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USGS2011

Factors influencing riverine fish assemblages in Massachusetts

The U.S. Geological Survey, in cooperation with the Massachusetts Department of Conservation and Recreation, Massachusetts Department of Environmental Protection, and the Massachusetts Department of Fish and Game, conducted an investigation of fish assemblages in small- to medium-sized Massachusetts streams. The objective of this study was to determine relations between fish-assemblage characteristics and anthropogenic factors, including impervious cover and estimated flow alteration, relative to the effects of environmental factors, including physical-basin characteristics and land use. The results of this investigation supersede those of a preliminary analysis published in 2010. Fish data were obtained for 669 fish-sampling sites from the Massachusetts Division of Fisheries and Wildlife fish-community database. A review of the literature was used to select fish metrics - species richness, abundance of individual species, and abundances of species grouped on life history traits - responsive to flow alteration. The contributing areas to the fish-sampling sites were delineated and used with a geographic information system to determine a set of environmental and anthropogenic factors that were tested for use as explanatory variables in regression models. Reported and estimated withdrawals and return flows were used together with simulated unaltered streamflows to estimate altered streamflows and indicators of flow alteration for each fish-sampling site. Altered streamflows and indicators of flow alteration were calculated on the basis of methods developed in a previous U.S. Geological Survey study in which unaltered daily streamflows were simulated for a 44-year period (water years 1961-2004), and streamflow alterations were estimated by use of water-withdrawal and wastewater-return data previously reported to the State for the 2000-04 period and estimated domestic-well withdrawals and septic-system discharges. A variable selection process, conducted using principal components analysis and Spearman rank correlation, was used to select a set of 15 non-redundant environmental and anthropogenic factors to test for use as explanatory variables in the regression analyses. Twenty-one fish species were used in a multivariate analysis of fish-assemblage patterns. Results of nonmetric multidimensional scaling and hierarchical cluster analysis were used to group fish species into fluvial and macrohabitat generalist habitat-use classes. Two analytical techniques, quantile regression and generalized linear modeling, were applied to characterize the association between fish-response variables and environmental and anthropogenic explanatory variables. Quantile regression demonstrated that as percent impervious cover and an indicator of percent alteration of August median flow from groundwater withdrawals increase, the relative abundance and species richness of fluvial fish decrease. The quantile regression plots indicate that (1) as many as seven fluvial fish species are expected in streams with little flow alteration or impervious cover, (2) no more than four fluvial fish species are expected in streams where flow alterations from groundwater withdrawals exceed 50 percent of the August median flow or the percent area of impervious cover exceeds 15 percent, and (3) few fluvial fish remain at high rates of withdrawal (approaching 100 percent) or high rates of impervious cover (between 25 and 30 percent). Three generalized linear models (GLMs) were developed to quantify the response of fluvial fish to multiple environmental and anthropogenic variables. All variables in the GLM equations were demonstrated to be significant (p less than 0.05, with most less than 0.01). Variables in the fluvial-fish relative-abundance model were channel slope, estimated percent alteration of August median flow from groundwater withdrawals, percent wetland in a 240-meter buffer strip, and percent impervious cover. Variables in the fluvial-fish species-richness model were drainage area, channel slope, total undammed reach length, percent wetland in a 240-meter buffer strip, and percent impervious cover. Variables in the brook trout relativeabundance model were drainage area, percent open water, and percent impervious cover. The variability explained by the GLM models, as measured by the pseudo R2, ranged from 18.2 to 34.6, and correlations between observed and predicted values ranged from 0.50 to 0.60. Results of GLM models indicated that, keeping all other variables the same, a one-unit (1 percent) increase in the percent depletion of August median flow would result in a 0.9-percent decrease in the relative abundance (in counts per hour) of fluvial fish. The results of GLM models also indicated that a unit increase in impervious cover (1 percent) resulted in a 3.7-percent decrease in the relative abundance of fluvial fish, a 5.4-percent decrease in fluvial-fish species richness, and an 8.7-percent decrease in brook trout relative abundance.

Massachusetts↗

USGS2021

Comparisons among three diet analyses demonstrate multiple patterns in the estimated adult diet of a freshwater piscivore, Salvelinus namaycush

Understanding trophic interactions is critical for successful resource management. However, studying diet patterns (e.g., spatial and seasonal changes) can require extensive effort. Using individual analyses to interpret patterns may be further complicated by assumptions and limitations of the analytical approach. We investigated and compared predicted adult lake trout (Salvelinus namaycush) diet composition and patterns using stomach content analysis (SCA), fatty acid analysis (FAS), and stable isotope analysis (SIA) individually and simultaneously. The three analyses were conducted for fall-captured fish in Lake Ontario and provided different diet composition estimates; SCA suggested alewife (Alosa pseudoharengus) was dominant by frequency and mass, while FAA and SIA suggested rainbow smelt (Osmerus mordax) contributed the most based on similarity among fatty acid signatures and two-stable isotope (carbon and nitrogen) mixing models, respectively. We hypothesize the disagreement among diet estimates is a result of a seasonal shift in diet variably expressed due to differing extent of time reflected by the diet metric: hours to days for SCA, weeks to months for FAA and several months for SIA. Despite variability in diet composition estimates among methods, similar patterns in lake trout diet were observed among the three diet analyses; the contribution of alewife in lake trout diet was greater for larger individuals and for males compared to females, particularly in the east and northeast regions of the lake where alewife density was relatively low. Thus, the complementary results from the three analyses suggest that length, location, sex, and season all influence lake trout diet. Individually, analyses often failed to identify these patterns in lake trout diet with significance, and some of the patterns have not been observed in previous studies of lake trout diet in Lake Ontario. The thorough description of lake trout diet obtained from a single sampling season demonstrates how simultaneous use of multiple diet analyses may allow investigation of spatial and seasonal diet composition and with reduced sampling effort.

Lake Ontario↗

USGS2002

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↗

USGS1999

WTAQ: A Computer Program for Calculating Drawdowns and Estimating Hydraulic Properties for Confined and Water-Table Aquifers

The computer program WTAQ calculates hydraulic-head drawdowns in a confined or water-table aquifer that result from pumping at a well of finite or infinitesimal diameter. The program is based on an analytical model of axial-symmetric ground-water flow in a homogeneous and anisotropic aquifer. The program allows for well-bore storage and well-bore skin at the pumped well and for delayed drawdown response at an observation well; by including these factors, it is possible to accurately evaluate the specific storage of a water-table aquifer from early-time drawdown data in observation wells and piezometers. For water-table aquifers, the program allows for either delayed or instantaneous drainage from the unsaturated zone. WTAQ calculates dimensionless or dimensional theoretical drawdowns that can be used with measured drawdowns at observation points to estimate the hydraulic properties of confined and water-table aquifers. Three sample problems illustrate use of WTAQ for estimating horizontal and vertical hydraulic conductivity, specific storage, and specific yield of a water-table aquifer by type-curve methods and by an automatic parameter-estimation method.

Water-Resources Investigations Report↗

USGS2018

Evaluating spatial and temporal variability in growth and mortality for recreational fisheries with limited catch data

Understanding the spatial and temporal variability in life-history traits among populations is essential for the management of recreational fisheries. However, valuable freshwater recreational fish species often suffer from a lack of catch information. In this study, we demonstrated the use of an approach to estimate the spatial and temporal variability in growth and mortality in the absence of catch data and apply the method to riverine smallmouth bass ( Micropterus dolomieu ) populations in Pennsylvania, USA. Our approach included a growth analysis and a length-based analysis that estimates mortality. Using a hierarchical Bayesian approach, we examined spatial variability in growth and mortality by assuming parameters vary spatially but remain constant over time and temporal variability by assuming parameters vary spatially and temporally. The estimated growth and mortality of smallmouth bass showed substantial variability over time and across rivers. We explored the relationships of the estimated growth and mortality with spring water temperature and spring flow. Growth rate was likely to be positively correlated with these two factors, while young mortality was likely to be positively correlated with spring flow. The spatially and temporally varying growth and mortality suggest that smallmouth bass populations across rivers may respond differently to management plans and disturbance such as environmental contamination and land-use change. The analytical approach can be extended to other freshwater recreational species that also lack of catch data. The approach could also be useful in developing population assessments with erroneous catch data or be used as a model sensitivity scenario to verify traditional models even when catch data are available.

Pennsylvania↗

USGS1962

Theory of aquifer tests

The development of water supplies from wells was placed on a rational basis with Darcy's development of the law governing the movement of fluids through sands and with Dupuit's application of that law to the problem of radial flow toward a pumped well. As field experience increased, confidence in the applicability of quantitative methods was gained and interest in developing solutions for more complex hydrologic problems was stimulated. An important milestone was Theis' development in 1935 of a solution for the nonsteady flow of ground water, which enabled hydrologists for the first time to predict future changes in ground-water levels resulting from pumping or recharging of wells. In the quarter century since, quantitative ground-water hydrology has been enlarging so rapidly as to discourage the preparation of comprehensive textbooks. This report surveys developments in fluid mechanics that apply to groundwater hydrology. It emphasizes concepts and principles, and the delineation of limits of applicability of mathematical models for analysis of flow systems in the field. It stresses the importance of the geologic variable and its role in governing the flow regimen. The report discusses the origin, occurrence, and motion of underground water in relation to the development of terminology and analytic expressions for selected flow systems. It describes the underlying assumptions necessary for mathematical treatment of these flow systems, with particular reference to the way in which the assumptions limit the validity of the treatment.

Water Supply Paper↗

USGS1975

Water-quality data from oil and gas wells in part of the Permian Basin, southeastern New Mexico and western Texas

Approximately 8,000 chemical analyses of water produced from formations of several geologic ages in south eastern New Mexico and western Texas are tabulated by both geographic location and geologic formation. Empirical and mathematical relationships between (1) the dissolved solids and the measured and computed resistivity of water, the chloride-ion concentration and the density, and (2) the concentration of chloride-ion and the density and the resistivity of water, were established. Resistivities of water computed following a method developed by Moore, Szasz, and Whitney (1966) using the concentration of the six most common constituents dissolved in natural water correlate favorably with the measured resistivities of natural water. The water analyses were obtained chiefly from oil companies and oil-service companies operating in the western part of the Permian basin. The data were associated with the proper well by searching location, operator, and reference number cross indexes prepared from the Permian Basin Well Data System files. The cross indexes were determined to be essential to efficient data processing operations. After preliminary screening for nonrepresentative data, all data were indexed to the Permian Basin Well Data System magnetic tape file scout records by the unique reference number. The data were then coded, punched into tabulating cards, and stored on magnetic tape for computer operations. Data verification steps not normally required when using data received from a laboratory following standardized analytical techniques on samples obtained under standardized and controlled procedures were performed in order to upgrade reliability of the information. Data errors detected included poorly located or identified samples; mistakes including reproducing, or key punching; laboratory errors; inconsistent reporting; and nonrepresentative or contaminated samples.

New Mexico, Texas↗

USGS2021

Compositional evolution of organic matter in Boquillas Shale across a thermal gradient at the single particle level

The molecular composition of petroliferous organic matter and its compositional evolution throughout thermal maturation provides insight for understanding petroleum generation. This information is critical for understanding hydrocarbon resources in unconventional reservoirs, as source rock organic matter is highly dispersed, in contact with the surrounding mineral matrix, and may occur as multiple organic matter maceral types. Here, Raman spectroscopy and optical microscopy approaches were applied to a marginally mature (vitrinite reflectance ~0.5%) sample of the Late Cretaceous Boquillas Shale before and after hydrous pyrolysis (HP) at 300 °C and 330 °C for 72 h. This analytical approach allowed for correlative examination of micro-scale changes in organic matter compositional properties (e.g., aromaticity) for a variety of organic matter macerals across a thermal gradient (from marginally mature into the late oil/wet gas window) at the single particle level. Results indicate that while the examined amorphous organic matter, solid bitumen, and vitrinite particles exhibit different aromatic signatures in the unheated shale, they effectively progress along a similar trend through composition space with thermal maturation. Examined inertinite fragments were generally insensitive to the applied thermal stress, reinforcing the idea that reservoir temperature may be secondary for dictating the molecular composition of inertinite. Additional analysis of Raman spectra for individual organic matter macerals was performed using multivariate curve resolution (MCR) and correlation of standard Raman and reflectance-derived thermal maturity proxies against MCR parameters shows consistent trends. This trend suggests that MCR may be a fast and statistically robust method for extracting compositional information from Raman spectra of sedimentary organic matter, and can be used to construct thermal maturity relationships. These findings inform our understanding of how different petroliferous organic matter maceral types evolve throughout thermal reactions and further demonstrate that Raman spectroscopy combined with petrographic analysis can provide complementary estimates of organic matter composition and thermal maturity.

International Journal of Coal Geology↗

USGS2004

Core-scale permeability of an actively venting, felsic-hosted hydrothermal system: The PACMANUS Hydrothermal Field

Permeability of the ocean crust is one of the most crucial parameters for constraining submarine fluid flow systems. Active hydrothermal fields are dynamic areas where fluid flow strongly affects the geochemistry and biology of the surrounding environment. There have been few permeability measurements in these regions, especially in felsic-hosted hydrothermal systems. We present a data set of 38 permeability and porosity measurements from the PACMANUS hydrothermal field, an actively venting, felsic hydrothermal field in the eastern Manus Basin. Permeability was measured using a complex transient method on 2.54-cm minicores. Permeability varies greatly between the samples, spanning over five orders of magnitude. Permeability decreases with both depth and decreasing porosity. When the alteration intensity of individual samples is considered, relationships between depth and porosity and permeability become more clearly defined. For incompletely altered samples (defined as >5% fresh rock), permeability and porosity are constant with depth. For completely altered samples (defined as <5% fresh rock), permeability and porosity decrease with depth. On average, the permeability values from the PACMANUS hydrothermal field are greater than those in other submarine environments using similar core-scale laboratory measurements; the average permeability, 4.5 x 10–16 m2, is two to four orders of magnitude greater than in other areas. Although the core-scale permeability is higher than in other seafloor environments, it is still too low to obtain the fluid velocities observed in the PACMANUS hydrothermal field based on simplified analytical calculations. It is likely that core-scale permeability measurements are not representative of bulk rock permeability of the hydrothermal system overall, and that the latter is predominantly fracture controlled.

Conference Paper↗

USGS2007

Chapter 8 Tool for monitoring hydrophilic contaminants in water: polar organic chemical integrative sampler (POCIS)

The development of the polar organic chemical integrative sampler (POCIS) provides environmental scientists and policy makers a tool for assessing the presence and potential impacts of the hydrophilic component of these organic contaminants. The POCIS provides a means for determining the time-weighted average (TWA) concentrations of targeted chemicals that can be used in risk assessments to determine the biological impact of hydrophilic organic compounds (HpOCs) on the health of the impacted ecosystem. Field studies have shown that the POCIS has advantages over traditional sampling methods in sequestering and concentrating ultra-trace to trace levels of chemicals over time resulting in increased method sensitivity, ability to detect chemicals with a relatively short residence time or variable concentrations in the water, and simplicity in use. POCIS extracts can be tested using bioassays and can be used in organism dosing experiments for determining toxicological significance of the complex mixture of chemicals sampled. The POCIS has been successfully used worldwide under various field conditions ranging from stagnant ponds to shallow creeks to major river systems in both fresh and brackish water.

Comprehensive Analytical Chemistry↗

USGS2013

Groundwater-quality data in the Cascade Range and Modoc Plateau study unit, 2010-Results from the California GAMA Program

Groundwater quality in the 39,000-square-kilometer Cascade Range and Modoc Plateau (CAMP) study unit was investigated by the U.S. Geological Survey (USGS) from July through October 2010, as part of the California State Water Resources Control Board (SWRCB) Groundwater Ambient Monitoring and Assessment (GAMA) Program’s Priority Basin Project (PBP). The GAMA PBP was developed in response to the California Groundwater Quality Monitoring Act of 2001 and is being conducted in collaboration with the SWRCB and Lawrence Livermore National Laboratory (LLNL). The CAMP study unit is the thirty-second study unit to be sampled as part of the GAMA PBP. The GAMA CAMP study was designed to provide a spatially unbiased assessment of untreated-groundwater quality in the primary aquifer system and to facilitate statistically consistent comparisons of untreated-groundwater quality throughout California. The primary aquifer system is defined as that part of the aquifer corresponding to the open or screened intervals of wells listed in the California Department of Public Health (CDPH) database for the CAMP study unit. The quality of groundwater in shallow or deep water-bearing zones may differ from the quality of groundwater in the primary aquifer system; shallow groundwater may be more vulnerable to surficial contamination. In the CAMP study unit, groundwater samples were collected from 90 wells and springs in 6 study areas (Sacramento Valley Eastside, Honey Lake Valley, Cascade Range and Modoc Plateau Low Use Basins, Shasta Valley and Mount Shasta Volcanic Area, Quaternary Volcanic Areas, and Tertiary Volcanic Areas) in Butte, Lassen, Modoc, Plumas, Shasta, Siskiyou, and Tehama Counties. Wells and springs were selected by using a spatially distributed, randomized grid-based method to provide statistical representation of the study unit (grid wells). Groundwater samples were analyzed for field water-quality indicators, organic constituents, perchlorate, inorganic constituents, radioactive constituents, and microbial indicators. Naturally occurring isotopes and dissolved noble gases also were measured to provide a dataset that will be used to help interpret the sources and ages of the sampled groundwater in subsequent reports. In total, 221 constituents were investigated for this study. Three types of quality-control samples (blanks, replicates, and matrix spikes) were collected at approximately 10 percent of the wells in the CAMP study unit, and the results for these samples were used to evaluate the quality of the data for the groundwater samples. Blanks rarely contained detectable concentrations of any constituent, suggesting that contamination from sample collection procedures was not a significant source of bias in the data for the groundwater samples. Replicate samples generally were within the limits of acceptable analytical reproducibility. Matrix-spike recoveries were within the acceptable range (70 to 130 percent) for approximately 90 percent of the compounds. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, untreated groundwater typically is treated, disinfected, and (or) blended with other waters to maintain water quality. Regulatory benchmarks apply to water that is served to the consumer, not to untreated groundwater. However, to provide some context for the results, concentrations of constituents measured in the untreated groundwater were compared with regulatory and non-regulatory health-based benchmarks established by the U.S. Environmental Protection Agency (USEPA) and CDPH, and to non-regulatory benchmarks established for aesthetic concerns by CDPH. Comparisons between data collected for this study and benchmarks for drinking water are for illustrative purposes only and are not indicative of compliance or non-compliance with those benchmarks. All organic constituents and most inorganic constituents that were detected in groundwater samples from the 90 grid wells in the CAMP study unit were detected at concentrations less than drinking-water benchmarks. Of the 148 organic constituents analyzed, 27 were detected in groundwater samples; concentrations of all detected constituents were less than regulatory and nonregulatory health-based benchmarks, and all were less than 1/10 of benchmark levels. One or more organic constituents were detected in 52 percent of the grid wells in the CAMP study unit: VOCs were detected in 30 percent, and pesticides and pesticide degradates were detected in 31 percent. Trace elements, major ions, nutrients, and radioactive constituents were sampled for at 90 grid wells in the CAMP study unit, and most detected concentrations were less than health-based benchmarks. Exceptions include three detections of arsenic greater than the USEPA maximum contaminant level (MCL-US) of 10 micrograms per liter (µg/L), two detections of boron greater than the CDPH notification level (NL-CA) of 1,000 µg/L, two detections of molybdenum greater than the USEPA lifetime health advisory level (HAL-US) of 40 µg/L, two detections of vanadium greater than the CDPH notification level (NL-CA) of 50 µg/L, one detection of nitrate, as nitrogen, greater than the MCL-US of 10 milligrams per liter (mg/L), two detections of uranium greater than the MCL-US of 30 µg/L and the MCL-CA of 20 picocuries per liter (pCi/L), one detection of radon-222 greater than the proposed MCL-US of 4,000 pCi/L, and two detections of gross alpha particle activity greater than the MCL-US of 15 pCi/L. Results for inorganic constituents with non-regulatory benchmarks set for aesthetic concerns showed that iron concentrations greater than the CDPH secondary maximum contaminant level (SMCL-CA) of 300 µg/L were detected in four grid wells. Manganese concentrations greater than the SMCL-CA of 50 µg/L were detected in nine grid wells. Chloride and TDS were detected at concentrations greater than the upper SMCL-CA benchmarks of 500 mg/L and 1,000 mg/L, respectively, in one grid well. Microbial indicators (total coliform and Escherichia coli [E. coli]) were detected in 11 percent of the 83 grid wells sampled for these analyses in the CAMP study unit. The presence of total coliform was detected in nine grid wells, and the presence of E. coli was detected in one of these same grid wells.

California↗

USGS2018

Critically assessing the utility of portable lead analyzers for wildlife conservation

Lead (Pb) exposure in wildlife is a widespread management and conservation concern. Quantitative determination of Pb concentrations in wildlife tissues is the foundation for estimating exposure and risk. Development of low‐cost, portable instruments has improved access and cost‐effectiveness of determining Pb concentrations in blood samples, while also facilitating the ability for wildlife researchers to conduct near real‐time Pb testing. However, these instruments, which use anodic stripping voltammetry (ASV) methodology, may produce an analytical bias in wildlife‐blood Pb concentrations. Additionally, their simplicity invites use without appropriate quality‐assurance–quality‐control measures. Together, these factors can reduce data quality and hamper the ability to evaluate it, raising concerns about use of these instruments to inform important conservation issues. We document the extent to which this bias is addressed in the wildlife toxicology literature, develop quantitative approaches for correcting the bias, and provide recommendations to ensure robust data quality when using these instruments. Of the 25 studies we reviewed that referenced ASV use for determining Pb exposure in wildlife, only 32% acknowledged the existence of bias from the instrument. Importantly, another 20% of the studies actually reported ASV and spectroscopic‐based results together without acknowledging their lack of equivalence. Using a multispecies data set of avian blood Pb concentrations, we found that ASV‐based estimates of paired blood Pb concentrations were 30–38% lower than those from standard spectrometric‐based methods. We provide regression equations based on this analysis of 453 blood samples to allow users of ASV instruments to adjust Pb concentrations to spectrometric‐equivalent values, and propose a series of guidelines to follow when using these instruments to improve data validity.

Wildlife Society Bulletin↗

USGS2000

Quality-assurance design applied to an assessment of agricultural pesticides in ground water from carbonate bedrock aquifers in the Great Valley of eastern Pennsylvania

Assessments to determine whether agricultural pesticides are present in ground water are performed by the Commonwealth of Pennsylvania under the aquifer monitoring provisions of the State Pesticides and Ground Water Strategy. Pennsylvania's Department of Agriculture conducts the monitoring and collects samples; the Department of Environmental Protection (PaDEP) Laboratory analyzes the samples to measure pesticide concentration. To evaluate the quality of the measurements of pesticide concentration for a groundwater assessment, a quality-assurance design was developed and applied to a selected assessment area in Pennsylvania. This report describes the quality-assurance design, describes how and where the design was applied, describes procedures used to collect and analyze samples and to evaluate the results, and summarizes the quality assurance results along with the assessment results. The design was applied in an agricultural area of the Delaware River Basin in Berks, Lebanon, Lehigh, and Northampton Counties to evaluate the bias and variability in laboratory results for pesticides. The design—with random spatial and temporal components—included four data-quality objectives for bias and variability. The spatial design was primary and represented an area comprising 30 sampling cells. A quality-assurance sampling frequency of 20 percent of cells was selected to ensure a sample number of five or more for analysis. Quality-control samples included blanks, spikes, and replicates of laboratory water and spikes, replicates, and 2-lab splits of groundwater. Two analytical laboratories, the PaDEP Laboratory and a U.S. Geological Survey Laboratory, were part of the design. Bias and variability were evaluated by use of data collected from October 1997 through January 1998 for alachlor, atrazine, cyanazine, metolachlor, simazine, pendimethalin, metribuzin, and chlorpyrifos. Results of analyses of field blanks indicate that collection, processing, transport, and laboratory analysis procedures did not contaminate the samples; there were no false-positive results. Pesticides were detected in water when pesticides were spiked into (added to) samples. There were no false negatives for the eight pesticides in all spiked samples. Negative bias was characteristic of analytical results for the eight pesticides, and bias was generally in excess of 10 percent from the ‘true’ or expected concentration (34 of 39 analyses, or 87 percent of the ground-water results) for pesticide concentrations ranging from 0.31 to 0.51 mg/L (micrograms per liter). The magnitude of the negative bias for the eight pesticides, with the exception of cyanazine, would result in reported concentrations commonly 75-80 percent of the expected concentration in the water sample. The bias for cyanazine was negative and within 10 percent of the expected concentration. A comparison of spiked pesticide-concentration recoveries in laboratory water and ground water indicated no effect of the ground-water matrix, and matrix interference was not a source of the negative bias. Results for the laboratory-water spikes submitted in triplicate showed large variability for recoveries of atrazine, cyanazine, and pendimethalin. The relative standard deviation (RSD) was used as a measure of method variability over the course of the study for laboratory waters at a concentration of 0.4 mg/L. An RSD of about 11 percent (or about ?0.05 mg/L)characterizes the method results for alachlor, chlorpyrifos, metolachlor, metribuzin, and simazine. Atrazine and pendimethalin have RSD values of about 17 and 23 percent, respectively. Cyanazine showed the largest RSD at nearly 51 percent. The pesticides with low variability in laboratory-water spikes also had low variability in ground water. The assessment results showed that atrazinewas the most commonly detected pesticide in ground water in the assessment area. Atrazine was detected in water from 22 of the 28 wells sampled, and recovery results for atrazine were some of the worst (largest negative bias). Concentrations of the eight pesticides in ground water from wells were generally less than 0.3 µg/L. Only six individual measurements of the concentrations in water from six of the wells were at or above 0.3 µg/L, ﬁve for atrazine and one for metolachlor. There were eight additional detections of metolachlor and simazine at concentrations less than 0.1 µg/L. No well water contained more than one pesticide at concentra-tions at or above 0.3 µg/L. Evidence exists, how-ever, for a pattern of co-occurrence of metolachlor and simazine at low concentrations with higher concentrations of atrazine. Large variability in replicate samples and negative bias for pesticide recovery from spiked samples indicate the need to use data for pesticide recovery in the interpretation of measured pesti-cide concentrations in ground water. Data from samples spiked with known amounts of pesticides were a critical component of a quality-assurance design for the monitoring component of the Pesti-cides and Ground Water Strategy. Trigger concentrations, the concentrations that require action under the Pesticides and Ground Water Strategy, should be considered maximums for action. This consideration is needed because of the magnitude of negative bias.

Water-Resources Investigations Report↗

USGS2015

A new panel of SNP markers for the individual identification of North American pumas

Pumas Puma concolor are one of the most studied terrestrial carnivores because of their widespread distribution, substantial ecological impacts, and conflicts with humans. Over the past decade, managing pumas has involved extensive efforts including the use of genetic methods. Microsatellites have been the most commonly used genetic markers; however, technical artifacts and little overlap of frequently used loci render large-scale comparison of puma genetic data across studies challenging. Therefore, a panel of genetic markers that can produce consistent genotypes across studies without the need for extensive calibrations is essential for range-wide genetic management of puma populations. Here, we describe the development of PumaPlex, a high-throughput assay to genotype 25 single nucleotide polymorphisms in pumas. We validated PumaPlex in 748 North American pumas Puma concolor couguar, and demonstrated its ability to generate reproducible genotypes and accurately identify individuals. Furthermore, in a test using fecal deoxyribonucleic acid (DNA) samples, we found that PumaPlex produced significantly more genotypes with fewer errors than 12 microsatellite loci, 8 of which are commonly used. Our results demonstrate that PumaPlex is a valuable tool for the genetic monitoring and management of North American puma populations. Given the analytical simplicity, reproducibility, and high-throughput capability of single nucleotide polymorphisms, PumaPlex provides a standard panel of markers that promotes the comparison of genotypes across studies and independent of the genotyping technology used.

Journal of Fish and Wildlife Management↗

USGS2006

New ghost-node method for linking different models with varied grid refinement

A flexible, robust method for linking grids of locally refined ground-water flow models constructed with different numerical methods is needed to address a variety of hydrologic problems. This work outlines and tests a new ghost-node model-linking method for a refined "child" model that is contained within a larger and coarser "parent" model that is based on the iterative method of Steffen W. Mehl and Mary C. Hill (2002, Advances in Water Res., 25, p. 497-511; 2004, Advances in Water Res., 27, p. 899-912). The method is applicable to steady-state solutions for ground-water flow. Tests are presented for a homogeneous two-dimensional system that has matching grids (parent cells border an integer number of child cells) or nonmatching grids. The coupled grids are simulated by using the finite-difference and finite-element models MODFLOW and FEHM, respectively. The simulations require no alteration of the MODFLOW or FEHM models and are executed using a batch file on Windows operating systems. Results indicate that when the grids are matched spatially so that nodes and child-cell boundaries are aligned, the new coupling technique has error nearly equal to that when coupling two MODFLOW models. When the grids are nonmatching, model accuracy is slightly increased compared to that for matching-grid cases. Overall, results indicate that the ghost-node technique is a viable means to couple distinct models because the overall head and flow errors relative to the analytical solution are less than if only the regional coarse-grid model was used to simulate flow in the child model's domain.

Conference Paper↗

USGS1964

Catalytic determination of vanadium in water

A kinetic determination of V(V) as a catalyst was spectrophotometrically performed by using the indicator reaction of Gallamine blue (GB + ) and bromate at pH 2.0. The reaction was followed by measuring absorbance change for a fixed-time of 3 min at 537 nm. The variables such as reagent concentration, pH, buffer concentration, ionic strength and temperature were optimized to improve the selectivity and sensitivity. Under the optimized conditions, the determination of V(V) was performed in the range 1–100 μg L −1 with limits of detection and quantification of 0.31 and 0.94 μg L −1 . The developed kinetic method is sufficiently sensitive, selective and simple. It was successfully applied to the speciative determination of total V and inorganic dissolved vanadium species, V(V) and V(IV) in environmental water samples. The oxidizing property of permanganate is used to differentiate between V(IV) and V(V) species. The V(IV) content was found by subtracting the V(V) content from those of total V. The recovery is above 95% for V(V) spiked samples. Additionally, the accuracy was validated by analysis of a certified water sample, CRM TMDA-53.3, and the results were in good agreement with the certified value.

Analytical Chemistry↗

USGS2007

230Th-U dating of surficial deposits using the ion microprobe (SHRIMP-RG): A microstratigraphic perspective

We used the sensitive high-resolution ion microprobe reverse-geometry (SHRIMP-RG) to date pedogenic opal using the 230 Th–U system. Due to the high-spatial resolution of an ion microprobe (typically 30 μm), regions of pure opal within a sample can be targeted and detrital material can be avoided. In addition, because the technique is non-destructive, the sample can be preserved for other types of analyses including electron microprobe or other stable isotope or trace element ion microprobe measurements. The technique is limited to material with U concentrations greater than ∼50 ppm. However, the high spatial resolution, small sample requirements, and the ability to avoid detrital material make this technique a suitable technique for dating many Pleistocene deposits formed in semi-arid environments. To determine the versatility of the method, samples from several different deposits were analyzed, including silica-rich pebble coatings from pedogenic carbonate horizons, a siliceous sinter deposit, and opaline silica deposited as a spring mound. U concentrations for 30-μm-diameter spots ranged from 50 to 1000 ppm in these types of materials. The 230 Th/ 232 Th activity ratios also ranged from ∼100 to 10 6 , eliminating the need for detrital Th corrections that reduce the precision of traditional U-Th ages for many milligram- and larger-sized samples. In pedogenic material, layers of high-U opal (ca. 500 ppm) are commonly juxtaposed next to layers of calcite with much lower U concentrations (1–2 ppm). If these types of samples are not analyzed using a technique with the appropriate spatial resolution, the ages may be strongly biased towards the age of the opal. Comparison with standard TIMS (Thermal Ionization Mass Spectrometry) measurements from separate microdrilled samples suggests that although the analytical precision of the ion microprobe (SHRIMP-RG) measurements is less than TIMS, the high spatial resolution results in better accuracy in the age determination for finely layered or complex deposits. The ion microprobe approach also may be useful for pre-screening samples to determine the age and degree of post-depositional alteration, analyzing finely layered samples or samples with complex growth histories, and obtaining simultaneous measurements of trace elements.

Quaternary International↗

USGS2019

Radiometric calibration of a non-imaging airborne spectrometer to measure the Greenland ice sheet surface

Methods to radiometrically calibrate a non-imaging airborne visible-to-shortwave infrared (VSWIR) spectrometer to measure the Greenland ice sheet surface are presented. Airborne VSWIR measurement performance for bright Greenland ice and dark bare rock/soil targets is compared against the MODerate resolution atmospheric TRANsmission (MODTRAN ® ) radiative transfer code (version 6.0), and a coincident Landsat 8 Operational Land Imager (OLI) acquisition on 29 July 2015 during an in-flight radiometric calibration experiment. Airborne remote sensing flights were carried out in northwestern Greenland in preparation for the Ice, Cloud, and land Elevation Satellite 2 (ICESat-2) laser altimeter mission. A total of nine science flights were conducted over the Greenland ice sheet, sea ice, and open-ocean water. The campaign's primary purpose was to correlate green laser pulse penetration into snow and ice with spectroscopic-derived surface properties. An experimental airborne instrument configuration that included a nadir-viewing (looking downward at the surface) non-imaging Analytical Spectral Devices (ASD) Inc. spectrometer that measured upwelling VSWIR (0.35 to 2.5 µ m) spectral radiance ( W m - 2 sr - 1 µ m - 1 "> W m − 2 sr − 1 µ m − 1 ) in the two-color Slope Imaging Multi-polarization Photon-Counting Lidar's (SIMPL) ground instantaneous field of view, and a zenith-viewing (looking upward at the sky) ASD spectrometer that measured VSWIR spectral irradiance (W m −2 nm −1 ) was flown. National Institute of Standards and Technology (NIST) traceable radiometric calibration procedures for laboratory, in-flight, and field environments are described in detail to achieve a targeted VSWIR measurement requirement of within 5 % to support calibration/validation efforts and remote sensing algorithm development. Our MODTRAN predictions for the 29 July flight line over dark and bright targets indicate that the airborne nadir-viewing spectrometer spectral radiance measurement uncertainty was between 0.6 % and 4.7 % for VSWIR wavelengths (0.4 to 2.0 µ m) with atmospheric transmittance greater than 80 %. MODTRAN predictions for Landsat 8 OLI relative spectral response functions suggest that OLI is measuring 6 % to 16 % more top-of-atmosphere (TOA) spectral radiance from the Greenland ice sheet surface than was predicted using apparent reflectance spectra from the nadir-viewing spectrometer. While more investigation is required to convert airborne VSWIR spectral radiance into atmospherically corrected airborne surface reflectance, it is expected that airborne science flight data products will contribute to spectroscopic determination of Greenland ice sheet surface optical properties to improve understanding of their potential influence on ICESat-2 measurements.

Atmospheric Measurement Techniques↗