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Compilation of minimum and maximum isotope ratios of selected elements in naturally occurring terrestrial materials and reagents

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope abundance variations potentially are large enough to result in future expansion of their atomic weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope-abundance variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio. There are no internationally distributed isotopic reference materials for the elements zinc, selenium, molybdenum, palladium, and tellurium. Preparation of such materials will help to make isotope ratio measurements among laboratories comparable. The minimum and maximum concentrations of a selected isotope in naturally occurring terrestrial materials for selected chemical elements reviewed in this report are given below: Isotope Minimum mole fraction Maximum mole fraction -------------------------------------------------------------------------------- 2H 0 .000 0255 0 .000 1838 7Li 0 .9227 0 .9278 11B 0 .7961 0 .8107 13C 0 .009 629 0 .011 466 15N 0 .003 462 0 .004 210 18O 0 .001 875 0 .002 218 26Mg 0 .1099 0 .1103 30Si 0 .030 816 0 .031 023 34S 0 .0398 0 .0473 37Cl 0 .240 77 0 .243 56 44Ca 0 .020 82 0 .020 92 53Cr 0 .095 01 0 .095 53 56Fe 0 .917 42 0 .917 60 65Cu 0 .3066 0 .3102 205Tl 0 .704 72 0 .705 06 The numerical values above have uncertainties that depend upon the uncertainties of the determinations of the absolute isotope-abundance variations of reference materials of the elements. Because reference materials used for absolute isotope-abundance measurements have not been included in relative isotope abundance investigations of zinc, selenium, molybdenum, palladium, and tellurium, ranges in isotopic composition are not listed for these elements, although such ranges may be measurable with state-of-the-art mass spectrometry. This report is available at the url: http://pubs.water.usgs.gov/wri014222.

Water-Resources Investigations Report↗

Effect of zeolite on toxicity of ammonia in freshwater sediments: Implications for toxicity identification evaluation procedures

Techniques for reducing ammonia toxicity in freshwater sediments were investigated as part of a project to develop toxicity identification and evaluation (TIE) procedures for whole sediments. Although ammonia is a natural constituent of freshwater sediments, pollution can lead to ammonia concentrations that are toxic to benthic invertebrates, and ammonia can also contribute to the toxicity of sediments that contain more persistent contaminants. We investigated the use of amendments of a natural zeolite mineral, clinoptilolite, to reduce concentrations of ammonia in sediment pore water. Zeolites have been widely used for removal of ammonia in water treatment and in aqueous TIE procedures. The addition of granulated zeolite to ammonia-spiked sediments reduced pore-water ammonia concentrations and reduced ammonia toxicity to invertebrates. Amendments of 20% zeolite (v/v) reduced ammonia concentrations in pore water by ???70% in spiked sediments with ammonia concentrations typical of contaminated freshwater sediments. Zeolite amendments reduced toxicity of ammonia-spiked sediments to three taxa of benthic invertebrates (Hyalella azteca, Lumbriculus variegatus, and Chironomus tentans), despite their widely differing sensitivity to ammonia toxicity. In contrast, zeolite amendments did not reduce acute toxicity of sediments containing high concentrations of cadmium or copper or reduce concentrations of these metals in pore waters. These studies suggest that zeolite amendments, used in conjunction with toxicity tests with sensitive taxa such as H. azteca, may be an effective technique for selective reduction of ammonia toxicity in freshwater sediments.

Environmental Toxicology and Chemistry↗

Direct effects of soil amendments on field emergence and growth of the invasive annual grass Bromus tectorum L. and the native perennial grass Hilaria jamesii (Torr.) Benth

Bromus tectorum L. is a non-native, annual grass that has invaded western North America. In SE Utah, B. tectorum generally occurs in grasslands dominated by the native perennial grass, Hilaria jamesii (Torr.) Benth. and rarely where the natives Stipa hymenoides Roem. and Schult. and S. comata Trin. & Rupr. are dominant. This patchy invasion is likely due to differences in soil chemistry. Previous laboratory experiments investigated using soil amendments that would allow B. tectorum to germinate but would reduce B. tectorum emergence without affecting H. jamesii. For this study we selected the most successful treatments (CaCl2, MgCl2, NaCl and zeolite) from a previous laboratory study and applied them in the field in two different years at B. tectorum-dominated field sites. All amendments except the lowest level of CaCl2 and zeolite negatively affected B. tectorum emergence and/or biomass. No amendments negatively affected the biomass of H. jamesii but NaCl reduced emergence. Amendment effectiveness depended on year of application and the length of time since application. The medium concentration of zeolite had the strongest negative effect on B. tectorum with little effect on H. jamesii. We conducted a laboratory experiment to determine why zeolite was effective and found it released large amounts of Na+, adsorbed Ca2+, and increased Zn2+, Fe2+, Mn2+, Cu2+, exchangeable Mg2+, exchangeable K, and NH 4+ in the soil. Our results suggest several possible amendments to control B. tectorum. However, variability in effectiveness due to abiotic factors such as precipitation and soil type must be accounted for when establishing management plans. ?? Springer 2006.

Plant and Soil↗

Ground-water flow and water quality in the Upper Floridan aquifer, southwestern Albany area, Georgia, 1998-2001

During 1997, the Dougherty County Health Department sampled more than 700 wells completed in the Upper Floridan aquifer in Dougherty County, Georgia, and determined that nitrate as nitrogen (hereinafter called nitrate) concentrations were above 10 milligrams per liter (mg/L) in 12 percent of the wells. Ten mg/L is the Georgia primary drinking-water standard. The ground-water flow system is complex and poorly understood in this predominantly agricultural area. Therefore, the U.S. Geological Survey (USGS) - in cooperation with Albany Water, Gas and Light Commission - conducted a study to better define ground-water flow and water quality in the Upper Florida aquifer in the southwestern Albany area, Georgia. Ground-water levels were measured in the southwestern Albany area, Georgia, during May 1998 and March 1999 (spring), and October 1998 and September 1999 (fall). Groundwater levels measured in 75 wells open only to the Upper Floridan aquifer were used to construct potentiometric-surface maps for those four time periods. These maps show that ground water generally flows from northwest to southeast at gradients ranging from about 2 to greater than 10 feet per mile. During spring and fall 1998, ground-water levels were high and mounding of the potentiometric surface occurred in the central part of the study area, indicating a local recharge area. Water levels declined from December through February, and by March 1999 the mound in the potentiometric surface had dissipated. Of the 75 wells in the potentiometric network, 24 were selected for a water-quality network. These 24 wells and 1 spring were sampled during fall 1998 and spring 1999. Samples were analyzed for major chemical constituents, selected minor constituents, selected nutrients, and chlorofluorocarbons (CFC). Water-quality field measurements - such as water temperature, pH, specific conductance (SC), and dissolved oxygen (DO) - were taken at each well. During August 2000, a ground-water sample was collected and analyzed for selected sewage tracers. During March 2001, water samples from selected wells were analyzed for nitrogen and oxygen isotopes. Age-dating analysis using CFCs yield apparent groundwater ages that range from modern to greater than 50 years. The chemistry of ground water in the Upper Floridan aquifer varies widely throughout the southwestern Albany area, Georgia, and in general represents the chemistry commonly found in recharge areas. From fall 1998 through spring 1999, median values of pH, SC, and DO concentration were 7.6 standard units, 266 microsiemens per centimeter at 25 degrees Celsius (uS/cm), and 5.6 mg/L, respectively. The SC is highest (350 - 400 uS/cm) where mounding of the potentiometric surface exists. Specific DO concentrations indicate an area of anoxic ground water in the north-central part of the study area. Water samples indicate that ground water in the study area is dominated by calcium and bicarbonate ions, which is consistent with the limestone lithology of the aquifer. About 25 percent of the samples contained sodium and chloride at ratios similar to those in rainfall, indicating a close proximity to recharge areas. The remaining water samples, however, had sodiumchloride ratios less than 0.90, the ratio in Tift County, Georgia, rainfall samples. These low sodium-chloride ratios are consistent with chloride enrichment. Minor constituent and nutrient concentrations typically are below laboratory reporting limits; however, the maximum nitrate concentration measured during the study period was 12.2 mg/L, and the median concentration for the study period was 3.0 mg/L. Samples collected during 1999 had a higher median nitrate concentration than the 1998 samples. Regression analysis indicated that nitrate concentrations are related exponentially to chloride concentrations. Four distinct groups of ground-water-quality samples, plus four unique samples, were identified using cluster analysis. Water-quality groups I and

Georgia↗

The prairie dog as a keystone species

The prairie dog has a pronounced impact on its grassland ecosystem (King 1955; Uresk and Bjugstad 1983; Miller et al. 1994; Society for Conservation Biology 1994; Wuerthner 1997; Johnsgard 2005). They maintain short vegetation by their grazing and by selective removal of tall plants and shrubs; provide shelter, foraging grounds, and nesting habitat for a diverse array of animals; serve as prey for many predators; and alter soil chemistry. Do these impacts mean that the prairie dog is a keystone species? To investigate, we first scrutinize the definition for a keystone species. We then document both vertebrates and invertebrates that associate with prairie dogs and their colony-sites. We examine ecosystem processes at colony-sites, and then assess whether the prairie dog is a legitimate keystone species. Finally, we explore the implications of keystone status for the conservation of prairie dogs.

Book chapter↗

Characterization of water-quality and bed-sediment conditions in Currituck Sound, North Carolina, prior to the Mid-Currituck Bridge construction, 2011–15

The North Carolina Turnpike Authority, a division of the North Carolina Department of Transportation, is planning to make transportation improvements in the Currituck Sound area by constructing a two-lane bridge from U.S. Highway 158 just south of Coinjock, North Carolina, to State Highway 12 on the Outer Banks just south of Corolla, North Carolina. The results of the Final Environmental Impact Study associated with the bridge and existing roadway improvements indicated potential water-quality and habitat impacts to Currituck Sound related to stormwater runoff, altered light levels, introduction of piles as hard substrate, and localized turbidity and siltation during construction. The primary objective of this initial study phase was to establish baseline water-quality conditions and bed-sediment chemistry of Currituck Sound in the vicinity of the planned alignment of the Mid-Currituck Bridge. These data will be used to evaluate the impacts associated with the bridge construction and bridge deck stormwater runoff. Between 2011 and 2015, discrete water-quality samples were collected monthly and after selected storm events from five locations in Currituck Sound. The sampling locations were distributed along the proposed alignment of the Mid-Currituck Bridge. Water samples were analyzed for physical parameters and water-quality constituents associated with bridge deck stormwater runoff and important in identifying impaired waters designated as “SC” (saltwater-aquatic life propagation/ protection and secondary recreation) under North Carolina’s water-quality classifications. Bed-sediment chemistry was also measured three times during the study at the five sampling locations. Continuous water-level and wind speed and direction data in Currituck Sound were also collected by the U.S. Geological Survey during the study period. For the water samples, measured concentrations were greater than water-quality thresholds on 52 occasions. In addition, there were 190 occurrences of censored results having a reporting level higher than specific thresholds. All 52 occurrences of concentrations greater than water-quality thresholds were confined to seven different physical properties or constituents, namely pH (25), turbidity (8), total recoverable chromium (6), total recoverable copper (6), dissolved copper (3), total recoverable mercury (2), and total recoverable nickel (2). Concentrations of 17 other constituents were never measured to be greater than their established water-quality thresholds during the study. The focus of the water-quality characterization was on concentrations of constituents identified as parameters of concern in a 2011 collaborative U.S. Geological Survey/North Carolina Department of Transportation study that characterized bridge deck stormwater runoff across North Carolina. The occurrence and distribution of parameters of concern identified in the 2011 study, including pH, nutrients, total recoverable and dissolved metals, and polycyclic aromatic hydrocarbons, and some additional pertinent physical properties (dissolved oxygen, specific conductance, and turbidity), were analyzed in water and bed-sediment samples. Statistical differences were identified between monthly and storm samples for the following physical properties and constituents: pH, dissolved oxygen, specific conductance, turbidity, Escherichia coli bacteria, total recoverable aluminum, and total recoverable iron. Seasonality was observed in pH, specific conductance, dissolved oxygen, turbidity, total phosphorus, and total nitrogen, and total recoverable aluminum, arsenic, iron, lead, and manganese during the study period. The volume and residence time of the water in Currituck Sound are such that the water chemistry is relatively uniform spatially, but variable temporally. One of the most variable constituents in bed sediments was the fraction of fines, those sediments less than 63 micrometers in diameter. Because most, if not all, of the measured constituents were presumably associated with this fraction, bulk-sediment concentrations are determined largely by the amount of fines present. Only four constituents were greater than bed-sediment thresholds: tin (5 samples), barium (4 samples), aluminum (2 samples), and diethyl phthalate (1 sample). The occurrences of concentrations being greater than referenced thresholds could be underestimated for diethyl phthalate, because the reporting level exceeded the threshold in nine samples. Thirty-five constituents had sampled concentrations that were never greater than quality thresholds, although 21 of these constituents (154 instances) had at least one sample with a reporting level that was greater than the corresponding threshold. Finally, 33 constituents had no quality thresholds. This study and previous studies of bed-sediment quality in Currituck Sound, although few, indicate that sedimentation in Currituck Sound near the proposed alignment of the MidCurrituck Bridge is characterized overall by low and transient input, frequent wind-driven resuspension, and little long-term deposition of fines. To the extent that it might alter water depths along the alignment, bridge construction might also alter the deposition and resuspension rates of fine sediments in Currituck Sound in the vicinity of the bridge. The characterization of water-quality and bed-sediment chemistry in Currituck Sound along the proposed alignment of the Mid-Currituck Bridge summarized herein provides a baseline for determining the effect of bridge construction and bridge deck runoff on environmental conditions in Currituck Sound.

North Carolina↗

Evaluation of nonpoint-source contamination, Wisconsin: Selected data for 1992 water year

This report presents the annual results of the U.S. Geological Survey's (USGS) watershed-management evaluation monitoring program in Wisconsin. The overall objective of each individual project in the program is to determine if the water chemistry in the receiving stream has changed as a result of the implementation of land-management practices in the watershed. This is accomplished through monitoring of water chemistry and ancillary variables before best-management practices (BMP's) are installed ('pre-BMP'), during installation ('transitional'), and after ('post-BMP') watershed- management plans have been completely implemented. Fecal-coliform (FC) counts ranged between 10 and 310,00/100 mL. A large range of values occurred within duplicate and triplicate samples as well as over time. The median percentage difference between duplicate and triplicate samples was 17 percent although 4 out of the total 60 duplicate and triplicate samples had differences greater than 100 percent. A decrease in FC counts generally occurred over the duration of the 4-day analyses. Linear regression models of the log-concentration values (dependent variable) with respect to time (independent variable) were calculated for all samples. Negative slopes were found for 14 of the 15 samples. Slopes varied from +0.5 to -38.4 percent gain/loss/day, with a median slope of -8.5 percent/day. A t-test was applied to the data to examine whether or not significant differences in FC counts exist with respect to holding times. Because the T-test only compares two treatments, the test was conducted 3 times (0 versus 24-hr holding time, 0 versus 48-hr holding time, and 0 versus 72-hr holding time). Setting the level of significance at p less than 0.05 and assuming equal variances, 27 percent (all from Bower and Otter Creeks) of the samples demonstrated a significant difference in colony count over the first 24 hr, 40 percent over 48 hr, and 47 percent over 72 hr. All samples that exhibited a significant change in colony count were because of a decrease in colony count of the sample.

Wisconsin↗

Moving beyond p<0.05 in ecotoxicology: A guide for practitioners

Statistical inferences play a critical role in ecotoxicology. Historically, Null Hypothesis Significance Testing (NHST) has been the dominant method for inference in ecotoxicology. As a brief and informal definition of the NHST approach, researchers compare (or test) an experimental treatment or observation against a hypothesis of no relationship or effect (the null hypothesis) using the collected data to see if the observed values are statistically significant given predefined error rates. The resulting probability of observing a value equal to or greater than the observed value assuming the null hypothesis is true is the p-value. Historically, criticisms of NHST have existed for almost a century and more recently these have grown to the point where statisticians, including the American Statistical Association, have felt the need to clarify the role of NHST and p-values in science beyond their current, common use. These limitations also exist in ecotoxicology. For example, a review of the 2010 Environmental Toxicology & Chemistry (ET&C) volume found many authors did not correctly report p-values. We repeated this review looking at the 2019 volume of ET&C and the incorrect reporting of p-values still occurred almost a decade later. Problems with NHST and p-values highlight the need for statistical inferences besides NHST, something that has long been known in ecotoxicology and the broader scientific and statistical communities. Furthermore, concerns such as these led the Executive Director of the American Statistical Association to recommend against use of statistical significance in 2019. In light of these criticisms, however, ecotoxicologists require alternative methods. In this paper, we describe some alternative methods including confidence intervals, regression analysis, dose-response curves, Bayes factors, survival analysis, and model selection. Lastly, we provide insights for what ecotoxicology might look like in a post-p-value world.

Environmental Toxicology and Chemistry↗

Ground-water quality data in the southeast San Joaquin Valley, 2005–2006— Results from the California GAMA program

Ground-water quality in the approximately 3,800 square-mile Southeast San Joaquin Valley study unit (SESJ) was investigated from October 2005 through February 2006 as part of the Priority Basin Assessment Project of Ground-Water Ambient Monitoring and Assessment (GAMA) Program. The GAMA Statewide Basin Assessment project was developed in response to the Ground-Water Quality Monitoring Act of 2001 and is being conducted by the California State Water Resources Control Board (SWRCB) in collaboration with the U.S. Geological Survey (USGS) and the Lawrence Livermore National Laboratory (LLNL). The SESJ study was designed to provide a spatially unbiased assessment of raw ground-water quality within SESJ, as well as a statistically consistent basis for comparing water quality throughout California. Samples were collected from 99 wells in Fresno, Tulare, and Kings Counties, 83 of which were selected using a spatially distributed, randomized grid-based method to provide statistical representation of the study area (grid wells), and 16 of which were sampled to evaluate changes in water chemistry along ground-water flow paths or across alluvial fans (understanding wells). The ground-water samples were analyzed for a large number of synthetic organic constituents (volatile organic compounds [VOCs], pesticides and pesticide degradates, and pharmaceutical compounds), constituents of special interest (perchlorate, N-nitrosodimethylamine, and 1,2,3-trichloropropane), naturally occurring inorganic constituents (nutrients, major and minor ions, and trace elements), radioactive constituents, and microbial indicators. Naturally occurring isotopes (tritium, and carbon-14, and stable isotopes of hydrogen, oxygen, nitrogen, and carbon), and dissolved noble gases also were measured to help identify the source and age of the sampled ground water. Quality-control samples (blanks, replicates, samples for matrix spikes) were collected at approximately 10 percent of the wells, and the results for these samples were used to evaluate the quality of the data for the ground-water samples. Assessment of the quality-control data resulted in censoring of less than 1 percent of the detections of constituents measured in ground-water samples. This study did not attempt to evaluate the quality of drinking water delivered to consumers; after withdrawal from the ground, water typically is treated, disinfected, and (or) blended with other waters to maintain acceptable drinking-water quality. Regulatory thresholds apply to the treated water that is served to the consumer, not to raw ground water. However, to provide some context for the results, concentrations of constituents measured in the raw ground water were compared with regulatory and other health-based thresholds established by the U.S. Environmental Protection Agency and California Department of Public Health (CDPH) and thresholds established for aesthetic concerns by CDPH. Two VOCs were detected above health-based thresholds: 1,2-dibromo-3-chloropropane (DBCP), and benzene. DBCP was detected above the U.S. Environmental Protections Agency’s maximum contaminant level (MCL-US) in three grid wells and five understanding wells. Benzene was detected above the CDPH’s maximum contaminant level (MCL-CA) in one grid well. All pesticide detections were below health-based thresholds. Perchlorate was detected above its maximum contaminate level for California in one grid well. Nitrate was detected above the MCL-US in six samples from understanding wells, of which one was a public supply well. Two trace elements were detected above MCLs-US: arsenic and uranium. Arsenic was detected above the MCL-US in four grid wells and two understanding wells; uranium was detected above the MCL-US in one grid well and one understanding well. Gross alpha radiation was detected above MCLs-US in five samples; four of them understanding wells, and uranium isotope activity was greater than the MCL-US for one understanding well. Radon-222 was detected above the proposed MCL-US in all wells sampled. Total coliforms were detected in two wells and somatic coliphage was detected in one well.

California↗

Water Quality of the Snake River and Five Eastern Tributaries in the Upper Snake River Basin, Grand Teton National Park, Wyoming, 1998-2002

To address water-resource management objectives of the National Park Service in Grand Teton National Park, the U.S. Geological Survey in cooperation with the National Park Service has conducted water-quality sampling in the upper Snake River Basin. Routine sampling of the Snake River was conducted during water years 1998-2002 to monitor the water quality of the Snake River through time. A synoptic study during 2002 was conducted to supplement the routine Snake River sampling and establish baseline water-quality conditions of five of its eastern tributaries?Pilgrim Creek, Pacific Creek, Buffalo Fork, Spread Creek, and Ditch Creek. Samples from the Snake River and the five tributaries were collected at 12 sites and analyzed for field measurements, major ions and dissolved solids, nutrients, selected trace metals, pesticides, and suspended sediment. In addition, the eastern tributaries were sampled for fecal-indicator bacteria by the National Park Service during the synoptic study. Major-ion chemistry of the Snake River varies between an upstream site above Jackson Lake near the northern boundary of Grand Teton National Park and a downstream site near the southern boundary of the Park, in part owing to the inputs from the eastern tributaries. Water type of the Snake River changes from sodium bicarbonate at the upstream site to calcium bicarbonate at the downstream site. The water type of the five eastern tributaries is calcium bicarbonate. Dissolved solids in samples collected from the Snake River were significantly higher at the upstream site (p-value<0.001), where concentrations in 43 samples ranged from 62 to 240 milligrams per liter, compared to the downstream site where concentrations in 33 samples ranged from 77 to 141 milligrams per liter. Major-ion chemistry of Pilgrim Creek, Pacific Creek, Buffalo Fork, Spread Creek, and Ditch Creek generally did not change substantially between the upstream sites near the National Park Service boundary with the National Forest and the downstream sites near the Snake River; however, variations in the major ions and dissolved solids existed between basins. Variations probably result from differences in geology between the tributary basins. Concentrations of dissolved ammonia, nitrite, and nitrate in all samples collected from the Snake River and the five eastern tributaries were less than water-quality criteria for surface waters in Wyoming. Concentrations of total nitrogen and total phosphorus in samples from the Snake River and the tributaries generally were less than median concentrations determined for undeveloped streams in the United States; however, concentrations in some samples did exceed ambient total-nitrogen and total-phosphorus criteria for forested mountain streams in the Middle Rockies ecoregion recommended by the U.S. Environmental Protection Agency to address cultural eutrophication. Sources for the excess nitrogen and phosphorus probably are natural because these basins have little development and cultivation. Concentrations of trace metals and pesticides were low and less than water-quality criteria for surface waters in Wyoming in samples collected from the Snake River and the five eastern tributaries. Atrazine, dieldrin, EPTC, or tebuthiuron were detected in estimated concentrations of 0.003 microgram per liter or less in 5 of 27 samples collected from the Snake River. An estimated concentration of 0.008 microgram per liter of metolachlor was detected in one sample from the Buffalo Fork. The estimated concentrations were less than the reporting levels for the pesticide analytical method. Suspended-sediment concentrations in 43 samples from the upstream site on the Snake River ranged from 1 to 604 milligrams per liter and were similar to suspended-sediment concentrations in 33 samples from the downstream site, which ranged from 1 to 648 milligrams per liter. Suspended-sediment concentrations in 38 samples collected from the tributary streams ranged from 1 t

Scientific Investigations Report↗

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↗

Loparite, a rare-earth ore (Ce, Na, Sr, Ca)(Ti, Nb, Ta, Fe+3)O3

The mineral loparite (Ce, NA, Sr, Ca)(Ti, Nb, Ta, Fe+3)O3 is the principal ore of the light-group rare-earth elements (LREE) in Russia. The complex oxide has a perovskite (ABO3) structure with coupled substitutions, polymorphism, defect chemistry and a tendency to become metamict. The A site generally contains weakly bonded, easily exchanged cations of the LREE, Na and Ca. The B site generally contains smaller, highly charged cations of Ti, Nb or Fe+3. Mine production is from Russia's Kola Peninsula. Ore is beneficiated to produce a 95% loparite concentrate containing 30% rare-earth oxides. Loparite concentrate is refined by either a chlorination process or acid decomposition process to recover rare-earths, titanium, niobium and tantalum. Rare-earths are separated by solvent extraction and selective precipitation/dissolution. The concentrate is processed at plants in Russia, Estonia and Kazakstan.

Journal of Alloys and Compounds↗

Selective trace enrichment of chlorotriazine pesticides from natural waters and sediment samples using terbuthylazine molecularly imprinted polymers

Two molecularly imprinted polymers were synthesized using either dichloromethane or toluene as the porogen and terbuthylazine as the template and were used as solid-phase extraction cartridges for the enrichment of six chlorotriazines (deisopropylatrazine, deethylatrazine, simazine, atrazine, propazine, and terbuthylazine) in natural water and sediment samples. The extracted samples were analyzed by liquid chromatography/diode array detection (LC/DAD). Several washing solvents, as well as different volumes, were tested for their ability to remove the matrix components nonspecifically adsorbed on the sorbents. This cleanup step was shown to be of prime importance to the successful extraction of the pesticides from the aqueous samples. The optimal analytical conditions were obtained when the MIP imprinted using dichloromethane was the sorbent, 2 mL of dichloromethane was used in the washing step, and the preconcentrated analytes were eluted with 8 mL of methanol. The recoveries were higher than 80% for all the chlorotriazines except for propazine (53%) when 50- or 100-mL groundwater samples, spiked at 1 ??g/L level, were analyzed. The limits of detection varied from 0.05 to 0.2 ??g/L when preconcentrating a 100-mL groundwater sample. Natural sediment samples from the Ebre Delta area (Tarragona, Spain) containing atrazine and deethylatrazine were Soxhlet extracted and analyzed by the methodology developed in this work. No significant interferences from the sample matrix were noticed, thus indicating good selectivity of the MIP sorbents used.

Analytical Chemistry↗

Effects of return flows on stream water quality and availability in the Upper Colorado, Delaware, and Illinois River Basins

Understanding effects of human water use and subsequent return flows on the availability and suitability of water for downstream uses is critical to efficient and effective watershed management. We compared spatially detailed estimates of stream chemistry within three watersheds in diverse settings to available standards to isolate effects of wastewater and irrigation return flows on the suitability of downstream waters for maintaining healthy aquatic ecosystems and for selected human uses. Mean-annual flow-weighted total and source-specific concentrations of nitrogen and phosphorus in individual stream reaches within the Upper Colorado, Delaware, and Illinois River Basins and of total dissolved solids within stream reaches of the Upper Colorado River Basin were estimated from previously calibrated regional watershed models. Estimated concentrations of both nitrogen and phosphorus in most stream reaches in all three watersheds (at least 78%, by length) exceed recommended standards for the protection of aquatic ecosystems, although concentrations in relatively few streams exceed such standards due to contributions from wastewater return flows, alone. Consequently, efforts to reduce wastewater nutrient effluent may provide important local downstream benefits but would likely have minimal impact on regional ecological conditions. Similarly, estimated mean-annual flow-weighted total dissolved solids concentrations in the Upper Colorado River Basin exceed standards for agricultural water use and (or) the secondary maximum contaminant level (SMCL) for drinking water in 52% of streams (by length), but rarely due to effects of irrigation return flows, alone. Dissolved solids in most tributaries of the Upper Colorado River are attributable primarily to natural sources.

Upper Colorado, Delaware, and Illinois River Basin↗

Relationships among foliar chemistry, foliar polyamines, and soil chemistry in red spruce trees growing across the northeastern United States

Forest trees are constantly exposed to various types of natural and anthropogenic stressors. A major long-term goal of our research is to develop a set of early physiological and biochemical markers of stress in trees before the appearance of visual symptoms. Six red spruce (Picea rubens Sarg.) stands from the northeastern United States were selected for collection of soil and foliage samples. All of the chosen sites had soil solution pH values below 4.0 in the Oa horizon but varied in their geochemistry. Some of these sites were apparently under some form of environmental stress as indicated by a large number of dead and dying red spruce trees. Samples of soil and needles (from apparently healthy red spruce trees) were collected from these sites four times during a two-year period. The needles were analyzed for perchloric acid-soluble polyamines and exchangeable inorganic ions. Soil and soil solution samples from the Oa and B horizons were analyzed for their exchange chemistry. The data showed a strong positive correlation between Ca and Mg concentrations in the needles and in the Oa horizon of the soil. However, needles from trees growing on relatively Ca-rich soils with a low exchangeable Al concentration and a low Al:Ca soil solution ratio had significantly lower concentrations of putrescine and spermidine than those growing on Ca-poor soils with a high exchangeable Al concentration and a high Al:Ca soil solution in the Oa horizon. The magnitude of this change was several fold higher for putrescine concentrations than for spermidine concentrations. Neither putrescine nor spermidine were correlated with soil solution Ca, Mg, and Al concentrations in the B horizon. The putrescine concentrations of the needles always correlated significantly with exchangeable Al (r2=0.73, p???0.05) and still solution Al:Ca ratios (r2=0.91, p???0.01) of the Oa horizon. This suggests that in conjunction with soil chemistry, putrescine and/or spermidine may be used as a potential early indicator of Al stress before the appearance of visual symptoms in red spruce trees.

Plant and Soil↗

Survival of cool and warm freshwater fish following chloramine-T exposure

Chloramine-T is presently available in the USA to control mortalities associated with bacterial gill disease or external columnaris only through an Investigational New Animal Drug Permit authorized by the US Food and Drug Administration (FDA). Its US approval hinges on FDA's acceptance of several key data, including those describing animal safety. Chloramine-T is presently applied in US aquaculture, by permit only, once daily on consecutive or alternate days for 1??h at 10 to 20??mg/L to control mortalities associated with bacterial gill disease or external columnaris. Our objective was to determine the safety of chloramine-T bath exposures at multiples of the proposed maximum treatment concentration (i.e., 0, 20, 60, 100, and 200??mg/L) administered on four consecutive days at 20????C to lake sturgeon Acipenser fulvescens, northern pike Esox lucius, and walleye Sander vitreum, or at 27????C to channel catfish Ictalurus punctatus, and largemouth bass Micropterus salmoides. All fish were tested as five to eight week old fry except for walleye and channel catfish which were tested as both fry and fingerling (fingerlings were at least four weeks older than the fry tested). Walleye and channel catfish were selected to evaluate the effects of life stage (fry vs. fingerling), temperature (walleye - 15, 20, or 25????C; channel catfish - 22, 27, or 32????C), exposure duration (60 vs. 180??min), and water chemistry (walleye only - reconstituted soft water vs. well water). Except for channel catfish fry, survival was significantly reduced only when fish were treated at 100 or 200??mg/L. Channel catfish fry survival was significantly reduced when exposed at 60??mg/L for 180??min at 27????C. Based on our mortality data, chloramine-T administered once daily for 60??min on four consecutive days at concentrations of up to 20??mg/L is not likely to adversely affect survival of cool or warmwater fish cultured in freshwater. Crown Copyright ?? 2007.

Aquaculture↗

Leaf litter breakdown, microbial respiration and shredder production in metal-polluted streams

1. If species disproportionately influence ecosystem functioning and also differ in their sensitivities to environmental conditions, the selective removal of species by anthropogenic stressors may lead to strong effects on ecosystem processes. We evaluated whether these circumstances held for several Colorado, U.S.A. streams stressed by Zn. 2. Benthic invertebrates and chemistry were sampled in five second-third order streams for 1 year. Study streams differed in dissolved metal concentrations, but were otherwise similar in chemical and physical characteristics. Secondary production of leaf-shredding insects was estimated using the increment summation and size-frequency methods. Leaf litter breakdown rates were estimated by retrieving litter-bags over a 171 day period. Microbial activity on leaf litter was measured in the laboratory using changes in oxygen concentration over a 48 h incubation period. 3. Dissolved Zn concentrations varied eightfold among two reference and three polluted streams. Total secondary production of shredders was negatively associated with metal contamination. Secondary production in reference streams was dominated by Taenionema pallidum. Results of previous studies and the current investigation demonstrate that this shredder is highly sensitive to metals in Colorado headwater streams. Leaf litter breakdown rates were similar between reference streams and declined significantly in the polluted streams. Microbial respiration at the most contaminated site was significantly lower than at reference sites. 4. Our results supported the hypothesis that some shredder species contribute disproportionately to leaf litter breakdown. Furthermore, the functionally dominant taxon was also the most sensitive to metal contamination. We conclude that leaf litter breakdown in our study streams lacked functional redundancy and was therefore highly sensitive to contaminant-induced alterations in community structure. We argue for the necessity of simultaneously measuring community structure and ecosystem function in anthropogenically stressed ecosystems.

Freshwater Biology↗

Geologic field-trip guide to Long Valley Caldera, California

This guide to the geology of Long Valley Caldera is presented in four parts: (1) An overview of the volcanic geology; (2) a chronological summary of the principal geologic events; (3) a road log with directions and descriptions for 38 field-trip stops; and (4) a summary of the geophysical unrest since 1978 and discussion of its causes. The sequence of stops is arranged as a four-day excursion for the quadrennial General Assembly of the International Association of Volcanology and Chemistry of the Earth’s Interior (IAVCEI), centered in Portland, Oregon, in August 2017. Most stops, however, are written freestanding, with directions that allow each one to be visited independently, in any order selected.

California↗