (DCE) above the initial baseline and upgradient TCE and DCE concentrations occurred. DCE concentrations subsequently declined where DNAPL dissolution was evident, concurrent with production of vinyl chloride and then predominantly ethene. Thus, overall biodegradation rates outpaced the DNAPL dissolution and desorption and DCE production in the source area. This success in complete degradation to predominantly ethene was achieved even in areas where the DCE concentrations reached a maximum of about 30,000 μg/L. Compound specific isotope analysis of carbon in TCE, cisDCE, trans-1,2-dichloroethene, and vinyl chloride was conducted to provide another line of evidence of the occurrence and extent of anaerobic biodegradation. Along a flow path in each plot that was affected by the injected amendments, carbon isotopes in the TCE and daughter cVOCs in the groundwater became isotopically heavier, indicating biodegradation. Enhanced biodegradation rates calculated from the field tests in GS1 and GS3 showed half-lives of 36.9–75.3 days for DCE degradation and 9.48–38.5 days for ethene production. Notably, these ethene production rates calculated from the field tests are consistent with the results of WBC-2-bioaugmented microcosms amended with either lactate or vegetable oil, which had half-lives for total organic chlorine removal that ranged from 11 to 15 days. These rates indicated rapid enhanced biodegradation, which is promising for application of a full-scale bioremediation remedy. Ultimately, however, the mass of residual or sorbed TCE in the aquifer that remains accessible for dissolution and biodegradation would likely control the time required for a full-scale bioremediation effort to achieve performance goals for TCE and cisDCE specified in the Record of Decision for Site K. The field pilot tests showed that the relatively low hydraulic head gradients and temporal changes in groundwater flow directions in the shallow aquifer would add complexity to a full-scale bioremediation effort. The radius of influence (ROI) at GS1 and GS3 (16.3 ft and 12.7 ft, respectively) were close to the design ROI of 15 ft. The estimated ROI at GS2 was about four times the design ROI, but may be less reliable at this location owing to groundwater flow direction. In addition, the low temperatures following WBC-2 injection in late November to early December 2021, in combination with the low hydraulic head gradients, were probably major factors in the delay observed before the onset of enhanced biodegradation following injection of the culture. Additional test injections could be beneficial to optimize the timing of donor and culture injections with the variable temperatures and hydraulic head in the shallow aquifer.

Minnesota↗

Ambient quality of ground water in the vicinity of Naval Submarine Base Bangor, Kitsap County, Washington, 1995

A study of the ambient ground-water quality in the vicinity of Naval Submarine Base (SUBASE) Bangor was conducted to provide the U.S. Navy with background levels of selected constituents. The Navy needs this information to plan and manage cleanup activities on the base. During March and April 1995, 136 water-supply wells were sampled for common ions, trace elements, and organic compounds; not all wells were sampled for all constituents. Man-made organic compounds were detected in only two of fifty wells, and the sources of these organic compounds were attributed to activities in the immediate vicinities of these off-base wells. Drinking water standards for trichloroethylene, iron, and manganese were exceeded in one of these wells, which was probably contaminated by an old local (off-base) dump. Ground water from wells open to the following hydrogeologic units (in order from shallow to deep) was investigated: the Vashon till confining unit (Qvt, three wells); the Vashon aquifer (Qva, 54 wells); the Upper confining unit (QC1, 16 wells); the Permeable interbeds within QC1 (QC1pi, 34 wells); and the Sea-level aquifer (QA1, 29 wells).The 50th and 90th percentile ambient background levels of 35 inorganic constituents were determined for each hydrogeologic unit. At least ten measurements were required for a constituent in each hydrogeologic unit for determination of ambient background levels, and data for three wells determined to be affected by localized activities were excluded from these analyses. The only drinking water standards exceeded by ambient background levels were secondary maximum contaminant levels for iron (300 micrograms per liter), in QC1 and QC1pi, and manganese (50 micrograms per liter), in all of the units. The 90th percentile values for arsenic in QC1pi, QA1, and for the entire study area are above 5 micrograms per liter, the Model Toxics Control Act Method A value for protecting drinking water, but well below the maximum contaminant level of 50 micrograms per liter for arsenic. The manganese standard was exceeded in 38 wells and the standard for iron was exceeded in 12 wells. Most of these wells were in QC1 or QC1pi and had dissolved oxygen concentrations of less than 1 milligram per liter and dissolved organic carbon concentrations greater than 1 milligram per liter. The dissolved oxygen concentration is generally lower in the deeper units, while pH increases; the recommended pH range of 6.5-8.5 standard units was exceeded in 9 wells. The common-ion chemistry was similar for all of the units.

Washington↗

Ground-water, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona— 2006-07

The N aquifer is the major source of water in the 5,400 square-mile Black Mesa area in northeastern Arizona. Availability of water is an important issue in northeastern Arizona because of continued water requirements for industrial and municipal use and the needs of a growing population. Precipitation in the Black Mesa area is typically about 6 to 14 inches per year. The water-monitoring program in the Black Mesa area began in 1971 and is designed to provide information about the long-term effects of ground-water withdrawals from the N aquifer for industrial and municipal uses. This report presents results of data collected for the monitoring program in the Black Mesa area from January 2006 to September 2007. The monitoring program includes measurements of (1) ground-water withdrawals, (2) ground-water levels, (3) spring discharge, (4) surface-water discharge, and (5) ground-water chemistry. Periodic testing of ground-water withdrawal meters is completed every 4 to 5 years. The Navajo Tribal Utility Authority (NTUA) yearly totals for the ground-water metered withdrawal data were unavailable in 2006 due to an up-grade within the NTUA computer network. Because NTUA data is often combined with Bureau of Indian Affairs data for the total withdrawals in a well system, withdrawals will not be published in this year's annual report. From 2006 to 2007, annually measured water levels in the Black Mesa area declined in 3 of 11 wells measured in the unconfined areas of the N aquifer, and the median change was 0.0 feet. Measurements indicated that water levels declined in 8 of 17 wells measured in the confined area of the aquifer. The median change for the confined area of the aquifer was 0.2 feet. From the prestress period (prior to 1965) to 2007, the median water-level change for 30 wells was -11.1 feet. Median water-level changes were 2.9 feet for 11 wells measured in the unconfined areas and -40.2 feet for 19 wells measured in the confined area. Spring flow was measured once in 2006 and once in 2007 at Moenkopi School Spring. Flow decreased by 18.9 percent at Moenkopi School Spring. During the period of record, flow fluctuated, and a decreasing trend was apparent. Continuous records of surface-water discharge in the Black Mesa area have been collected from streamflow gages at the following sites: Moenkopi Wash at Moenkopi (1976 to 2006), Dinnebito Wash near Sand Springs (1993 to 2006), Polacca Wash near Second Mesa (1994 to 2006), and Pasture Canyon Springs (August 2004 to December 2006). Median flows during November, December, January, and February of each water year were used as an index of the amount of ground-water discharge to the above named sites. For the period of record at each streamflow-gaging station, the median winter flows have generally remained even, showing neither a significant increase nor decrease in flows. There is not a long enough period of record for Pasture Canyon Spring for a trend to be apparent. In 2007, water samples were collected from 1 well and 1 spring in the Black Mesa area and were analyzed for selected chemical constituents. Concentrations of dissolved solids, chloride, and sulfate have varied at Peabody well 5 for the period of record, and there is an apparent increasing trend. Dissolved-solids, chloride, and sulfate concentrations increased at Moenkopi School Spring during the more than 12 years of record.

Arizona↗

Groundwater, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona—2013–2015

The Navajo (N) aquifer is an extensive aquifer and the primary source of groundwater in the 5,400-square-mile Black Mesa area in northeastern Arizona. Availability of water is an important issue in northeastern Arizona because of continued water requirements for industrial and municipal use by a growing population and because of low precipitation in the arid climate of the Black Mesa area. Precipitation in the area typically is between 6 and 16 inches per year. The U.S. Geological Survey water-monitoring program in the Black Mesa area began in 1971 and provides information about the long-term effects of groundwater withdrawals from the N aquifer for industrial and municipal uses. This report presents results of data collected as part of the monitoring program in the Black Mesa area from January 2013 to December 2015. The monitoring program includes measurements of (1) groundwater withdrawals (pumping), (2) groundwater levels, (3) spring discharge, (4) surface-water discharge, and (5) groundwater chemistry. In 2013, total groundwater withdrawals were 3,980 acre-feet (ft), in 2014 total withdrawals were 4,170 acre-ft, and in 2015 total withdrawals were 3,970 acre-ft. From 2013 to 2015 total withdrawals varied by less than 5 percent. From 2014 to 2015, annually measured water levels in the Black Mesa area declined in 9 of 15 wells that were available for comparison in the unconfined areas of the N aquifer, and the median change was -0.1 feet. Water levels declined in 3 of 16 wells measured in the confined area of the aquifer. The median change for the confined area of the aquifer was 0.6 feet. From the prestress period (prior to 1965) to 2015, the median water-level change for 34 wells in both the confined and unconfined areas was -13.2 feet; the median water-level changes were -1.7 feet for 16 wells measured in the unconfined areas and -42.3 feet for 18 wells measured in the confined area. Spring flow was measured at four springs in 2014. Flow fluctuated during the period of record for Burro Spring and Unnamed Spring near Dennehotso, but a decreasing trend was statistically significant (p<0.05) at Moenkopi School Spring and Pasture Canyon Spring. Discharge at Burro Spring has remained relatively constant since it was first measured in the 1980s and discharge at Unnamed Spring near Dennehotso has fluctuated for the period of record. Trend analysis for discharge at Moenkopi and Pasture Canyon Springs yielded a slope significantly different (p<0.05) from zero. Continuous records of surface-water discharge in the Black Mesa area were collected from streamflow-gaging stations at the following sites: Moenkopi Wash at Moenkopi 09401260 (1976 to 2015), Dinnebito Wash near Sand Springs 09401110 (1993 to 2015), Polacca Wash near Second Mesa 09400568 (1994 to 2015), and Pasture Canyon Springs 09401265 (2004 to 2015). Median winter flows (November through February) of each water year were used as an index of the amount of groundwater discharge at the above-named sites. For the period of record of each streamflow-gaging station, the median winter flows have generally remained constant, which suggests no change in groundwater discharge. In 2014, water samples collected from four springs in the Black Mesa area were analyzed for selected chemical constituents, and the results were compared with previous analyses. Dissolved solids, chloride, and sulfate concentrations increased at Moenkopi School Spring during the more than 25 years of record at that site. Concentrations of dissolved solids, chloride, and sulfate at Pasture Canyon Spring have not varied significantly (p>0.05) since the early 1980s, and there is no increasing or decreasing trend in those data. Concentrations of dissolved solids, chloride, and sulfate at Burro Spring and Unnamed Spring near Dennehotso have varied for the period of record, but there is no increasing or decreasing statistical trend in the data.

Arizona↗

Analysis of water use associated with hydraulic fracturing and determination of baseline water quality in watersheds within the shale play of eastern Ohio, 2021–23

The U.S. Geological Survey, in cooperation with the Ohio Department of Natural Resources, performed a two-part study to (1) assess water use and temporal trends and changes in streamflow, and to (2) characterize 2021–23 baseline water quality, as they relate to oil and gas extraction activities in selected eastern Ohio watersheds. Between calendar years 2010 and 2019, hydraulic fracturing water withdrawals totaling about 27,168 million gallons were reported at 643 locations in Ohio. In 2021, wells developed with hydraulic fracturing were the source of most of the oil and gas produced in Ohio. Daily streamflow time-series data from seven study gages and two reference gages were used to assess temporal trends and changes in streamflow. The study gages were in basins with reported water withdrawals for hydraulic fracturing. The reference gages, which have long periods of record and were subject to minimal streamflow regulation, were in nearby basins with no hydraulic fracturing water withdrawals. Trend slopes for the period of record annual minimum and median daily streamflows and for annual daily streamflow nonexceedance probabilities less than 0.9 were all uniformly positive at the study and reference gages. This trend indicates a consistently increasing pattern over the periods of record, except for high flows. In addition, analyses of annual streamflow statistics showed no general indication that low flows or extreme low flows at the reference or study gages have lowered, become more frequent, or lengthened in duration since 2010, when records for hydraulic fracturing water withdrawals began in Ohio. In fact, in almost all cases, the opposite was indicated. Nonexceedance percentiles of daily streamflows were compared between the full and pre-2012 periods of record for reference and study gages. The streamflows associated with nonexceedance percentiles in the lower quartile of daily streamflows determined for the full period of record were larger than or equal to those determined for the pre-2012 period of record for all study and reference gages. This indicates that low flows did not decrease during the post-2011 period of record when water was withdrawn for hydraulic fracturing. Water-quality data were collected eight times at each of eight sampling sites (six of which were colocated with the study gages). Sampling was done during a variety of flow conditions to assess baseline water quality. In 2021, the 8 sampling sites had drainage basins that were wholly or partially within 7 of the 10 most active counties in Ohio for oil and gas development. As part of the record of baseline conditions, water-quality data were used to assess (1) water types based on major-ion chemistry; (2) sources of salinity to streams; (3) exceedances of aquatic life use criteria; and (4) the correlations between water chemistry and drainage-basin characteristics, such as density of oil and gas wells, density of wastewater treatment plants, or the percentage of different types of land cover (agriculture, developed, forest). Seven of the water-quality sampling sites were designated as coal-mine impacted based on criteria developed for assessing mine-drainage impacts in Ohio. Mine drainage from historical coal mining in the region likely affected the quality of these streams and complicated the use of some constituents typically used as indicators of oil and gas influence. Based on major-ion chemistry, three main types of water were in the study area―sulfate (three sites), calcium-bicarbonate (one site), and mixed bicarbonate-chloride (four sites) type waters. One site had samples with a higher proportion of sodium and chloride ions than other stream samples, indicating potential contamination with oil-field brine or road salt. Binary mixing curves revealed that 11 samples from 4 of the sampling sites likely contained a component of brine. The results of the baseline assessment of surface-water quality in the study area showed no exceedances of Ohio Environmental Protection Agency aquatic life use criteria. Spearman’s rank correlation coefficients indicated no significant positive correlations with the density of vertical or horizontal oil and gas wells.

Ohio↗

Ecological restructuring in experimental aquatic mesocosms due to the application of diflubenzuron

Diflubenzuron is a chitin-inhibiting insecticide that is registered for use in controlling a multitude of invertebrate pests. The selective mode of action of diflubenzuron provided us with a unique tool for examining the indirect responses of an experimental aquatic ecosystem following direct impacts at the primary consumer (invertebrate) trophic level. Twelve outdoor aquatic mesocosms (0.1 ha each) were randomly assigned to three treatments of diflubenzuron (four mesocosms/treatment): control, monthly (five total 10-μg/L applications), or biweekly (twice monthly; nine total 10-μg/L applications). Direct impacts on invertebrates (numbers and species composition of insects and zooplankton) and indirect impacts on fish (mortality, growth, and reproduction of bluegill sunfish and largemouth bass), phytoplankton (biomass and productivity), and water quality were measured over 16 weeks posttreatment. Both monthly and biweekly treatments of diflubenzuron decreased total numbers (fivefold reduction) and species richness (twofold reduction) and increased dominance (twofold increase) of zooplankton within 4 weeks posttreatment; Cladocerans, Copepods, and Rotifers were all sensitive. Diflubenzuron reduced species richness of emergent insects, which resulted in increased dominance by a few species; however, impacts on emergent insects were confounded by a treatment × time interaction. Direct reductions in invertebrate grazers caused indirect increases in algal biomass. Indirect effects on biomass (50% reduction) and individual weight (50% reduction) of juvenile bluegill occurred because of apparent decreases in invertebrate food resources. No statistically significant impacts were observed on adult bluegill or largemouth bass for the duration of the experiment. Results indicated that diflubenzuron had both direct and indirect impacts on the experimental aquatic ecosystems under the conditions tested.

Environmental Toxicology and Chemistry↗

Optical resolution of rotenoids

Optical resolution of selected rotenoids containing 1-3 asymmetric centers in dihydrobenzopyranofuroben-zopyranone and dihydrobisbenzopyranopyranone series has been achieved on two chiral high-performance liquid chromatographic (hplc) stationary phases. In most cases, the absolute stereochemistry at the cis -B/C ring junction of the rotenoidal antipodes can be related to their elution order. Generally, the 6a&alpha;,12a&alpha;-enantiomers were more strongly retained by the chiral substrate than their corresponding optical antipodes. The elution-configuration relationship provides potential utility for predicting the absolute configuration of related rotenoidal compounds. Chiral phase hplc on amino-acid-bonded-silica yielded results explicable in terms of Pirkle's bonding schemes for chiral recognition. Resolution data for 12a-hydroxy-, 12a-methoxy-, and 12-hydroxyiminorotenoids further corroborate the mechanistic rationale, and demonstrate that nonpolar &pi;-&pi; interactions appeared to be important for enantiomeric separation on helic poly-triphenylmethylacryl-ate-silica (CPOT). In the latter system, steric effects and conformational factors in association with the modification of E-ring structures might play significant roles in the chiral separation process in view of the reversal to the elution order observed for all methoxylated rotenoids and elliptone derivatives including the parent deguelin. The unique separability (&alpha; = 1.44) of 12a-hydroxyelliptone on CPOT was suggestive of structural effects of the 5-side chain on the resolution of the rotenoids having a five-membered-E-ring. The results obtained with two different types of chiral phases are complementary and useful for optical resolution of a wide variety of natural and synthetic rotenoidal compounds.

Journal of Heterocyclic Chemistry↗

Groundwater, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona - 2010-2011

The Navajo (N) aquifer is an extensive aquifer and the primary source of groundwater in the 5,400-square-mile Black Mesa area in northeastern Arizona. Availability of water is an important issue in northeastern Arizona because of continued water requirements for industrial and municipal use by a growing population and because of low precipitation in the arid climate of the Black Mesa area. Precipitation in the area is typically between 6 to 14 inches per year. The U.S. Geological Survey water-monitoring program in the Black Mesa area began in 1971 and provides information about the long-term effects of groundwater withdrawals from the N aquifer for industrial and municipal uses. This report presents results of data collected as part of the monitoring program in the Black Mesa area from January 2010 to September 2011. The monitoring program includes measurements of (1) groundwater withdrawals, (2) groundwater levels, (3) spring discharge, (4) surface-water discharge, and (5) groundwater chemistry. In 2010, total groundwater withdrawals were 4,040 acre-ft, industrial withdrawals were 1,170 acre-ft, and municipal withdrawals were 2,870 acre-ft. Total withdrawals during 2010 were about 42 percent less than total withdrawals in 2005 because of Peabody Western Coal Company's discontinued use of water to transport coal in a slurry. From 2009 to 2010 total withdrawals decreased by 5 percent; industrial withdrawals decreased by approximately 16 percent, and total municipal withdrawals increased by 1 percent. From 2010 to 2011, annually measured water levels in the Black Mesa area declined in 7 of 15 wells that were available for comparison in the unconfined areas of the N aquifer, and the median change was 0.0 foot. Water levels declined in 11 of 18 wells measured in the confined area of the aquifer. The median change for the confined area of the aquifer was -0.7 foot. From the prestress period (prior to 1965) to 2011, the median water-level change for 33 wells in both the confined and unconfined areas was -15.0 feet. Also, from the prestress period to 2011, the median water-level changes were -1.2 foot for 15 wells measured in the unconfined areas and -41.2 feet for 18 wells measured in the confined area. Spring flow was measured at three springs in 2011. Flow fluctuated during the period of record, but a decreasing trend was apparent at Moenkopi School Spring and Pasture Canyon Spring. Discharge at Burro Spring has remained relatively constant since it was first measured in the 1980s. Continuous records of surface-water discharge in the Black Mesa area were collected from streamflow-gaging stations at the following sites: Moenkopi Wash at Moenkopi 09401260 (1976 to 2010), Dinnebito Wash near Sand Springs 09401110 (1993 to 2010), Polacca Wash near Second Mesa 09400568 (1994 to 2010), and Pasture Canyon Springs 09401265 (2004 to 2010). Median winter flows (November through February) of each water year were used as an index of the amount of groundwater discharge at the above-named sites. For the period of record of each streamflow-gaging station, the median winter flows have generally remained constant, which suggests no change in groundwater discharge. In 2011, water samples collected from 11 wells and 4 springs in the Black Mesa area were analyzed for selected chemical constituents, and the results were compared with previous analyses. Concentrations of dissolved solids, chloride, and sulfate have varied at all 11 wells for the period of record, but neither increasing nor decreasing trends over time were found. Dissolved-solids, chloride, and sulfate concentrations increased at Moenkopi School Spring during the more than 12 years of record at that site. Concentrations of dissolved solids, chloride, and sulfate at Pasture Canyon Spring have not varied much since the early 1980s, and there is no increasing or decreasing trend in those data. Concentrations of dissolved solids, chloride, and sulfate at Burro Spring and Unnamed Spring near Dennehotso have varied for the period of record, but there is no increasing or decreasing trend in the data.

Arizona↗

Completion summary for boreholes USGS 148, 148A, and 149 at the Materials and Fuels Complex, Idaho National Laboratory, Idaho

In 2019, the U.S. Geological Survey (USGS), in cooperation with the U.S. Department of Energy, drilled and constructed boreholes USGS 148A and USGS 149 for stratigraphic framework analyses and long-term groundwater monitoring of the eastern Snake River Plain aquifer at the Idaho National Laboratory (INL) in southeastern Idaho. Initially, boreholes USGS 148A and USGS 149 were continuously cored to allow the USGS and INL subcontractor to collect select geophysical and seismic data and evaluate properties of recovered core material. The USGS geophysical data and descriptions of core material are described in this report; however, data collected by the INL contractor, including seismic data, are not included as part of the report. The unsaturated zone at both borehole locations is relatively thick, depth to water was measured at approximately 663.6 feet (ft) below land surface (BLS) in USGS 148A, and at approximately 654.1 ft BLS at USGS 149. On completion of coring and data collection, both boreholes (USGS 148A and USGS 149) were repurposed as monitoring wells. Well USGS 148A was constructed to a depth of 759 ft BLS and instrumented with a dedicated submersible pump and measurement line; well USGS 149 was constructed to a depth of 974 ft BLS and instrumented with a multilevel monitoring system (Westbay TM ). Geophysical data, collected by the USGS, were used to characterize the subsurface geology and aquifer conditions. Natural gamma log measurements were used to assess sediment-layer thickness and location. Neutron and gamma-gamma source logs were used to confirm fractured and vesicular basalt identified for aquifer testing and multilevel monitoring well zone testing. Acoustic televiewer logs, collected for well USGS 149, were used to identify fractures and assess groundwater movement when compared with neutron measurements. Furthermore, gyroscopic deviation measurements were used to measure horizontal and vertical displacement for the constructed boreholes USGS 148A and USGS 149. A single-well aquifer test was done in well USGS 148A during November 6–7, 2019, to provide estimates of transmissivity and hydraulic conductivity. Estimates for transmissivity and hydraulic conductivity were 6.34×10 3 feet squared per day and 3.17 feet per day, respectively. The aquifer test was run overnight (21.3 hours) and measured drawdown was relatively small (0.09 ft) at sustained pumping rates ranging from 15.7 to 16.1 gallons per minute. The transmissivity estimates for well USGS 148A were slightly lower than those determined from previous aquifer tests for wells near the Materials and Fuels Complex, but well within range of other aquifer tests done at the INL. Water-quality samples, collected from well USGS 148A and from four zones in well USGS 149, were analyzed for cations, anions, metals, nutrients, volatile organic compounds, stable isotopes, and radionuclides. Water samples for most of the inorganic constituents showed similar chemistry in USGS 148A and all four zones in USGS 149. Water samples for stable isotopes of oxygen and hydrogen indicated some possible influence of irrigation on the water quality. Nitrate plus nitrite concentrations indicated influence from anthropogenic sources. The volatile organic compound and radiochemical data indicated that wastewater disposal practices at the Materials and Fuels Complex or from drilling had no detectable influence on these wells.

Idaho↗

Studies on geological background and source of fluorine in drinking water in the North China Plate fluorosis areas

Endemic fluorosis in northern China is usually produced by high fluorine (F) content in drinking water. Thirty-one samples of drinking waters, mainly well waters and nearly 200 samples of rocks, loess, and coal were analyzed for F content using the combustion hydrolysis-fluoride-ion selective electrode (ISE) method. The geologic cross sections of two well-known fluorosis basins were studied. The solubility of F in different rock types collected from fluorosis areas was determined. Results showed that areas of endemic fluorosis in northern China are located in coal-bearing basins which are comprised of three stratagraphic portions. The lowest portion is Precambrian granitic rocks or Cambrian-Ordovician carbonates. The middle portion consists of Permo-Carboniferous or Jurassic coal-bearing sequences. The upper portion is 0-400 m Pleistocene loess. Flourine content in the Precambrian granite-gneiss contained (a) 1090-1460 ppm, in the Cambrian-Ordovician limestone and dolomite, (b) 52-133 ppm, in black shales and coal gob of Permo-Carboniferous coal-bearing strata, (c) 200-700 ppm, and (d) Pleistocene loess 454-542 ppm. The solubility of F in black shales of coal-bearing sequences was higher than in Precambrian granitic rocks, and both were more soluble than loess. F solubility from Precambrian granitic rocks was moderate, but Precambrian granitic rocks have high F content and thus contribute an appreciable amount of ion to the shallow groundwater (well water). Varying F content in shallow groundwater is controlled by geological conditions. The sources of F in the shallow groundwater from fluorosis areas in northern China are mainly derived from black shales of coal-bearing sequences and Precambrian granitic basement in the basins of northern China. ?? 2008 Taylor & Francis.

Toxicological and Environmental Chemistry↗