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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↗

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↗

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↗

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↗

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↗

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↗

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↗

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↗

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↗

Essentials of iron, chromium, and calcium isotope analysis of natural materials by thermal ionization mass spectrometry

The use of isotopes to understand the behavior of metals in geological, hydrological, and biological systems has rapidly expanded in recent years. One of the mass spectrometric techniques used to analyze metal isotopes is thermal ionization mass spectrometry, or TIMS. While TIMS has been a useful analytical technique for the measurement of isotopic composition for decades and TIMS instruments are widely distributed, there are significant difficulties associated with using TIMS to analyze isotopes of the lighter alkaline earth elements and transition metals. Overcoming these difficulties to produce relatively long-lived and stable ion beams from microgram-sized samples is a non-trivial task. We focus here on TIMS analysis of three geologically and environmentally important elements (Fe, Cr, and Ca) and present an in-depth look at several key aspects that we feel have the greatest potential to trouble new users. Our discussion includes accessible descriptions of different analytical approaches and issues, including filament loading procedures, collector cup configurations, peak shapes and interferences, and the use of isotopic double spikes and related error estimation. Building on previous work, we present quantitative simulations, applied specifically in this study to Fe and Ca, that explore the effects of (1) time-variable evaporation of isotopically homogeneous spots from a filament and (2) interferences on the isotope ratios derived from a double spike subtraction routine. We discuss how and to what extent interferences at spike masses, as well as at other measured masses, affect the double spike-subtracted isotope ratio of interest (44Ca/40Ca in the case presented, though a similar analysis can be used to evaluate 56Fe/54Fe and 53Cr/52Cr). The conclusions of these simulations are neither intuitive nor immediately obvious, making this examination useful for those who are developing new methodologies. While all simulations are carried out in the context of a specific isotope system, it should be noted that the same methods can be used to evaluate any isotope system of interest. ?? 2008 Elsevier B.V.

Chemical Geology↗

Guidelines for calibration of uncrewed aircraft systems imagery

Executive Summary This report outlines quality assurance (QA) processes, including radiometric and geometric calibration guidelines, and guidelines for data acquisition and quality control to be followed by U.S. Geological Survey (USGS) researchers for acquiring and processing uncrewed aircraft systems (UAS) data. These QA processes ensure that UAS data can be used for quantitative analysis and are comparable with other standard geospatial data. Remote sensing data play a critical role in monitoring Earth’s resources. Traditionally, the USGS and Department of the Interior have used well calibrated metric sensors mounted on satellite or aircraft platforms to collect these data. These sensors and platforms are stable, and data have been processed using standard pipelines. These processes ensured that the data are generally consistent with each other and benefitted a diverse group of users. These data are shared among multiple researchers around the world through the internet and other means, using standard formats and metadata. In the last few years, UAS platforms have democratized the remote sensing data collection further, bringing an unparalleled level of control of time, sensors, and processes to individual researchers. Together with the development of cheaper and lighter sensors and relaxation of prohibitions against UAS operation in the National Airspace System by the Federal Aviation Authority, researchers can collect remote sensing data using UAS platforms. Researchers often customize the sensors on these UAS systems based on their specific requirements and use ad hoc processing steps to generate data. A challenge is that these data are often produced by a wide array of sensors and processes that render them potentially inconsistent with each other. Therefore, unlike data collected from metric sensors, UAS-based data are designed to benefit only specific user groups. The data thus generated often lack traceability to known standards, making them difficult to use with other geospatial data. This report provides radiometric and geometric calibration guidelines, as well as guidelines for data acquisition and quality control, that can be followed by USGS researchers in acquiring and processing UAS data. Instead of calibrating sensors, researchers collecting UAS data can focus on calibrating the data. Various radiometric calibration processes are provided, and the two panel empirical line method is highlighted for radiometric calibration. For geometric calibration, USGS and Department of the Interior researchers are experienced in following standard calibration procedures provided by standard UAS data processing software. However, researchers may be aided in paying attention to the tie points and the accuracy of the ground control points used for geometric calibration and data production. The accuracy of ground control points are related to the requirements of the project. The ground control points and the quality of tie points directly contribute to the geometric accuracy of the data, regardless of the ground sample distance of the imagery. The guidelines outlined in this report are intended to ensure that the data are in common units and are quantifiable and comparable with other data. These QA and calibration processes can be critical in ensuring that these datasets are used to the maximum extent possible. Including the calibration parameters (and their uncertainties) as part of metadata can allow for easier data discovery and analytical filters.

Open-File Report↗

Influence of demand and capacity in transportation simulations of short-notice, distant-tsunami evacuations

Distant tsunamis require short-notice evacuations in coastal communities to minimize threats to life safety. Given the available time to evacuate and potential distances out of hazard zones, coastal transportation planners and emergency managers can expect large proportions of populations to evacuate using vehicles. A community-wide, short-notice, distant-tsunami evacuation is challenging because it creates a sudden, significant, and concentrated demand on road-network systems. Transportation planners and emergency managers need methods to help them determine if a road network can handle an evacuation surge and if not, where interventions can best reduce overall clearance times. We use the coastal community of Bay Farm Island (City of Alameda, California, USA) and the distant-tsunami threat posed by Aleutian-Alaskan earthquakes as a case study to explore the use of agent-based, transportation simulation to support short-notice, tsunami-evacuation planning. Results demonstrate how vehicle simulation can characterize network performance during a tsunami evacuation in the absence of real-world measurements of vehicle demand and flow. Changes in vehicle demand had the greatest influence on reductions in clearance times and recommended reductions varied based on time of day. Doubling the capacity of certain road segments based on traditional vehicle-capacity ratios and level-of-service thresholds reduced overall clearance time in some cases but increased it in other cases. The proposed simulation approach can serve as an analytical foundation for future efforts to characterize distant-tsunami evacuations in other coastal communities throughout the world.

California↗

Gaussian statistics for palaeomagnetic vectors

With the aim of treating the statistics of palaeomagnetic directions and intensities jointly and consistently, we represent the mean and the variance of palaeomagnetic vectors, at a particular site and of a particular polarity, by a probability density function in a Cartesian three-space of orthogonal magnetic-field components consisting of a single (unimoda) non-zero mean, spherically-symmetrical (isotropic) Gaussian function. For palaeomagnetic data of mixed polarities, we consider a bimodal distribution consisting of a pair of such symmetrical Gaussian functions, with equal, but opposite, means and equal variances. For both the Gaussian and bi-Gaussian distributions, and in the spherical three-space of intensity, inclination, and declination, we obtain analytical expressions for the marginal density functions, the cumulative distributions, and the expected values and variances for each spherical coordinate (including the angle with respect to the axis of symmetry of the distributions). The mathematical expressions for the intensity and off-axis angle are closed-form and especially manageable, with the intensity distribution being Rayleigh-Rician. In the limit of small relative vectorial dispersion, the Gaussian (bi-Gaussian) directional distribution approaches a Fisher (Bingham) distribution and the intensity distribution approaches a normal distribution. In the opposite limit of large relative vectorial dispersion, the directional distributions approach a spherically-uniform distribution and the intensity distribution approaches a Maxwell distribution. We quantify biases in estimating the properties of the vector field resulting from the use of simple arithmetic averages, such as estimates of the intensity or the inclination of the mean vector, or the variances of these quantities. With the statistical framework developed here and using the maximum-likelihood method, which gives unbiased estimates in the limit of large data numbers, we demonstrate how to formulate the inverse problem, and how to estimate the mean and variance of the magnetic vector field, even when the data consist of mixed combinations of directions and intensities. We examine palaeomagnetic secular-variation data from Hawaii and Re??union, and although these two sites are on almost opposite latitudes, we find significant differences in the mean vector and differences in the local vectorial variances, with the Hawaiian data being particularly anisotropic. These observations are inconsistent with a description of the mean field as being a simple geocentric axial dipole and with secular variation being statistically symmetrical with respect to reflection through the equatorial plane. Finally, our analysis of palaeomagnetic acquisition data from the 1960 Kilauea flow in Hawaii and the Holocene Xitle flow in Mexico, is consistent with the widely held suspicion that directional data are more accurate than intensity data.

Geophysical Journal International↗

A procedure for partitioning bulk sediments into distinct grain-size fractions for geochemical analysis

A method to separate sediments into discrete size fractions for geochemical analysis has been tested. The procedures were chosen to minimize the destruction or formation of aggregates and involved gentle sieving and settling of wet samples. Freeze-drying and sonication pretreatments, known to influence aggregates, were used for comparison. Freeze-drying was found to increase the silt/clay ratio by an average of 180 percent compared to analysis of a wet sample that had been wet sieved only. Sonication of a wet sample decreased the silt/clay ratio by 51 percent. The concentrations of metals and organic carbon in the separated fractions changed depending on the pretreatment procedures in a manner consistent with the hypothesis that aggregates consist of fine-grained organic- and metal-rich particles. The coarse silt fraction of a freeze-dried sample contained 20–44 percent higher concentrations of Zn, Cu, and organic carbon than the coarse silt fraction of the wet sample. Sonication resulted in concentrations of these analytes that were 18–33 percent lower in the coarse silt fraction than found in the wet sample. Sonication increased the concentration of lead in the clay fraction by an average of 40 percent compared to an unsonicated sample. Understanding the magnitude of change caused by different analysis protocols is an aid in designing future studies that seek to interpret the spatial distribution of contaminated sediments and their transport mechanisms.

Environmental Geology↗

Quality assurance and quality control of geochemical data—A primer for the research scientist

Geochemistry is a constantly expanding science. More and more, scientists are employing geochemical tools to help answer questions about the Earth and earth system processes. Scientists may assume that the responsibility of examining and assessing the quality of the geochemical data they generate is not theirs but rather that of the analytical laboratories to which their samples have been submitted. This assumption may be partially based on knowledge about internal and external quality assurance and quality control (QA/QC) programs in which analytical laboratories typically participate. Or there may be a perceived lack of time or resources to adequately examine data quality. Regardless of the reason, the lack of QA/QC protocols can lead to the generation and publication of erroneous data. Because the interpretations drawn from the data are primary products to U.S. Geological Survey (USGS) stakeholders, the consequences of publishing erroneous results can be significant. The principal investigator of a scientific study ultimately is responsible for the quality and interpretation of the project's findings, and thus must also play a role in the understanding, implementation, and presentation of QA/QC information about the data. Although occasionally ignored, QA/QC protocols apply not only to procedures in the laboratory but also in the initial planning of a research study and throughout the life of the project. Many of the tenets of developing a sound QA/QC program or protocols also parallel the core concepts of developing a good study: What is the main objective of the study? Will the methods selected provide data of enough resolution to answer the hypothesis? How should samples be collected? Are there known or unknown artifacts or contamination sources in the sampling and analysis methods? Assessing data quality requires communication between the scientists responsible for designing the study and those collecting samples, analyzing samples, treating data, and interpreting results. This primer has been developed to provide basic information and guidance about developing QA/QC protocols for geochemical studies. It is not intended to be a comprehensive guide but rather an introduction to key concepts tied to a list of relevant references for further reading. The guidelines are presented in stepwise order beginning with presampling considerations and continuing through final data interpretation. The goal of this primer is to outline basic QA/QC practices that scientists can use before, during, and after chemical analysis to ensure the validity of the data they collect with the goal of providing defendable results and conclusions.

Open-File Report↗

A stratigraphic approach to inferring depositional ages from detrital geochronology data

With the increasing use of detrital geochronology data for provenance analyses, we have also developed new constraints on the age of otherwise undateable sedimentary deposits. Because a deposit can be no older than its youngest mineral constituent, the youngest defensible detrital mineral age defines the maximum depositional age of the sampled bed. Defining the youngest `defensible' age in the face of uncertainty (e.g., analytical and geological uncertainty, or sample contamination) is challenging. The current standard practice of finding multiple detrital minerals with indistinguishable ages provides confidence that a given age is not an artifact; however, we show how requiring this overlap reduces the probability of identifying the true youngest component age. Barring unusual complications, the principle of superposition dictates that sedimentary deposits must get younger upsection. This fundamental constraint can be incoporated into the analysis of depositional ages in sedimentary sections through the use of Bayesian statistics, allowing for the inference of bounded estimates of true depositional ages and uncertainties from detrital geochronology so long as some minimum age constraints are present. We present two approaches for constructing a Bayesian model of deposit ages, first solving directly for the ages of deposits with the prior constraint that the ages of units must obey stratigraphic ordering, and second describing the evolution of ages with a curve that represents the sediment accumulation rate. Using synthetic examples we highlight how this method preforms in less-than-ideal circumstances. In an example from the Magallanes Basin of Patagonia, we demonstrate how introducing other age information from the stratigraphic section (e.g., fossil assemblages or radiometric dates) and formalizing the stratigraphic context of samples provides additional constraints on and information regarding depositional ages or derived quantities (e.g., sediment accumulation rates) compared to isolated analysis of individual samples.

Frontiers in Earth Science↗

Determination of thorium by fluorescent x-ray spectrometry

A fluorescent x-ray spectrographic method for the determination of thoria in rock samples uses thallium as an internal standard. Measurements are made with a two-channel spectrometer equipped with quartz (d = 1.817 A.) analyzing crystals. Particle-size effects are minimized by grinding the sample components with a mixture of silicon carbide and aluminum and then briquetting. Analyses of 17 samples showed that for the 16 samples containing over 0.7% thoria the average error, based on chemical results, is 4.7% and the maximum error, 9.5%. Because of limitations of instrumentation, 0.2% thoria is considered the lower limit of detection. An analysis can be made in about an hour.

Analytical Chemistry↗

Evolution of Ore Deposits and Technology Transfer Project: Isotope and Chemical Methods in Support of the U.S. Geological Survey Science Strategy, 2003-2008

Principal functions of the U.S. Geological Survey (USGS) Mineral Resources Program are providing assessments of the location, quantity, and quality of undiscovered mineral deposits, and predicting the environmental impacts of exploration and mine development. The mineral and environmental assessments of domestic deposits are used by planners and decisionmakers to improve the stewardship of public lands and public resources. Assessments of undiscovered mineral deposits on a global scale reveal the potential availability of minerals to the United States and other countries that manufacture goods imported to the United States. These resources are of fundamental relevance to national and international economic and security policy in our globalized world economy. Performing mineral and environmental assessments 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 diverse 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 benefited 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 (referred to hereinafter as the Project), a 5-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 to ore-deposit-related studies. The analytical capabilities and scientific approaches developed within the Project have wide applicability within Earth-system science. For this reason the Project Laboratories represent a valuable catalyst for interdisciplinary collaborations of the type that should be formed in the coming years for the United States to meet its natural-resources and natural-science needs. This circular presents an overview of the Project. Descriptions of the Project laboratories are given first including descriptions of the types of chemical or isotopic analyses that are made and the utility of the measurements. This is followed by summaries of select measurements that were carried out by the Project scientists. The studies are grouped by science direction. Virtually all of them were collaborations with USGS colleagues or with scientists from other governmental agencies, academia, or the private sector.

Circular↗