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Developing integrated methods to address complex resource and environmental issues

Introduction This circular provides an overview of selected activities that were conducted within the U.S. Geological Survey (USGS) Integrated Methods Development Project, an interdisciplinary project designed to develop new tools and conduct innovative research requiring integration of geologic, geophysical, geochemical, and remote-sensing expertise. The project was supported by the USGS Mineral Resources Program, and its products and acquired capabilities have broad applications to missions throughout the USGS and beyond. In addressing challenges associated with understanding the location, quantity, and quality of mineral resources, and in investigating the potential environmental consequences of resource development, a number of field and laboratory capabilities and interpretative methodologies evolved from the project that have applications to traditional resource studies as well as to studies related to ecosystem health, human health, disaster and hazard assessment, and planetary science. New or improved tools and research findings developed within the project have been applied to other projects and activities. Specifically, geophysical equipment and techniques have been applied to a variety of traditional and nontraditional mineral- and energy-resource studies, military applications, environmental investigations, and applied research activities that involve climate change, mapping techniques, and monitoring capabilities. Diverse applied geochemistry activities provide a process-level understanding of the mobility, chemical speciation, and bioavailability of elements, particularly metals and metalloids, in a variety of environmental settings. Imaging spectroscopy capabilities maintained and developed within the project have been applied to traditional resource studies as well as to studies related to ecosystem health, human health, disaster assessment, and planetary science. Brief descriptions of capabilities and laboratory facilities and summaries of some applications of project products and research findings are included in this circular. The work helped support the USGS mission to “provide reliable scientific information to describe and understand the Earth; minimize loss of life and property from natural disasters; manage water, biological, energy, and mineral resources; and enhance and protect our quality of life.” Activities within the project include the following: Spanned scales from microscopic to planetary; Demonstrated broad applications across disciplines; Included life-cycle studies of mineral resources; Incorporated specialized areas of expertise in applied geochemistry including mineralogy, hydrogeology, analytical chemistry, aqueous geochemistry, biogeochemistry, microbiology, aquatic toxicology, and public health; and Incorporated specialized areas of expertise in geophysics including magnetics, gravity, radiometrics, electromagnetics, seismic, ground-penetrating radar, borehole radar, and imaging spectroscopy. This circular consists of eight sections that contain summaries of various activities under the project. The eight sections are listed below: Laboratory Facilities and Capabilities, which includes brief descriptions of the various types of laboratories and capabilities used for the project; Method and Software Development, which includes summaries of remote-sensing, geophysical, and mineralogical methods developed or enhanced by the project; Instrument Development, which includes descriptions of geophysical instruments developed under the project; Minerals, Energy, and Climate, which includes summaries of research that applies to mineral or energy resources, environmental processes and monitoring, and carbon sequestration by earth materials; Element Cycling, Toxicity, and Health, which includes summaries of several process-oriented geochemical and biogeochemical studies and health-related research activities; Hydrogeology and Water Quality, which includes descriptions of innovative geophysical, remote-sensing, and geochemical research pertaining to hydrogeology and water-quality applications; Hazards and Disaster Assessment, which includes summaries of research and method development that were applied to natural hazards, human-caused hazards, and disaster assessments; and Databases and Framework Studies, which includes descriptions of fundamental applications of geophysical studies and of the importance of archived data.

Circular↗

Tissue distribution and temporal and spatial assessment of per- and polyfluoroalkyl substances (PFAS) in smallmouth bass (Micropterus dolomieu) in the mid-Atlantic United States

Per- and polyfluoroalkyl substances (PFAS) have become an environmental issue worldwide. A first step to assessing potential adverse effects on fish populations is to determine if concentrations of concern are present in a region and if so, in which watersheds. Hence, plasma from adult smallmouth bass Micropterus dolomieu collected at 10 sites within 4 river systems in the mid-Atlantic region of the United States, from 2014 to 2019, was analyzed for 13 PFAS. These analyses were directed at better understanding the presence and associations with land use attributes in an important sportfish. Four substances, PFOS, PFDA, PFUnA, and PFDoA, were detected in every plasma sample, with PFOS having the highest concentrations. Sites with mean plasma concentrations of PFOS below 100 ng/ml had the lowest percentage of developed landcover in the upstream catchments. Sites with moderate plasma concentrations (mean PFOS concentrations between 220 and 240 ng/ml) had low (< 7.0) percentages of developed land use but high (> 30) percentages of agricultural land use. Sites with mean plasma concentrations of PFOS > 350 ng/ml had the highest percentage of developed land use and the highest number PFAS facilities that included military installations and airports. Four of the sites were part of a long-term monitoring project, and PFAS concentrations of samples collected in spring 2017, 2018, and 2019 were compared. Significant annual differences in plasma concentrations were noted that may relate to sources and climatic factors. Samples were also collected at two sites for tissue (plasma, whole blood, liver, gonad, muscle) distribution analyses with an expanded analyte list of 28 PFAS. Relative tissue distributions were not consistent even within one species of similar ages. Although the long-chained legacy PFAS were generally detected more frequently and at higher concentrations, emerging compounds such as 6:2 FTS and GEN X were detected in a variety of tissues.

Delaware, Maryland, New York, Pennsylvania, Virgin↗

Transcriptomic effects-based monitoring for endocrine active chemicals: Assessing relative contribution of treated wastewater to downstream pollution

The present study investigated whether a combination of targeted analytical chemistry information with unsupervised, data-rich biological methodology (i.e., transcriptomics) could be utilized to evaluate relative contributions of wastewater treatment plant (WWTP) effluents to biological effects. The effects of WWTP effluents on fish exposed to ambient, receiving waters were studied at three locations with distinct WWTP and watershed characteristics. At each location, 4 d exposures of male fathead minnows to the WWTP effluent and upstream and downstream ambient waters were conducted. Transcriptomic analyses were performed on livers using 15 000 feature microarrays, followed by a canonical pathway and gene set enrichment analyses. Enrichment of gene sets indicative of teleost brain–pituitary–gonadal–hepatic (BPGH) axis function indicated that WWTPs serve as an important source of endocrine active chemicals (EACs) that affect the BPGH axis (e.g., cholesterol and steroid metabolism were altered). The results indicated that transcriptomics may even pinpoint pertinent adverse outcomes (i.e., liver vacuolization) and groups of chemicals that preselected chemical analytes may miss. Transcriptomic Effects-Based monitoring was capable of distinguishing sites, and it reflected chemical pollution gradients, thus holding promise for assessment of relative contributions of point sources to pollution and the efficacy of pollution remediation.

Environmental Science & Technology↗

High-resolution U-series dates from the Sima de los Huesos hominids yields 600 +∞ -66 : implications for the evolution of the early Neanderthal lineage

The Sima de los Huesos site of the Atapuerca complex near Burgos, Spain contains the skeletal remains of at least 28 individuals in a mud-breccia underlying an accumulation of the Middle Pleistocene cave bear (Ursus deningeri). We report here on new high-precision dates on the recently discovered speleothem SRA-3 overlaying human bones within the Sima de los Huesos. Earlier analyses of this speleothem by TIMS (thermal-ionization mass-spectrometry) showed the lower part to be indistinguishable from internal isotopic equilibrium at the precision of the TIMS instrumentation used, yielding minimum age of 350 kyr (kyr = 103 yr before present). Reanalysis of six samples of SRA-3 by inductively-coupled plasma-multicollector mass-spectrometry (ICP-MS) produced high-precision analytical results allowing calculation of finite dates. The new dates cluster around 600 kyr. A conservative conclusion takes the lower error limit ages as the minimum age of the speleothem, or 530 kyr. This places the SH hominids at the very beginnings of the Neandertal evolutionary lineage.

Atapuerca↗

Isotope and Chemical Methods in Support of the U.S. Geological Survey Science Strategy, 2003-2008

Principal functions of the Mineral Resources Program are providing information to decision-makers related to mineral deposits on federal lands and predicting the environmental consequences of the mining or natural weathering of those deposits. Performing these functions requires that predictions be made of the likelihood of undiscovered deposits. The predictions are based on geologic and geoenvironmental models that are constructed for the various types of mineral deposits from detailed descriptions of actual deposits and detailed understanding of the processes that formed them. Over the past three decades the understanding of ore-forming processes has benefitted greatly from the integration of laboratory-based geochemical tools with field observations and other data sources. Under the aegis of the Evolution of Ore Deposits and Technology Transfer Project (EODTTP), a five-year effort that terminated in 2008, the Mineral Resources Program provided state-of-the-art analytical capabilities to support applications of several related geochemical tools.

Fact Sheet↗

Quality-Assurance Data for Routine Water Analyses by the U.S. Geological Survey Laboratory in Troy, New York--July 1999 through June 2001

The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance and quality-control data were stored in the laboratory's LabMaster data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality-control samples analyzed from July 1999 through June 2001. Results for the quality-control samples for 18 analytical procedures were evaluated for bias and precision. Control charts indicate that data for eight of the analytical procedures were occasionally biased for either high-concentration or low-concentration samples but were within control limits; these procedures were: acid-neutralizing capacity, total monomeric aluminum, total aluminum, calcium, chloride and nitrate (ion chromatography and colormetric method) and sulfate. The total aluminum and dissolved organic carbon procedures were biased throughout the analysis period for the high-concentration sample, but were within control limits. The calcium and specific conductance procedures were biased throughout the analysis period for the low-concentration sample, but were within control limits. The magnesium procedure was biased for the high-concentration and low concentration samples, but was within control limits. Results from the filter-blank and analytical-blank analyses indicate that the procedures for 14 of 15 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. The data-quality objective was not met for dissolved organic carbon. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 17 of the 18 analytes. At least 90 percent of the samples met data-quality objectives for all analytes except ammonium (81 percent of samples met objectives), chloride (75 percent of samples met objectives), and sodium (86 percent of samples met objectives). Results of the USGS interlaboratory Standard Reference Sample (SRS) Project indicated good data quality over the time period, with most ratings for each sample in the good to excellent range. The P-sample (low-ionic-strength constituents) analysis had one satisfactory rating for the specific conductance procedure in one study. The T-sample (trace constituents) analysis had one satisfactory rating for the aluminum procedure in one study and one unsatisfactory rating for the sodium procedure in another. The remainder of the samples had good or excellent ratings for each study. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 89 percent of the samples met data-quality objectives for 10 of the 14 analytes; the exceptions were ammonium, total aluminum, dissolved organic carbon, and sodium. Results indicate a positive bias for the ammonium procedure in all studies. Data-quality objectives were not met in 50 percent of samples analyzed for total aluminum, 38 percent of samples analyzed for dissolved organic carbon, and 27 percent of samples analyzed for sodium. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 91 percent of the samples analyzed for calcium, chloride, fluoride, magnesium, pH, potassium, and sulfate. Data-quality objectives were met by 75 percent of the samples analyzed for sodium and 58 percent of the samples analyzed for specific conductance.

Open-File Report↗

Quality-Assurance Data for Routine Water Analyses by the U.S. Geological Survey Laboratory in Troy, New York - July 2001 Through June 2003

The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance and quality-control data were stored in the laboratory's Lab Master data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality control samples analyzed from July 2001 through June 2003. Results for the quality-control samples for 19 analytical procedures were evaluated for bias and precision. Control charts indicate that data for six of the analytical procedures were occasionally biased for either high-concentration or low-concentration samples but were within control limits; these procedures were: acid-neutralizing capacity, chloride, magnesium, nitrate (ion chromatography), potassium, and sodium. The calcium procedure was biased throughout the analysis period for the high-concentration sample, but was within control limits. The total monomeric aluminum and fluoride procedures were biased throughout the analysis period for the low-concentration sample, but were within control limits. The total aluminum, pH, specific conductance, and sulfate procedures were biased for the high-concentration and low-concentration samples, but were within control limits. Results from the filter-blank and analytical-blank analyses indicate that the procedures for 16 of 18 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. The data-quality objective was not met for the dissolved organic carbon or specific conductance procedures. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 18 of the 21 analytes. At least 90 percent of the samples met data-quality objectives for all procedures except total monomeric aluminum (83 percent of samples met objectives), total aluminum (76 percent of samples met objectives), ammonium (73 percent of samples met objectives), dissolved organic carbon (86 percent of samples met objectives), and nitrate (81 percent of samples met objectives). The data-quality objective was not met for the nitrite procedure. Results of the USGS interlaboratory Standard Reference Sample (SRS) Project indicated satisfactory or above data quality over the time period, with most performance ratings for each sample in the good-to-excellent range. The N-sample (nutrient constituents) analysis had one unsatisfactory rating for the ammonium procedure in one study. The T-sample (trace constituents) analysis had one unsatisfactory rating for the magnesium procedure and one marginal rating for the potassium procedure in one study and one unsatisfactory rating for the sodium procedure in another. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 90 percent of the samples met data-quality objectives for 10 of the 14 analytes; the exceptions were acid-neutralizing capacity, ammonium, dissolved organic carbon, and sodium. Data-quality objectives were not met in 37 percent of samples analyzed for acid-neutralizing capacity, 28 percent of samples analyzed for dissolved organic carbon, and 30 percent of samples analyzed for sodium. Results indicate a positive bias for the ammonium procedure in one study and a negative bias in another. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 90 percent of the samples analyzed for calcium, chloride, magnesium, pH, potassium, and sodium. Data-quality objectives were met by 78 percent of

Open-File Report↗

Quality-assurance data for routine water analyses by the U.S. Geological Survey laboratory in Troy, New York - July 2003 through June 2005

The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance and quality-control data were stored in the laboratory's Lab Master data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality control samples analyzed from July 2003 through June 2005. Results for the quality-control samples for 20 analytical procedures were evaluated for bias and precision. Control charts indicate that data for five of the analytical procedures were occasionally biased for either high-concentration or low-concentration samples but were within control limits; these procedures were: acid-neutralizing capacity, total monomeric aluminum, pH, silicon, and sodium. Seven of the analytical procedures were biased throughout the analysis period for the high-concentration sample, but were within control limits; these procedures were: dissolved organic carbon, chloride, nitrate (ion chromatograph), nitrite, silicon, sodium, and sulfate. The calcium and magnesium procedures were biased throughout the analysis period for the low-concentration sample, but were within control limits. The total aluminum and specific conductance procedures were biased for the high-concentration and low-concentration samples, but were within control limits. Results from the filter-blank and analytical-blank analyses indicate that the procedures for 17 of 18 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. The data-quality objective was not met for dissolved organic carbon. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 18 of the 22 analytes. At least 85 percent of the samples met data-quality objectives for all analytes except total monomeric aluminum (82 percent of samples met objectives), total aluminum (77 percent of samples met objectives), chloride (80 percent of samples met objectives), fluoride (76 percent of samples met objectives), and nitrate (ion chromatograph) (79 percent of samples met objectives). The ammonium and total dissolved nitrogen did not meet the data-quality objectives. Results of the USGS interlaboratory Standard Reference Sample (SRS) Project indicated good data quality over the time period, with ratings for each sample in the satisfactory, good, and excellent ranges or less than 10 percent error. The P-sample (low-ionic-strength constituents) analysis had one marginal and two unsatisfactory ratings for the chloride procedure. The T-sample (trace constituents)analysis had two unsatisfactory ratings and one high range percent error for the aluminum procedure. The N-sample (nutrient constituents) analysis had one marginal rating for the nitrate procedure. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 84 percent of the samples met data-quality objectives for 11 of the 14 analytes; the exceptions were ammonium, total aluminum, and acid-neutralizing capacity. The ammonium procedure did not meet data quality objectives in all studies. Data-quality objectives were not met in 23 percent of samples analyzed for total aluminum and 45 percent of samples analyzed acid-neutralizing capacity. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 86 percent of the samples analyzed for calcium, chloride, fluoride, magnesium, pH, potassium, sodium, and sulfate. Data-quality objectives were not met by samples analyzed for fluoride.

Open-File Report↗

Quality-Assurance Data for Routine Water Analyses by the U.S. Geological Survey Laboratory in Troy, New York - July 2005 through June 2007

The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance and quality-control data were stored in the laboratory's Lab Master data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality control samples analyzed from July 2005 through June 2007. Results for the quality-control samples for 19 analytical procedures were evaluated for bias and precision. Control charts indicate that data for eight of the analytical procedures were occasionally biased for either high-concentration or low-concentration samples but were within control limits; these procedures were: total aluminum, calcium, magnesium, nitrate (colorimetric method), potassium, silicon, sodium, and sulfate. Eight of the analytical procedures were biased throughout the analysis period for the high-concentration sample, but were within control limits; these procedures were: total aluminum, calcium, dissolved organic carbon, chloride, nitrate (ion chromatograph), potassium, silicon, and sulfate. The magnesium and pH procedures were biased throughout the analysis period for the low-concentration sample, but were within control limits. The acid-neutralizing capacity, total monomeric aluminum, nitrite, and specific conductance procedures were biased for the high-concentration and low-concentration samples, but were within control limits. Results from the filter-blank and analytical-blank analyses indicated that the procedures for 16 of 17 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. The data-quality objective was not met for dissolved organic carbon. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 18 of the 21 analytes. At least 93 percent of the samples met data-quality objectives for all analytes except acid-neutralizing capacity (85 percent of samples met objectives), total monomeric aluminum (83 percent of samples met objectives), total aluminum (85 percent of samples met objectives), and chloride (85 percent of samples met objectives). The ammonium and total dissolved nitrogen did not meet the data-quality objectives. Results of the USGS interlaboratory Standard Reference Sample (SRS) Project met the Troy Laboratory data-quality objectives for 87 percent of the samples analyzed. The P-sample (low-ionic-strength constituents) analysis had two outliers each in two studies. The T-sample (trace constituents) analysis and the N-sample (nutrient constituents) analysis had one outlier each in two studies. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 85 percent of the samples met data-quality objectives for 11 of the 14 analytes; the exceptions were acid-neutralizing capacity, total aluminum and ammonium. Data-quality objectives were not met in 41 percent of samples analyzed for acid-neutralizing capacity, 50 percent of samples analyzed for total aluminum, and 44 percent of samples analyzed for ammonium. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 86 percent of the samples analyzed for calcium, magnesium, pH, potassium, and sodium. Data-quality objectives were met by 76 percent of the samples analyzed for chloride, 80 percent of the samples analyzed for specific conductance, and 77 percent of the samples analyzed for sulfate.

Open-File Report↗

Early developments in petroleum geochemistry

Petroleum geochemistry is the outgrowth of the application of the principles and methods of organic chemistry to petroleum refining and petroleum geology . This paper reviews 120 years of petroleum geochemistry, from about 1860 to 1980, and includes a discussion of the formal recognition of petroleum geochemistry as an earth-science discipline starting in 1959 when a general petroleum geochemistry symposium was first organized at Fordham University, New York. A chronology of significant events, including concepts, techniques, and textbook publications, is presented. Because petroleum geochemistry has been a tool for petroleum exploration from the beginning, the early developments of surface prospecting, source-rock identification, and oil/oil and oil/source correlation are discussed, along with the application of geochemistry to petroleum migration, accumulation, and alteration. In addition the paper deals with the biomarker revolution, which began in earnest about 1964, and with early models of geothermal history. Concepts in petroleum geochemistry have continually evolved, enhanced by the development of new analytical techniques, leading to new discoveries concerning the origin and occurrence of petroleum.

Organic Geochemistry↗

Concentration of organic contaminants in fish and their biological effects in a wastewater-dominated urban stream

Data are presented on the concentrations of alkylphenol and alkylphenol ethoxylates (APEs) and persistent organic compounds in largemouth bass collected from a waste-water dominated stream in downtown Chicago. The fish residue concentrations of APEs are compared to concentrations of the APEs in the water that were collected at weekly intervals over two months bracketing the fall (2006) and a spring (2007) fish collection. The concentrations of APEs were significantly higher in the spring-collected fish (5.42 μg/g) versus the fall (0.99 μg/g) tand these differences were shared by differences in the water concentrations (spring — 11.47 versus fall — 3.44 μg/L). The differences in water concentration were negatively correlated with water temperatures observed over the two sampling times. Fish residue concentrations of persistent organic compounds (PCBs, PBDEs, toxaphene, and many legacy pesticides including the DDT family) did not vary from fall to spring. Some of these residue concentrations were comparable to the highest NPE (nonylphenol ethoxylate) homologue concentrations, e.g. NP1EO was 3.5 μg/g in the bass for the spring, the PBDE-congener 47 and p,p′-DDE averaged 1.0 μg/g and 0.5 μg/g, respectively, over both seasons. All the other persistent single-analyte concentrations were lower. Biological endpoints for endocrine effects measured in the same fish showed that there was an apparent positive correlation for physiological effects based on increased vitellogenin levels in males versus concentration of NPEs; however there were no observable histological differences in fall versus spring fish samples.

Science of the Total Environment↗

Quality-Assurance Data for Routine Water Analyses by the U.S. Geological Survey Laboratory in Troy, New York-July 1997 through June 1999

The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance/quality-control data for the time period addressed in this report were stored in the laboratory's SAS data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality- control samples analyzed from July 1997 through June 1999. Results for the quality-control samples for 18 analytical procedures were evaluated for bias and precision. Control charts indicate that data for eight of the analytical procedures were occasionally biased for either high-concentration and (or) low-concentration samples but were within control limits; these procedures were: acid-neutralizing capacity, total monomeric aluminum, total aluminum, ammonium, calcium, chloride, specific conductance, and sulfate. The data from the potassium and sodium analytical procedures are insufficient for evaluation. Results from the filter-blank and analytical-blank analyses indicate that the procedures for 11 of 13 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. Blank analysis results for chloride showed that 22 percent of blanks did not meet data-quality objectives and results for dissolved organic carbon showed that 31 percent of the blanks did not meet data-quality objectives. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 14 of the 18 analytes. At least 90 percent of the samples met data-quality objectives for all analytes except total aluminum (70 percent of samples met objectives) and potassium (83 percent of samples met objectives). Results of the USGS interlaboratory Standard Reference Sample (SRS) Project indicated good data quality for most constituents over the time period. The P-sample (low-ionic-strength constituents) analysis had good ratings in two of these studies and a satisfactory rating in the third. The results of the T-sample (trace constituents) analysis indicated high data quality with good ratings in all three studies. The N-sample (nutrient constituents) studies had one each of excellent, good, and satisfactory ratings. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 80 percent of the samples met data-quality objectives for 9 of the 13 analytes; the exceptions were dissolved organic carbon, ammonium, chloride, and specific conductance. Data-quality objectives were not met for dissolved organic carbon in two NWRI studies, but all of the samples were within control limits for the last study. Data-quality objectives were not met in 41 percent of samples analyzed for ammonium, 25 percent of samples analyzed for chloride, and 30 percent of samples analyzed for specific conductance. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 84 percent of the samples analyzed for calcium, chloride, magnesium, pH, and potassium. Data-quality objectives were met by 73 percent of those analyzed for sulfate. The data-quality objective was not met for sodium. The data are insufficient for evaluation of the specific conductance results.

Open-File Report↗

Effects of nonmotorized recreation on ungulates in the western United States—A science synthesis to inform National Environmental Policy Act analyses

The U.S. Geological Survey is working with Federal land management agencies to develop a series of science syntheses to support National Environmental Policy Act (NEPA) analyses. This report synthesizes science information about the potential effects of nonmotorized recreation on ungulates in the western United States. We conducted a structured literature search to find published science, data, and analysis methods about the characteristics of nonmotorized recreation, ungulate exposure and response to nonmotorized recreation, and approaches to mitigate negative effects of nonmotorized recreation on ungulates. The sections of the report align with standard elements of the NEPA analysis process. We found that timing, intensity, duration, and spatial distribution of nonmotorized recreation are important factors to understand when assessing effects of recreation on ungulates. Several aspects of ungulate biology, which vary by species, population, and individual, affect ungulate susceptibility to effects from recreation, including diet, migration and movement, and seasonal biology. Techniques for assessing effects include basic spatial analyses based on buffers around trails and recreation sites and more technical analytical methods based on displacement or avoidance of recreation sites. Options for mitigating negative effects of nonmotorized recreation on ungulates include timing and type-of-use restrictions, recreator education, and project design features to avoid human-ungulate conflicts. Public land managers can use this report by incorporating it by reference in NEPA analyses or as a general reference to find literature or identify gaps in the literature about the effects of noise from nonmotorized recreation on ungulates.

Scientific Investigations Report↗

Hydrologic compartmentalization and analytic-element groundwater-flow simulations for a draining mine tunnel

Draining mine tunnels contribute contaminants to groundwater and surface water, but remediation strategies may be hindered as hydrogeologic characterization and modeling of these heterogeneous features generally relies on sparse data sets. The Captain Jack mine site in Colorado, USA, presents a unique data set allowing for temporal evaluation of groundwater connectivity in the vicinity of an abandoned mine, where a hydraulic bulkhead is impounding water within the mine workings. This study applied statistical analysis of system pressure responses to bulkheading and used an analytic-element modeling approach to characterize heterogeneity and groundwater flow. Groundwater-level elevation data collected over a period of 4 years, both prior to and after bulkheading, indicate that the mine workings act as a sink to the local groundwater system. Despite groundwater flow being generally oriented towards the mine workings, there are also large vertical and horizontal hydraulic gradients which persist through time. Although the groundwater system is highly compartmentalized, statistical analysis using Kendall’s Tau indicates correlations between hydraulic head changes in the mine workings and several wells completed in crystalline bedrock, indicating the influence of fracture flow. An analytic-element model was parameterized to account for uncertainty in hydraulic conductivity, recharge, and discharge. Model results reproduced the range of observed hydraulic heads in the mine workings and adjacent igneous dikes but failed to closely simulate hydraulic heads in several wells located distal from the mine workings in granitic bedrock. The modeling approach shows potential promise, however, for conducting preliminary modeling to guide data collection at other similar mine sites.

Colorado↗

Applications of optical sensors for high-frequency water-quality monitoring and research

The recent commercial availability of in-situ optical sensors, together with new techniques for data collection and analysis, provides the opportunity to monitor a wide range of water-quality constituents over time scales during which environmental conditions actually change. Traditional approaches for data collection (daily to monthly discrete samples) are often limited by high sample collection, processing, and analytical costs, difficult site access, and logistical challenges, particularly for long-term sampling at a large number of sites. Optical sensors that continuously measure constituents in the environment by absorbance or fluorescence properties (Figure 1) have had a long history of use in oceanography for measuring highly resolved concentrations and fluxes of organic matter, nutrients, and algal material. However, much of the work using commercially-available optical sensors in rivers and streams has taken place in only the last few years. Figure 1. [NOT SHOWN] Optical sensor technology is now sufficiently developed to warrant broader application for research and monitoring in coastal and freshwater systems, and the United States Geological Survey (a U.S. science agency) is now using these sensors in a variety of research and monitoring programs to better understand water quality in-situ and in real-time. Examples are numerous and range from the applications of nitrate sensors for calculating loads to estuaries susceptible to hypoxia (Pellerin et al., 2014) to the use of fluorometers to estimate methymercury fluxes (Bergamaschi et al., 2011) and disinfection byproduct formation (Carpenter et al., 2013). Transmitting these data in real-time provides information that can be used for early trend detection, help identify monitoring gaps critical for water management, and provide science-based decision support across a range of issues related to water quality, freshwater ecosystems, and human health. Despite the value of these sensors, collecting data that meet high-quality standards requires investment in and adherence to tested and established methods and protocols for sensor operation and data management (Pellerin et al., 2013). For example, optical sensor measurements can be strongly influenced by a variety of matrix effects, including water temperature, inner filtering from highly colored water, and scattering of light by suspended particles (Downing et al., 2012). Characterizing and correcting sensors for these effects &ndash; as well as the continued development of common methodologies and protocols for sensor use &ndash; will be critical to ensuring comparable measurements across sites and over time. In addition, collaborative efforts such as the Nutrient Sensor Challenge (www.nutrients-challenge.org) will continue to accelerate the development, production and use of affordable, reliable and accurate sensors for a range of environments. REFERENCES Bergamaschi .B.A., Fleck J.A., Downing B.D., Boss E., Pellerin B.A., Ganju N.K., Schoellhamer D.H., Byington A.A., Heim W.A., Stephenson M., Fujii R. (2011), Methyl mercury dynamics in a tidal wetland quantified using in situ optical measurements. Limnology and Oceanography, 56(4): 1355-1371. Carpenter K.D., Kraus T.E.C., Goldman J.H., Saraceno J., Downing B.D., Bergamaschi B.A., McGhee G., Triplett T. (2013), Sources and Characteristics of Organic Matter in the Clackamas River, Oregon, Related to the Formation of Disinfection By-products in Treated Drinking Water: U.S. Geological Survey Scientific Investigations Report 2013&ndash;5001, 78 p. Downing .B.D., Pellerin B.A., Bergamaschi B.A., Saraceno J., Kraus T.E.K. (2012), Seeing the light: The effects of particles, temperature and inner filtering on in situ CDOM fluorescence in rivers and streams. Limnology and Oceanography: Methods, 10: 767-775. Pellerin B.A., Bergamaschi B.A., Downing B.D., Saraceno J., Garrett J.D., Olsen L.D. (2013), Optical Techniques for the Determination of Nitrate in En

Conference Paper↗

Geophysical log analysis of selected test and residential wells at the Shenandoah Road National Superfund Site, East Fishkill, Dutchess County, New York

The U.S. Geological Survey collected and analyzed geophysical logs from 20 test wells and 23 residential wells at the Shenandoah Road National Superfund Site in East Fishkill, New York, from 2006 through 2010 as part of an Interagency Agreement to provide hydrogeologic technical support to the U.S. Environmental Protection Agency, Region 2. The geophysical logs collected include caliper, gamma, acoustic and optical televiewer, deviation, electromagnetic-induction, magnetic-susceptibility, fluid-property, and flow under ambient and pumped conditions. The geophysical logs were analyzed along with single-well aquifer test data and drilling logs to characterize the lithology, fabric, fractures, and flow zones penetrated by the wells. The results of the geophysical log analysis were used as part of the hydrogeologic characterization of the site and in the design of discrete-zone monitoring installations in the test wells and selected residential wells. Most of the logged test and residential wells penetrated gneiss of the Hudson Highlands Complex or dolostones in the Wappinger Group, and some wells penetrated both the dolostone and gneiss. The bedrock fabric reflects the regional northeast-southwest structural trend, as well as localized folding, and includes foliation in the gneiss and bedding in the dolostone. Many fractures were oriented along the bedrock fabric, whereas others were orthogonal to the fabric. Total wellbore transmissivity of the wells was estimated from short-term, single-well aquifer test data through the use of the Cooper-Jacob analytical solution. An empirical relation was established to estimate total wellbore transmissivity from specific-capacity data for wells with insufficient transient drawdown measurements. Wellbore transmissivity estimates ranged from 0.36 to 370 feet squared per day (ft 2 /d), whereas specific capacities ranged from 0.03 to 2.1 gallons per minute per foot ((gal/min)/ft). Transmissivity and hydraulic heads of individual fracture zones were estimated from the total wellbore transmissivity and flow logs through use of an analytical model based on the Thiem equation. The model-estimated transmissivity of 95 fracture zones delineated in the 43 wells ranged from 0.25 to 340 ft 2 /d, with a median value of 6.7 ft 2 /d. The difference between model-estimated fracture-zone heads and the composite heads in each well ranged from less 0.01 to more than 10 feet (ft). Flow-log analysis generally provided an order of magnitude estimate for the fracture-zone hydraulic-head difference on the basis of a comparison of estimated and measured values. The geophysical logs and their analyses are available for display and download from the U.S. Geological Survey, New York Water Science Center, online geophysical log archive ( http://ny.water.usgs.gov/maps/geologs/ ) in LAS (Log ASCII Standard), PDF, and WellCad formats.

New York↗

Occurrence of mixed organic and inorganic chemicals in groundwater and tapwater, town of Campbell, Wisconsin, 2021–22

In response to previous reports of per- and polyfluoroalkyl substances (PFAS) contamination in French Island’s (located in the Mississippi River within the town of Campbell, Wisconsin) primary source of drinking water, 11 locations were sampled by the U.S. Geological Survey (USGS) in October 2021 to assess the potential presence of contaminant mixtures, including PFAS, in tapwater. Three locations were assessed seven times each over the course of three days. These samples were chosen to evaluate the water quality of the deeper Mount Simon bedrock aquifer and the water quality of the shallower sand and gravel (alluvial) aquifer at two locations. The other eight sample locations were spatially distributed within Campbell and were sampled once each. For each of these 11 sites, tapwater samples were analyzed for disinfection byproducts (DBP), pesticides, PFAS, pharmaceuticals, semi-volatile organic compounds (SVOC), volatile organic compounds (VOC), cations, anions, trace elements, alkalinity, microbial indicators, as well as measurements of water temperature, specific conductance, and pH. Of the 506 organic compounds analyzed in each water-quality sample, 74 (14 percent) were detected at least one time in any of the samples collected. Of the 14 percent, detected analytes included 27 pesticides (5 percent), 14 PFAS (3 percent), 6 pharmaceuticals (1 percent), 7 SVOC (1 percent), and 20 VOC (4 percent). No DBP were detected. The total number of organic compounds detected per sample ranged from 0–20 (median of 10), with the sum of concentrations ranging from not detected (nd)–2.53 micrograms per liter (μg/L; median of 0.333 μg/L). Of the inorganic constituents measured, eight were not detected above their reporting limit in any of the samples. The inorganic constituents that were not detected were antimony, arsenic, beryllium, cadmium, cobalt, molybdenum, selenium, and vanadium. Along with the 11 sites sampled throughout Campbell, Wisconsin, beginning in October 2021, four more wells were sampled on the Upper Midwest Environmental Sciences Center (UMESC) campus for PFAS. Three of these sites withdraw water from the shallow alluvial aquifer (the same source water for tapwater site 002) and one from the Mount Simon aquifer (the same source of water for tapwater site 001). This sampling is ongoing with results from samples through December 2022 summarized in this report. Of the 33 PFAS analyzed in samples from the four UMESC locations, 15 individual PFAS were detected at least one time in any of the samples analyzed with the sum of PFAS concentrations ranging from nd–1.49 μg/L (median of 0.309 μg/L).

Wisconsin↗

Geologic implications of gas hydrates in the offshore of India: results of the National Gas Hydrate Program Expedition 01

The Indian National Gas Hydrate Program Expedition 01 (NGHP-01) is designed to study the occurrence of gas hydrate along the passive continental margin of the Indian Peninsula and in the Andaman convergent margin, with special emphasis on understanding the geologic and geochemical controls on the occurrence of gas hydrate in these two diverse settings. The NGHP-01 expedition established the presence of gas hydrates in the Krishna-Godavari and Mahanadi Basins, and the Andaman Sea. The expedition discovered in the Krishna-Godavari Basin one of the thickest gas hydrate accumulations ever documented, in the Andaman Sea one of the thickest and deepest gas hydrate stability zones in the world, and established the existence of a fully developed gas hydrate petroleum system in all three basins. The primary goal of NGHP-01 was to conduct scientific ocean drilling/coring, logging, and analytical activities to assess the geologic occurrence, regional context, and characteristics of gas hydrate deposits along the continental margins of India. This was done in order to meet the long-term goal of exploiting gas hydrate as a potential energy resource in a cost effective and safe manner. During its 113.5-day voyage, the D/V JOIDES Resolution cored and/or drilled 39 holes at 21 sites (1 site in Kerala-Konkan, 15 sites in Krishna-Godavari, 4 sites in Mahanadi, and 1 site in the Andaman deep offshore area), penetrated more than 9250 m of sedimentary section, and recovered nearly 2850 m of core. Twelve holes were logged with logging-while-drilling (LWD) tools and an additional 13 holes were wireline logged. The science team utilized extensive on-board laboratory facilities to examine and prepare preliminary reports on the physical properties, geochemistry, and sedimentology of all the data collected prior to the end of the expedition. Samples were also analyzed in additional post-expedition shore-based studies conducted in leading laboratories around the world. One of the specific objectives of this expedition was to test gas hydrate formation models and constrain model parameters, especially those that account for the formation of concentrated gas hydrate accumulations. The necessary data for characterizing the occurrence of in situ gas hydrate, such as interstitial water chlorinities, core-derived gas chemistry, physical and sedimentological properties, thermal images of the recovered cores, and downhole measured logging data (LWD and/or conventional wireline log data), were obtained from most of the drill sites established during NGHP-01. Almost all of the drill sites yielded evidence for the occurrence of gas hydrate; however, the inferred in situ concentration of gas hydrate varied substantially from site to site. For the most part, the interpretation of downhole logging data, core thermal images, interstitial water analyses, and pressure core images from the sites drilled during NGHP-01 indicate that the occurrence of concentrated gas hydrate is mostly associated with the presence of fractures in the sediments, and in some limited cases, by coarser grained (mostly sand-rich) sediments.

Marine and Petroleum Geology↗