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Report of the U.S. Geological Survey's analytical evaluation program; standard reference water samples M-82 (major constituents), T-83 (trace constituents), N-8 (nutrients), and P-2 (precipitation snowmelt)

The U.S. Geological Survey began an interlaboratory testing program of reference water samples in 1962. Principal purposes of the program are to provide a means for participating water laboratories to: (1) identify analytical problem areas; (2) ascertain the accuracy and precision of common water analyses and analytical methods and; (3) provide reference samples for continuing quality assurance testing. Participation in this continuing quality assurance program is mandatory for all domestic laboratories providing water analysis data for Survey use. Analytical data submitted by the participating laboratories that analyzed the respective reference samples distributed in October 1982 are presented. Relative performance ratings achieved by the laboratories for each determination and statistical evaluation of the data are given in 14 tables. (Author 's abstract)

Open-File Report

Method of analysis and quality-assurance practices by the U. S. Geological Survey Organic Geochemistry Research Group—Determination of four selected mosquito insecticides and a synergist in water using liquid-liquid extraction and gas chromatography/mass spectrometry

A method of analysis and quality-assurance practices were developed for the determination of four mosquito insecticides (malathion, metho-prene, phenothrin, and resmethrin) and one synergist (piperonyl butoxide) in water. The analytical method uses liquid-liquid extraction (LLE) and gas chromatography/mass spectrometry (GC/MS). Good precision and accuracy were demonstrated in reagent water, urban surface water, and ground water. The mean accuracies as percentages of the true compound concentrations from water samples spiked at 10 and 50 nanograms per liter ranged from 68 to 171 percent, with standard deviations in concentrations of 27 nanograms per liter or less. The method detection limit for all compounds was 5.9 nanograms per liter or less for 247-milliliter samples. This method is valuable for acquiring information about the fate and transport of these mosquito insecticides and one synergist in water.

Kansas

Dissolved organic matter in the deep TALDICE ice core: A nano-UPLC-nano-ESI-HRMS method

Trace organic compounds in deep ice cores supply important paleoclimatic information. Untargeted analyses of dissolved organic matter provide an overview of molecular species in ice samples however, sample volumes usually required for these analyses are generally not available from deep ice cores. Here, we developed an analytical method using a nano-UPLC-nano-ESI-HRMS to detect major molecular species in ice cores. Samples (4 µL) from the TALos Dome Ice CorE (TALDICE), allowed investigating molecular species across a range of depths including during glacial and interglacial periods. We detected 317 chemical species that were tentatively assigned to fatty acids, hydroxy fatty acids and their degradation products (oxo-fatty acids and dicarboxylic acids), as well as oxidation byproducts of isoprene and monoterpenes. These compounds indicate that the main sources of the organic fraction are microbes as well as primary and secondary aerosols. Interglacial samples encompass a wide range of species including compounds from the oxidation of isoprene and monoterpenes as well as unsaturated fatty acids, while the glacial samples contained less diverse species. This difference may be due to decreased temperatures during the glacial period inhibiting terrestrial vegetation growth and increasing the sea ice extent, thereby weakening the emission sources.

Science of the Total Environment

Annual changes in seasonal river water temperatures in the eastern and western United States

Changes in river water temperatures are anticipated to have direct effects on thermal habitat and fish population vital rates, and therefore, understanding temporal trends in water temperatures may be necessary for predicting changes in thermal habitat and how species might respond to such changes. However, many investigations into trends in water temperatures use regression methods that assume long-term monotonic changes in temperature, when in fact changes are likely to be nonmonotonic. Therefore, our objective was to highlight the need and provide an example of an analytical method to better quantify the short-term, nonmonotonic temporal changes in thermal habitat that are likely necessary to determine the effects of changing thermal conditions on fish populations and communities. To achieve this objective, this study uses Bayesian dynamic linear models (DLMs) to examine seasonal trends in river water temperatures from sites located in the eastern and western United States, regions that have dramatically different riverine habitats and fish communities. We estimated the annual rate of change in water temperature and found little evidence of seasonal changes in water temperatures in the eastern U.S. We found more evidence of warming for river sites located in the western U.S., particularly during the fall and winter seasons. Use of DLMs provided a more detailed view of temporal dynamics in river thermal habitat compared to more traditional methods by quantifying year-to-year changes and associated uncertainty, providing managers with the information needed to adapt decision making to short-term changes in habitat conditions that may be necessary for conserving aquatic resources in the face of a changing climate.

Upper Colorado River Basin

Comparison of enzyme-linked immunosorbent assay and gas chromatography procedures for the detection of cyanazine and metolachlor in surface water samples

Enzyme-linked immunosorbent assay (ELISA) data from surface water reconnaissance were compared to data from samples analyzed by gas chromatography for the pesticide residues cyanazine (2-[[4-chloro-6-(ethylamino)-l,3,5-triazin-2-yl]amino]-2-methylpropanenitrile ) and metolachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide). When ELISA analyses were duplicated, cyanazine and metolachlor detection was found to have highly reproducible results; adjusted R2s were 0.97 and 0.94, respectively. When ELISA results for cyanazine were regressed against gas chromatography results, the models effectively predicted cyanazine concentrations from ELISA analyses (adjusted R2s ranging from 0.76 to 0.81). The intercepts and slopes for these models were not different from 0 and 1, respectively. This indicates that cyanazine analysis by ELISA is expected to give the same results as analysis by gas chromatography. However, regressing ELISA analyses for metolachlor against gas chromatography data provided more variable results (adjusted R2s ranged from 0.67 to 0.94). Regression models for metolachlor analyses had two of three intercepts that were not different from 0. Slopes for all metolachlor regression models were significantly different from 1. This indicates that as metolachlor concentrations increase, ELISA will over- or under-estimate metolachlor concentration, depending on the method of comparison. ELISA can be effectively used to detect cyanazine and metolachlor in surface water samples. However, when detections of metolachlor have significant consequences or implications it may be necessary to use other analytical methods.

Journal of Agricultural and Food Chemistry

Catalog of Mount St. Helens 2004 - 2005 tephra samples with major- and trace-element geochemistry

This open-file report presents a catalog of information about 135 ash samples along with geochemical analyses of bulk ash, glass and individual mineral grains from tephra deposited as a result of volcanic activity at Mount St. Helens, Washington, from October 1, 2004 until August 15, 2005. This data, in conjunction with that in a companion report on 2004-2007 Mount St. Helens dome samples by Thornber and others (2008a) are presented in support of the contents of the U.S. Geological Survey Professional Paper 1750 (Sherrod and others, ed., 2008). Readers are referred to appropriate chapters in USGS Professional Paper 1750 for detailed narratives of eruptive activity during this time period and for interpretations of sample characteristics and geochemical data presented here. All ash samples reported herein are currently archived at the David A. Johnston Cascades Volcano Observatory in Vancouver, Washington. The Mount St. Helens 2004?2005 Tephra Sample Catalogue along with bulk, glass and mineral geochemistry are tabulated in 6 worksheets of the accompanying Microsoft Excel file, of2008-1131.xls. Samples in all tables are organized by collection date. Table 1 is a detailed catalog of sample information for tephra deposited downwind of Mount St. Helens between October 1, 2004 and August 18, 2005. Table 2 provides major- and trace-element analyses of 8 bulk tephra samples collected throughout that interval. Major-element compositions of 82 groundmass glass fragments, 420 feldspar grains, and 213 mafic (clinopyroxene, amphibole, hypersthene, and olivine) mineral grains from 12 ash samples collected between October 1, 2004 and March 8, 2005 are presented in tables 3 through 5. In addition, trace-element abundances of 198 feldspars from 11 ash samples (same samples as major-element analyses) are provided in table 6. Additional mineral and bulk ash analyses from 2004 and 2005 ash samples are published in chapters 30 (oxide thermometry; Pallister and others, 2008), 32 (amphibole major elements; Thornber and others, 2008b) and 37 (210Pb; 210Pb/226Pa; Reagan and others, 2008) of U.S. Geological Survey Professional Paper 1750 (Sherrod and others, 2008). A brief overview of sample collection methods is given below as an aid to deciphering the tephra sample catalog. This is followed by an explanation of the categories of sample information (column headers) in table 1. A summary of the analytical methods used to obtain the geochemical data in this report introduces the presentation of major- and trace-element geochemistry of Mount St. Helens 2004-2005 tephra samples in tables 2-6. Rhyolite glass standard analyses are reported (Appendix 1) to demonstrate the accuracy and precision of similar glass analyses presented herein.

Washington

Sediment and chemical contaminant loads in tributaries to the Anacostia River, Washington, District of Columbia, 2016–17

A study was conducted by the U.S. Geological Survey (USGS) in cooperation with the Washington, D.C., Department of Energy & Environment to estimate the loads of suspended-sediment-bound chemical compounds in five gaged tributaries and four ungaged tributaries of the Anacostia River (known locally as “Lower Anacostia River”) in Washington, D.C. Tributaries whose discharge is measured by the USGS are the Northeast and Northwest Branches of the Anacostia River, referred to in this report as “Northeast Branch” (NEB) and “Northwest Branch” (NWB), respectively; Watts Branch (WB); and Hickey Run (HR). A USGS streamflow-gaging station was established in 2016 on Beaverdam Creek (known locally as “Lower Beaverdam Creek” [LBDC]) to support this study. The ungaged streams studied include Nash Run; Pope Branch; an unnamed stream at Fort DuPont, referred to in this report as “Fort DuPont Creek”; and an unnamed stream at Fort Stanton, referred to in this report as “Fort Stanton Creek.” The gaged streams were sampled during four to five storms and two low-flow events during January, March, May, and July 2017. The ungaged streams were sampled during one storm and one low-flow event during July 2017. Storm sampling involved collecting large-volume (60- to 70-liter) composite samples, then removing sediment by filtration in the laboratory. Low-flow samples were obtained by filtering streamwater directly in the field. Continuously recording data sondes were deployed throughout the study to measure turbidity and other water-quality characteristics. During sampling, multiple discrete samples of streamwater were collected to determine suspended-sediment concentration (SSC) and particulate organic carbon (POC) concentration. Shortly after each storm, bed sediment was collected for chemical analysis. Sediment samples were analyzed for 209 polychlorinated biphenyl (PCB) congeners; 35 polyaromatic hydrocarbon (PAH) compounds, including 20 nonalkylated and 15 alkylated species; and 20 organochlorine pesticide (OP) compounds. Sediment from one storm was analyzed for 23 metals. Relations were developed among turbidity, discharge, and measured SSC by using multiple linear regression of log-transformed data. These relations were used to estimate SSC from continuous records of discharge and turbidity and were subsequently used to estimate sediment loads for the 2017 calendar year. USGS continuous records of turbidity in NEB, NWB, Watts Branch, and Hickey Run were available for 2013–17, which allowed sediment loads to be calculated for these years. Sediment loads for the ungaged streams were estimated by using loads measured in Watts Branch adjusted on the basis of stream-basin areas. Sediment loads for 2017 total 3.10×10 7 kilograms (kg), with 1.02×107 kg (33 percent of total) from the NEB, 1.55×10 7 kg (50 percent) from the NWB, 4.45×10 6 kg (14 percent) from LBDC, 5.62×10 5 kg (2 percent) from Watts Branch, and 2.82×10 5 kg (1 percent) from Hickey Run. Sediment yields were highest from NWB and LBDC (3.13×10 5 kilograms per year per square mile [kg/yr/mi 2 ] and 3.01 kg/yr/mi 2 , respectively). As a result of gaps in turbidity and discharge data, the load for LBDC reported here was calculated from measurements representing only 88 percent of the year (2017), and thus underestimates the actual load. All other gaged tributaries had datasets covering 100 percent of the year and are considered to fully represent actual loads. Estimated sediment loads for the ungaged streams during 2017 total 3.5×10 5 kg, with 1.2×10 5 kg from Nash Run, 6.2×10 4 kg from Pope Branch, 1.1×10 5 kg from Fort DuPont Creek, and 5.6×10 4 kg from Fort Stanton Creek. Concentrations of PCBs, PAHs, and chlorinated pesticides in streamwater are presented for stormflow and low-flow conditions. Average concentrations (in stormflow and low-flow samples) of total PCBs (sum of all congeners, including coelutions) are 5.9 micrograms per kilogram (µg/kg) for NEB, 6.6 µg/kg for NWB, 130 µg/kg for LBDC, 34 µg/kg for Watts Branch, and 69 µg/kg for Hickey Run. Average concentrations of total PAHs (tPAH) (total of nonalkylated and alkylated species) are 2,000 µg/kg for NEB, 3,300 µg/kg for NWB, 2,200 µg/kg for LBDC, 2,400 µg/kg for Watts Branch, and 18,000 µg/kg for Hickey Run. tPAH concentrations among the ungaged streams were highest in Nash Run (5,500 µg/kg); concentrations in the other ungaged streams were less than (<) 700 µg/kg. The general magnitude of tPCB and tPAH concentrations in streamwater samples was low-flow samples greater than (>) stormflow samples greater than or equal to (≥) bed-sediment samples. PCB congener profiles in the three types of samples were nearly identical in each stream and were similar in all streams except for LBDC, where the dominant PCBs shifted to the lighter di- through tetra- homologs. LBDC showed higher tPCB concentrations and a distinct congener profile from the other streams. The similarity in congener makeup supported that averaging PCB concentrations in stormflow and low-flow samples was appropriate for calculating chemical loads. Loads of tPCB, tPAH (total of alkylated and nonalkylated forms), and pesticides were estimated for each stream by multiplying average contaminant concentrations by the respective sediment loads. Total PCB loads for 2017 were estimated to be 820 grams (g) with 8 percent (60 g) from NEB, 12 percent (95 g) from NWB, 75 percent (590 g) from LBDC, 3 percent (25 g) from Watts Branch, and 2.5 percent (19 g) from Hickey Run. PCB toxicity totaled 3.8×10 −3 µg/kg, with the largest contribution (47 percent) derived from LBDC. Total PAH loads (sum of alkylated and nonalkylated forms) for 2017 were estimated to be 89,000 g, with 23 percent (20,000 g) from NEB, 59 percent (52,000 g) from NWB, 11 percent (9,800 g) from LBDC, 2 percent (1,400 g) from Watts Branch, and 6 percent (5,200 g) from Hickey Run. These results indicate that the largest contributor (75 percent) of PCBs to the Anacostia River is LBDC, although it contributes only 15 percent of the sediment and its basin area represents only 10 percent of the area of the Anacostia River watershed. The majority of the PAH load originates from NWB (59 percent of total) and NEB (22 percent). The ungaged tributaries contribute extremely small loads of PCBs and PAHs, totaling 8.1 g and 765 kg, respectively. More than 94 percent of the total load from the ungaged tributaries is derived from the Nash Run Basin. Various organochlorine pesticides were present in suspended and bed sediment from all gaged and ungaged tributaries; however, elevated detection levels associated with the analytical methods resulted in numerous unquantifiable concentrations in the suspended-sediment samples. Only the pesticide chlordane was found in measurable concentrations in all gaged tributaries. As a result, in this report, a combination of analytical data from suspended-sediment and bed-sediment samples was used to estimate the maximum pesticide loading for each tributary. Chlordane was the principal compound present in the gaged tributaries; the highest average concentration (average of stormflow and low-flow samples from each stream) was 62 µg/kg in sediment from Watts Branch. Chlordane loads for 2017 totaled 1,100 g, of which 7 percent (430 g) was from NEB, 28 percent (320 g) was from NWB, 28 percent (310 g) was from LBDC, 5 percent (56 g) was from Watts Branch, and 1 percent (11 g) was from Hickey Run. Chlordane was not present in suspended or bed sediment from any of the ungaged tributaries. Loads of the other pesticides were estimated by using the highest concentration measured in the combined suspended-sediment and bed-sediment data for each stream. Notable loads include dieldrin (860 g from NWB), methoxychlor (205 g from LBDC), endrin aldehyde (150 g from NWB), and 4,4-DDT (79 g from Watts Branch). Compared with pesticide loads from the gaged streams, those from the ungaged streams were minimal, with only the Pope Branch contribution exceeding 1 gram per year for 4,4-DDE (1.05 g) and 4,4’-DDT (1.3 g). The results of this study show that the dominant source of PCBs and chlordane is LBDC, despite its relatively small basin area. PAHs are ubiquitous throughout the study area, with the largest sources being NEB and NWB; this finding is a result of the large sediment load originating from these basins. The small, ungaged streams supply only minimal PCB and PAH loads, with Nash Run being the largest contributor.

District of Columbia

Incorporating temporal variation in seabird telemetry data: time variant kernel density models

A key component of the Mid-Atlantic Baseline Studies project was tracking the individual movements of focal marine bird species (Red-throated Loon [Gavia stellata], Northern Gannet [Morus bassanus], and Surf Scoter [Melanitta perspicillata]) through the use of satellite telemetry. This element of the project was a collaborative effort with the Department of Energy (DOE), Bureau of Ocean Energy Management (BOEM), the U.S. Fish and Wildlife Service (USFWS), and Sea Duck Joint Venture (SDJV), among other organizations. Satellite telemetry is an effective and informative tool for understanding individual animal movement patterns, allowing researchers to mark an individual once, and thereafter follow the movements of the animal in space and time. Aggregating telemetry data from multiple individuals can provide information about the spatial use and temporal movements of populations. Tracking data is three dimensional, with the first two dimensions, X and Y, ordered along the third dimension, time. GIS software has many capabilities to store, analyze and visualize the location information, but little or no support for visualizing the temporal data, and tools for processing temporal data are lacking. We explored several ways of analyzing the movement patterns using the spatiotemporal data provided by satellite tags. Here, we present the results of one promising method: time-variant kernel density analysis (Keating and Cherry, 2009). The goal of this chapter is to demonstrate new methods in spatial analysis to visualize and interpret tracking data for a large number of individual birds across time in the mid-Atlantic study area and beyond. In this chapter, we placed greater emphasis on analytical methods than on the behavior and ecology of the animals tracked. For more detailed examinations of the ecology and wintering habitat use of the focal species in the midAtlantic, see Chapters 20-22.

Report

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-Comparison of a nitric acid in-bottle digestion procedure to other whole-water digestion procedures

A hydrochloric acid in-bottle digestion procedure is used to partially digest wholewater samples prior to determining recoverable elements by various analytical methods. The use of hydrochloric acid is problematic for some methods of analysis because of spectral interference. The inbottle digestion procedure has been modified to eliminate such interference by using nitric acid instead of hydrochloric acid in the digestion. Implications of this modification are evaluated by comparing results for a series of synthetic whole-water samples. Results are also compared with those obtained by using U.S. Environmental Protection Agency (1994) (USEPA) Method 200.2 total-recoverable digestion procedure. Percentage yields that use the nitric acid inbottle digestion procedure are within 10 percent of the hydrochloric acid in-bottle yields for 25 of the 26 elements determined in two of the three synthetic whole-water samples tested. Differences in percentage yields for the third synthetic whole-water sample were greater than 10 percent for 16 of the 26 elements determined. The USEPA method was the most rigorous for solubilizing elements from particulate matter in all three synthetic whole-water samples. Nevertheless, the variability in the percentage yield by using the USEPA digestion procedure was generally greater than the in-bottle digestion procedure, presumably because of the difficulty in controlling the digestion conditions accurately.

Open-File Report

Occurrence, distribution, and concentration of hydrocarbons in and near the Shell Valley Aquifer, North Dakota

Water samples from 27 wells completed in and near the Shell Valley aquifer were analyzed for benzene, toluene, ethylbenzene, and xylene (BTEX), polynuclear aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB), and pentachlorophenol (PCP) using the enzyme-linked immunoassay method. The analyses indicated the presence of PAH, PCB, and PCP in the study area. However, an individual compound at a high concentration or many compounds at low concentrations could cause the detections. Therefore, selected samples were analyzed using the gas chromatography (GC) method, which can detect individual compounds and determine the concentrations of those compounds. Concentrations for all compounds detected using the GC method were less than the minimum reporting levels (MRLs) for each constituent, indicating numerous compounds at low concentrations probably caused the immunoassay detections. The GC method also can detect compounds other than BTEX, PAH, PCB, and PCP. Concentrations for 81 of the additional compounds were determined and were less than the MRLs. Four compounds that could not be quantified accurately using the requested analytical methods also were detected. Acetone was detected in 4 of the 27 wells, 2-butanone was detected in 3 of the 27 wells, prometon was detected in 1 of the 27 wells, and tetrahydrofuran was detected in 9 of the 27 wells. Acetone, 2-butanone, and tetrahydrofuran probably leached from the polyvinyl chloride (PVC) pipe and joint glue and probably are not contaminants from the aquifer. Prometon is a herbicide that controls most annual and many perennial broadleaf weeds and primarily is used on roads and railroad tracks. The one occurrence of prometon could be caused by overspraying for weeds.

North Dakota

Determination of heat purgeable and ambient purgeable volatile organic compounds in water by gas chromatography/mass spectrometry

Two new analytical methods have been developed by the U.S. Geological Survey (USGS) National Water Quality Laboratory (NWQL) that allow the determination of 37 heat purgeable volatile organic compounds (VOCs) (USGS Method O-4437-16 [NWQL Laboratory Schedule (LS) 4437]) and 49 ambient purgeable VOCs (USGS Method O-4436-16 [NWQL LS 4436]) in unfiltered water. This report documents the procedures and initial performance of both methods. The compounds chosen for inclusion in the methods were determined as having high priority by the USGS National Water-Quality Assessment (NAWQA) Program. Both methods use a purge-and-trap technique with gas chromatography/mass spectrometry. The compounds are extracted from the sample by bubbling helium through a 25-milliliter sample. For the polar and less volatile compounds, the sample is heated at 60 degrees Celsius, whereas the less polar and more volatile compounds are purged using a separate analytical procedure at ambient temperature. The compounds are trapped on a sorbent trap, desorbed into a gas chromatograph/mass spectrometer for separation, and then identified and quantified. Sample preservation is recommended for both methods by adding a 1:1 solution of hydrochloric acid (HCl [1:1]) to water samples to adjust the pH to 2. Analysis within 14 days from sampling is recommended. The heat purgeable method (USGS Method O-4437-16) operates with the mass spectrometer in the simultaneous full scan/selected ion monitoring mode. This method supersedes USGS Method O-4024-03 (NWQL LS 4024). Method detection limits (MDLs) for fumigant compounds 1,2-dibromoethane, 1,2-dichloropropane, 1,2,3-trichloropropane, chloropicrin, and 1,2-dibromo-3-chloropropane range from 0.002 to 0.010 microgram per liter (µg/L). The MDLs for all remaining heat purgeable VOCs range from 0.006 µg/L for tert -butyl methyl ether to 3 µg/L for alpha -terpineol. Calculated holding times indicate that 36 of the 37 heat purgeable VOCs are stable for a minimum of 14 days preserved with HCl (1:1) to pH 2, and many are stable longer. Acrolein was retained in the method validation and initial method implementation and subsequently deleted because of instability and inconsistent performance. 2-Chloromethyl oxirane, methyl oxirane, and oxirane were tested using this method, but the compounds degraded quickly with the HCl (1:1) used for microbial preservation. The ambient purgeable method, USGS Method O-4436-16, operates with the mass spectrometer in the full scan mode. This method is a modification of USGS Method O-4127-96 (NWQL LS 2020). Several compounds were retained from Method O-4127-96 and will continue to be determined in Method O-4436-16. Eleven high priority compounds were added. MDLs for the high priority compounds range from 0.007 µg/L for 2,2-dichloro-1,1,1-trifluoroethane to 0.04 µg/L for 1,2,3,4-tetrahydronaphthalene and 1,3-butadiene. Historical MDLs for the compounds retained from Method O-4127-96 range from 0.009 µg/L for trans -1,2-dichloroethene to 0.1 µg/L for bromomethane. The calculated holding times for the compounds indicate the majority of the compounds are stable for a minimum of 14 days, or longer, at pH 2 with HCl (1:1) preservation. Four semivolatile compounds, 1,2-dimethylnaphthalene, 1,6-dimethylnaphthalene, 2,6-di- tert -butyl phenol, and 2-chloronapthalene, were tested and deleted from the method due to poor performance. Benzyl chloride was tested and deleted due to instability.

Techniques and Methods

Quality-assurance results for routine water analysis in US Geological Survey laboratories, water year 1991

The US. Geological Survey operates a quality- assurance program based on the analyses of reference samples for the National Water Quality Laboratory in Arvada, Colorado, and the Quality of Water Service Unit in Ocala, Florida. Reference samples containing selected inorganic, nutrient, and low ionic-strength constituents are prepared and disguised as routine samples. The program goal is to determine precision and bias for as many analytical methods offered by the participating laboratories as possible. The samples typically are submitted at a rate of approximately 5 percent of the annual environmental sample load for each constituent. The samples are distributed to the laboratories throughout the year. Analytical data for these reference samples reflect the quality of environmental sample data produced by the laboratories because the samples are processed in the same manner for all steps from sample login through data release. The results are stored permanently in the National Water Data Storage and Retrieval System. During water year 1991, 86 analytical procedures were evaluated at the National Water Quality Laboratory and 37 analytical procedures were evaluated at the Quality of Water Service Unit. An overall evaluation of the inorganic (major ion and trace metal) constituent data for water year 1991 indicated analytical imprecision in the National Water Quality Laboratory for 5 of 67 analytical procedures: aluminum (whole-water recoverable, atomic emission spectrometric, direct-current plasma); calcium (atomic emission spectrometric, direct); fluoride (ion-exchange chromatographic); iron (whole-water recoverable, atomic absorption spectrometric, direct); and sulfate (ion-exchange chromatographic). The results for 11 of 67 analytical procedures had positive or negative bias during water year 1991. Analytical imprecision was indicated in the determination of two of the five National Water Quality Laboratory nutrient constituents: orthophosphate as phosphorus and phosphorus. A negative or positive bias condition was indicated in three of five nutrient constituents. There was acceptable precision and no indication of bias for the 14 low ionic-strength analytical procedures tested in the National Water Quality Laboratory program and for the 32 inorganic and 5 nutrient analytical procedures tested in the Quality of Water Service Unit during water year 1991.

Water-Resources Investigations Report

Steroid determination in fish plasma using capillary electrophoresis

A capillary separation method that incorporates pH-mediated stacking is employed for the simultaneous determination of circulating steroid hormones in plasma from Perca flavescens (yellow perch) collected from natural aquatic environments. The method can be applied to separate eight steroid standards: progesterone, 17α,20β-dihydroxypregn-4-en-3-one, 17α-hydroxyprogesterone, testosterone, estrone, 11-ketotestosterone, ethynyl estradiol, and 17β-estradiol. Based on screening of plasma, the performance of the analytical method was determined for 17α,20β-dihydroxypregn-4-en-3-one, testosterone, 11-ketotestosterone, and 17β-estradiol. The within-day reproducibility in migration time for these four steroids in aqueous samples was ≤2%. Steroid quantification was accomplished using a calibration curve obtained with external standards. Plasma samples from fish collected from the Choptank and Severn Rivers, Maryland, USA, stored for up to one year were extracted with ethyl acetate and then further processed with anion exchange and hydrophobic solid phase extraction cartridges. The recovery of testosterone and 17β-estradiol from yellow perch plasma was 84 and 85%, respectively. Endogenous levels of testosterone ranged from 0.9 to 44 ng/ml, and when detected 17α,20β-dihydroxypregn-4-en-3-one ranged from 5 to 34 ng/ml. The reported values for testosterone correlated well with the immunoassay technique. Endogenous concentrations of 17β-estradiol were ≤1.7 ng/ml. 11-Ketotestosterone was not quantified because of a suspected interferant. Higher levels of 17α,20β-dihydroxypregn-4-en-3-one were found in male and female fish in which 17β-estradiol was not detected. Monitoring multiple steroids can provide insight into hormonal fluctuations in fish.

Maryland

Strategic Plan for the North American Breeding Bird Survey: 2006-2010

Executive Summary The mission of the North American Breeding Bird Survey (BBS) is to provide scientifically credible measures of the status and trends of North American bird populations at continental and regional scales to inform biologically sound conservation and management actions. Determining population trends, relative abundance, and distributions of North American avifauna is critical for identifying conservation priorities, determining appropriate conservation actions, and evaluating those actions. The BBS program, jointly coordinated by the U.S. Geological Survey and Environment Canada’s Canadian Wildlife Service, provides the U.S. and Canadian Federal governments, state and provincial agencies, other conservation practitioners, and the general public with science-based avian population trend estimates and other information for regional and national species’ population assessments. Despite the demonstrated value of the BBS for furthering avian conservation across North America, its importance is often underappreciated, and it is underfunded compared with many other government-supported programs that report on status of the environment. Today, BBS resources, adjusted for inflation, are below the amount allocated in the 1970s and are still only sufficient to support two biologists. Yet the number of routes, participants, data, and data requests has quadrupled. Data and information management and delivery requirements and security concerns, non-existent in 1966, impose further demands on BBS resources. In addition, the Mexican expansion of the BBS offers new hope for a truly continental approach to avian conservation, but also brings additional challenges. Meeting the goals of this plan will take cooperation among myriad stakeholders; yet, even with collaboration, most objectives of this plan will be unattainable if BBS program support is not increased. The BBS developed this strategic plan to help set priorities and identify resources required for the program to continue to meet the evolving needs of the conservation community for information on bird population change. By setting clear goals, strategies, and measures of success, this plan provides a cohesive framework and vision for maintenance and development of the BBS. The plan identifies two major goals for the BBS, with a number of strategies and objectives to achieve these goals. Over the next 5 years, progress made in addressing each long-term goal and its associated 5-year strategies and objectives will gage the plan’s success. Specific actions, projected outcomes, and measures of success related to accomplishing these are outlined in Table 1, with a timeline in Table 2. The two main goals for the program, with a summary of the strategies to achieve them, are: Goal 1: Collect scientifically credible measures of the status and trends of North American bird populations at continental and regional scales. The North American Breeding Bird Survey will continue to support North American natural resource conservation through the collection of scientifically credible measures of the status and trends of continental bird populations. While doing this, the BBS will work to improve the science behind the program to better meet its mission and the changing needs of the avian conservation community. In partnership with collaborators, the BBS will address detection probability bias and habitat bias, improve analytical methods, and more fully assess and account for observer quality. Moreover, the BBS will improve the quality and breadth of avian population data through strategic increases in route density and the establishment of a Mexican BBS program. Goal 2: Ensure BBS data and analytical results are widely available and easily accessible for use by the avian conservation and management communities. At the heart of the BBS lies a four-million-record database containing more than 40 years of data on more than 600 bird species. These data are of no value if not well maintained, appropriately analyzed, and widely and easily accessible. The USGS has greatly improved data management and accessibility in recent years. Trend estimates were first made available via the Internet in the mid-1990s, followed closely by the raw data with baseline metadata and standard operating procedures. Nevertheless, numerous enhancements to data management and the usability of BBS results will greatly improve the ability of the BBS to serve avian conservation goals. The BBS needs to ensure that BBS data and results presented on the web site use the best data-management practices and statistical methods, with adequate documentation for users to understand them and any differences between different trend estimates. Moreover, the BBS needs to increase communication with BBS partners and stakeholders to ensure that it continues to meet the avian population status and trends needs of the conservation community and to encourage the development of new products. Working with collaborators, the BBS will develop tools for integrating environmental parameters like habitat change into the analyses, and for integrating BBS data with other avian survey results. In addition, the BBS will continue to improve data and database management through the incorporation of additional data and data fields, such as georeferenced stop locations and more complete metadata for the raw data and results, thus enhancing the uses that can be made of the data.

Circular

Measurements of HFC-134a and HCFC-22 in groundwater and unsaturated-zone air: implications for HFCs and HCFCs as dating tracers

A new analytical method using gas chromatography with an atomic emission detector (GC–AED) was developed for measurement of ambient concentrations of hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) in soil, air, and groundwater, with the goal of determining their utility as groundwater age tracers. The analytical detection limits of HCFC-22 (difluorochloromethane, CHClF 2 ) and HFC-134a (1,2,2,2-tetrafluoroethane, C 2 H 2 F 4 ) in 1 L groundwater samples are 4.3 × 10 − 1 and 2.1 × 10 − 1 pmol kg − 1 , respectively, corresponding to equilibrium gas-phase mixing ratios of approximately 5–6 parts per trillion by volume (pptv). Under optimal conditions, post-1960 (HCFC-22) and post-1995 (HFC-134a) recharge could be identified using these tracers in stable, unmixed groundwater samples. Ambient concentrations of HCFC-22 and HFC-134a were measured in 50 groundwater samples from 27 locations in northern and western parts of Virginia, Tennessee, and North Carolina (USA), and 3 unsaturated-zone profiles were collected in northern Virginia. Mixing ratios of both HCFC-22 and HFC-134a decrease with depth in unsaturated-zone gas profiles with an accompanying increase in CO 2 and loss of O 2 . Apparently, ambient concentrations of HCFC-22 and HFC-134a are readily consumed by methanotrophic bacteria under aerobic conditions in the unsaturated zone. The results of this study indicate that soils are a sink for these two greenhouse gases. These observations contradict the previously reported results from microcosm experiments that found that degradation was limited above-ambient HFC-134a. The groundwater HFC and HCFC concentrations were compared with concentrations of chlorofluorocarbons (CFCs, CFC-11, CFC-12, CFC-113) and sulfur hexafluoride (SF 6 ). Nearly all samples had measured HCFC-22 or HFC-134a that were below concentrations predicted by the CFCs and SF6, with many samples showing a complete loss of HCFC-22 and HFC-134a. This study indicates that HCFC-22 and HFC-134a are not conservative as environmental tracers and leaves in question the usefulness of other HCFCs and HFCs as candidate age tracers.

North Carolina, Tennessee, Virginia

Catalog of Mount St. Helens 2004-2007 dome samples with major- and trace-element chemistry

Sampling and analysis of eruptive products at Mount St. Helens is an integral part of volcano monitoring efforts conducted by the U.S. Geological Survey?s Cascades Volcano Observatory (CVO). The objective of our eruption sampling program is to enable petrological assessments of pre-eruptive magmatic conditions, critical for ascertaining mechanisms for eruption triggering and forecasting potential changes in eruption behavior. This report provides a catalog of near-vent lithic debris and new dome-lava collected during 34 intra-crater sampling forays throughout the October 2004 to October 2007 (2004-7) eruptive interval at Mount St. Helens. In addition, we present comprehensive bulk-rock geochemistry for a time-series of representative (2004-7) eruption products. This data, along with that in a companion report on Mount St. Helens 2004 to 2006 tephra by Rowe and others (2008), are presented in support of the contents of the U.S. Geological Survey Professional Paper 1750 (Sherrod and others, eds., 2008). Readers are referred to appropriate chapters in USGS Professional Paper 1750 for detailed narratives of eruptive activity during this time period and for interpretations of sample characteristics and geochemical data. The suite of rock samples related to the 2004-7 eruption of Mount St. Helens and presented in this catalog are archived at the David A. Johnson Cascades Volcano Observatory, Vancouver, Wash. The Mount St. Helens 2004-7 Dome Sample Catalogue with major- and trace-element geochemistry is tabulated in 3 worksheets of the accompanying Microsoft Excel file, of2008-1130.xls. Table 1 provides location and sampling information. Table 2 presents sample descriptions. In table 3, bulk-rock major and trace-element geochemistry is listed for 44 eruption-related samples with intra-laboratory replicate analyses of 19 dacite lava samples. A brief overview of the collection methods and lithology of dome samples is given below as an aid to deciphering the dome sample catalog. This is followed by an explanation of the categories of sample information (column headers) in Tables 1 and 2. A summary of the analytical methods used to obtain the geochemical data in this report introduces the presentation of major- and trace-element geochemistry of 2004-7 Mount St. Helens dome samples in table 3. Intra-laboratory results for the USGS AGV-2 standard are presented (tables 4 and 5), which demonstrate the compatibility of chemical data from different sources.

Open-File Report

Palynological assessment of organic tissues and metallic minerals in the Jerritt Canyon gold deposit, Nevada (U.S.A.)

Organic tissues and metallic minerals were studied in acid residues and thin section of the Jerritt Canyon (Bell Mine) gold deposit. The purpose was to compare gold-bearing and gold-free rocks, characterize their differences, and assess a possible relationship between the invisible gold and the organic tissues in these early Paleozoic, carbonaceous limestones, dolomites, and claystones. The most visually abundant acid-resistant component in the sooty, unoxidized, gold-bearing rocks is a black, rectangular, carbon-bearing mineraloid. In X-ray diffraction, it is poorly crystalline; in nuclear magnetic resonance, it is a highly aromatized structure. The increase in gold content that accompanies the increase in content of this protographite suggests that it may be the major gold-bearing compound. Less abundant among the acid-resistant residues are uncarbonized organic tissues that are typical of marine settings. The tissues not in the vicinity of silicified veins are medium to dark brown. The dominant tissues are the amorphous remains of algae and their zooplankton predators. These uncarbonized indigenous tissues indicate that temperatures were lower than those determined by geochemical and fluid inclusion methods. The presence of different kinds of carbon-bearing compounds could account for the discrepancy between the palynological and geochemical data. The uncarbonized organic tissues comprise such a small percentage of these rocks that they could be easily missed by bulk analytical methods. The presence of uncarbonized tissues helps to constrain the duration of the high heat flow that is shown by the fluid inclusion data. The presence of mixed signals suggests that the protographite may be the product of chemical rather than thermal reactions.

Nevada

Methods for estimating annual exceedance probability discharges for streams in Arkansas, based on data through water year 2013

In 2013, the U.S. Geological Survey initiated a study to update regional skew, annual exceedance probability discharges, and regional regression equations used to estimate annual exceedance probability discharges for ungaged locations on streams in the study area with the use of recent geospatial data, new analytical methods, and available annual peak-discharge data through the 2013 water year. An analysis of regional skew using Bayesian weighted least-squares/Bayesian generalized-least squares regression was performed for Arkansas, Louisiana, and parts of Missouri and Oklahoma. The newly developed constant regional skew of -0.17 was used in the computation of annual exceedance probability discharges for 281 streamgages used in the regional regression analysis. Based on analysis of covariance, four flood regions were identified for use in the generation of regional regression models. Thirty-nine basin characteristics were considered as potential explanatory variables, and ordinary least-squares regression techniques were used to determine the optimum combinations of basin characteristics for each of the four regions. Basin characteristics in candidate models were evaluated based on multicollinearity with other basin characteristics (variance inflation factor < 2.5) and statistical significance at the 95-percent confidence level ( p ≤ 0.05). Generalized least-squares regression was used to develop the final regression models for each flood region. Average standard errors of prediction of the generalized least-squares models ranged from 32.76 to 59.53 percent, with the largest range in flood region D. Pseudo coefficients of determination of the generalized least-squares models ranged from 90.29 to 97.28 percent, with the largest range also in flood region D. The regional regression equations apply only to locations on streams in Arkansas where annual peak discharges are not substantially affected by regulation, diversion, channelization, backwater, or urbanization. The applicability and accuracy of the regional regression equations depend on the basin characteristics measured for an ungaged location on a stream being within range of those used to develop the equations.

Arkansas