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A new formula for the analytical solution of the radial dispersion problem

A new formula is presented for the analytical solution of the radial dispersion problem, which analyzes the dispersive transport of a tracer in radial flow from a recharge well. This formula is simpler than a solution presented by previous investigators, but the two solutions are shown to be equivalent. Because the analytical solution consists of an integral of an oscillatory function, it is evaluated as an alternating series, the terms of which are the integrals over successive half cycles of the integrand. An efficient algorithm is used to accelerate convergence of the series. The accuracies of previous solutions obtained by finite difference, numerical Laplace transform, and perturbation methods are examined by comparison with the analytical solution. Numerical values of the solution are tabulated for readers interested in checking the accuracies of solute transport codes.

Water Resources Research↗

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-Evaluation of alkaline persulfate digestion as an alternative to Kjeldahl digestion for determination of total and dissolved nitrogen and phosphorus in water

Alkaline persulfate digestion was evaluated and validated as a more sensitive, accurate, and less toxic alternative to Kjeldahl digestion for routine determination of nitrogen and phosphorus in surface- and ground-water samples in a large-scale and geographically diverse study conducted by U.S. Geological Survey (USGS) between October 1, 2001, and September 30, 2002. Data for this study were obtained from about 2,100 surface- and ground-water samples that were analyzed for Kjeldahl nitrogen and Kjeldahl phosphorus in the course of routine operations at the USGS National Water Quality Laboratory (NWQL). These samples were analyzed independently for total nitrogen and total phosphorus using an alkaline persulfate digestion method developed by the NWQL Methods Research and Development Program. About half of these samples were collected during nominally high-flow (April-June) conditions and the other half were collected during nominally low-flow (August-September) conditions. The number of filtered and whole-water samples analyzed from each flow regime was about equal.By operational definition, Kjeldahl nitrogen (ammonium + organic nitrogen) and alkaline persulfate digestion total nitrogen (ammonium + nitrite + nitrate + organic nitrogen) are not equivalent. It was necessary, therefore, to reconcile this operational difference by subtracting nitrate + nitrite concentra-tions from alkaline persulfate dissolved and total nitrogen concentrations prior to graphical and statistical comparisons with dissolved and total Kjeldahl nitrogen concentrations. On the basis of two-population paired t-test statistics, the means of all nitrate-corrected alkaline persulfate nitrogen and Kjeldahl nitrogen concentrations (2,066 paired results) were significantly different from zero at the p = 0.05 level. Statistically, the means of Kjeldahl nitrogen concentrations were greater than those of nitrate-corrected alkaline persulfate nitrogen concentrations. Experimental evidence strongly suggests, however, that this apparent low bias resulted from nitrate interference in the Kjeldahl digestion method rather than low nitrogen recovery by the alkaline persulfate digestion method. Typically, differences between means of Kjeldahl nitrogen and nitrate-corrected alkaline persulfate nitrogen in low-nitrate concentration (< 0.1 milligram nitrate nitrogen per liter) subsets of filtered surface- and ground-water samples were statistically equivalent to zero at the p =level.Paired analytical results for dissolved and total phosphorus in Kjeldahl and alkaline persulfate digests were directly comparable because both digestion methods convert all forms of phosphorus in water samples to orthophosphate. On the basis of two-population paired t-test statistics, the means of all Kjeldahl phosphorus and alkaline persulfate phosphorus concentrations (2,093 paired results) were not significantly different from zero at the p = 0.05 level. For some subsets of these data, which were grouped according to water type and flow conditions at the time of sample collection, differences between means of Kjeldahl phosphorus and alkaline persulfate phosphorus concentrations were not equivalent to zero at the p = 0.05 level. Differences between means of these subsets, however, were less than the method detection limit for phosphorus (0.007 milligram phosphorus per liter) by the alkaline persulfate digestion method, and were therefore analytically insignificant.This report provides details of the alkaline persulfate digestion procedure, interference studies, recovery of various nitrogen- and phosphorus-containing compounds, and other analytical figures of merit. The automated air-segmented continuous flow methods developed to determine nitrate and orthophosphate in the alkaline persulfate digests also are described. About 125 microliters of digested sample are required to determine nitrogen and phosphorus in parallel at a rate of about 100 samples per hour with less than 1-percent sample in

Water-Resources Investigations Report↗

Performance evaluation and methods comparison of transcriptomic-based approaches for the characterization of wastewater treatment effluent

Wastewater treatment effluents (WWTE) present complex risks to aquatic ecosystems that are difficult to characterize using traditional methods. This study systematically evaluated the consistency and performance of transcriptomic-based approaches over time with repeated sampling and with differing experimental approaches (selection of reference condition, grab vs. composite sampling, deployed vs. laboratory exposed). RNA-seq was performed on larval fathead minnow (FHM) exposed in the laboratory to moderately hard reconstituted water (MRHW) or individual grab samples collected from an upstream site and a WWTE in the morning and afternoon over two successive days, as well as FHM deployed concurrently with grab sampling at the same sites. Composite transcriptional profiles were generated by pooling count data from grab sample exposures. The choice of comparator significantly affected results. The use of the upstream site as the reference consistently yielded fewer differentially expressed genes (DEGs) and minimal overlap compared to DEG sets from the other comparisons. Using MRHW as a comparator, DEG sets showed high consistency across grab samples, with morning samples demonstrating larger, highly consistent gene expression sets (96 % overlap) compared to afternoon samples, revealing clear and consistent within-day expression patterns. With the MHRW comparator, DEG sets from grab sample composites and deployments also overlapped substantially, indicating that transcriptional profiles accurately reflect WWTE composition regardless of exposure method. Comparisons with non-targeted (NTA) and targeted analytical datasets confirmed that gene expression interpretations aligned with effluent composition while highlighting limitations of relying solely on targeted analyte sets for connecting expression to specific chemicals. Though highly dependent on experimental design, these results demonstrate that transcriptomic-based methods provide significant utility for characterizing the bioactivity of complex environmental mixtures, and when paired with NTA datasets, have the potential to deliver a comprehensive assessment of their environmental risk.

Environmental Pollution↗

Fission-track and K-Ar ages of Tertiary ash-flow tuffs, north-central Nevada

Ages obtained from three Tertiary ash-flow tuffs in central Nevada by fission-track and K-Ar dating are concordant. Samples dated by these methods from the same localities give the same age within the limits of analytical uncertainty. Samples of three units from widely separated localities were dated further to confirm the concordance of the dating methods and to establish that ages can be used, in conjunction with normal geologic techniques, as a criteria for correlation. The minerals dated by K-Ar were biotite and sanidine; and sphene zircon and apatite were used to determine the fission track ages. The Bates Mountain Tuff was dated at 24.0 m.y. (F.T.) and 24.0 m.y. (K-Ar). The Fish Creek Mountains Tuff has a fission-track age of 24.4 m.y., and a K-Ar age of 23.9 m.y. The average fission-track age for the Caetano Tuff is 34.9 m.y., and it has an average K-Ar age of 32.3 m.y. The amount of analytical uncertainty is slightly greater in the fission track method. Sampling, preparation, and determination of the age by the fission-track method is competitive with the K-Ar method.

Nevada↗

A transient laboratory method for determining the hydraulic properties of 'tight' rocks-II. Application

In Part I a general analytical solution for the transient pulse test was presented. Part II presents a graphical method for analyzing data from a test to obtain the hydraulic properties of the sample. The general solution depends on both hydraulic conductivity and specific storage and, in theory, analysis of the data can provide values for both of these hydraulic properties. However, in practice, one of two limiting cases may apply in which case it is possible to calculate only hydraulic conductivity or the product of hydraulic conductivity times specific storage. In this paper we examine the conditions when both hydraulic parameters can be calculated. The analyses of data from two tests are presented. In Appendix I the general solution presented in Part I is compared with an earlier analysis, in which compressive storage in the sample is assumed negligible, and the error in calculated hydraulic conductivity due to this simplifying assumption is examined.

International Journal of Rock Mechanics and Mining↗

Comparison of passive and pumped sampling methods for analysis of groundwater quality, Kirtland Air Force Base, Albuquerque, New Mexico, 2019

A plume of ethylene dibromide (EDB) dissolved in groundwater extends northeast from the Bulk Fuels Facility on Kirtland Air Force Base, New Mexico. The leading edge of the EDB plume is upgradient from several water-supply wells. In 2013, the U.S. Geological Survey (USGS), in cooperation with the Albuquerque Bernalillo County Water Utility Authority and the U.S. Air Force, installed four sentinel well nests and two aquifer-test pumping wells between the EDB plume and the water-supply wells to serve as an early warning if the plume travels toward the water-supply wells. Since 2015, the USGS has used submersible pumps to sample the sentinel wells quarterly. In February 2017, the USGS began using dual-membrane passive diffusion bag samplers for quarterly sampling in the wells. To ensure that the passive samplers are obtaining representative samples of the groundwater contaminants, the USGS, in cooperation with the U.S. Air Force, initiated a study in 2019 to compare results from pump sampling and passive samplers and to use vertical profiling to determine the optimal depth for passive sampler placement in the screened interval to better inform long-term monitoring of the site. Vertical profiling included deploying passive samplers throughout the submerged screened interval of four shallow sentinel wells. After retrieval of the passive samplers, pump samples were collected. The results of analyses of both types of samples were compared. Volatile organic compound results for this study were all below the raised reporting levels, which is a level five times the maximum concentration detected in a blank and determined by an in-depth quality assessment; therefore, this study focused on inorganic constituent results, including major ions, trace elements, and stable isotopes of water, to calculate the relative percent difference (RPD) between the pump and passive sampling method results as a way to determine where passive samplers would be best placed in each of the wells. Several analytes had an RPD of more than plus or minus 50 percent, and several analytes were not within the estimated variability for each sampling method. Additionally, the variability within each sampling method was quantified and compared. Factors that likely contributed to the lack of comparison between each sampling method included temporal variability, flow regime, volume of sample integrated through different aquifer intervals, and reduction/oxidation processes. RPD and method variability were used to determine the intervals within each well with the greatest agreement between sampling methods. Optimal sampling depths for each well were then correlated to the intervals where quarterly sampling has been occurring.

New Mexico↗

Relationship and variation of qPCR and culturable enterococci estimates in ambient surface waters are predictable

The quantitative polymerase chain reaction (qPCR) method provides rapid estimates of fecal indicator bacteria densities that have been indicated to be useful in the assessment of water quality. Primarily because this method provides faster results than standard culture-based methods, the U.S. Environmental Protection Agency is currently considering its use as a basis for revised ambient water quality criteria. In anticipation of this possibility, we sought to examine the relationship between qPCR-based and culture-based estimates of enterococci in surface waters. Using data from several research groups, we compared enterococci estimates by the two methods in water samples collected from 37 sites across the United States. A consistent linear pattern in the relationship between cell equivalents (CCE), based on the qPCR method, and colony-forming units (CFU), based on the traditional culturable method, was significant (P < 0.05) at most sites. A linearly decreasing variance of CCE with increasing CFU levels was significant (P < 0.05) or evident for all sites. Both marine and freshwater sites under continuous influence of point-source contamination tended to reveal a relatively constant proportion of CCE to CFU. The consistency in the mean and variance patterns of CCE versus CFU indicates that the relationship of results based on these two methods is more predictable at high CFU levels (e.g., log 10 CFU > 2.0/100 mL) while uncertainty increases at lower CFU values. It was further noted that the relative error in replicated qPCR estimates was generally higher than that in replicated culture counts even at relatively high target levels, suggesting a greater need for replicated analyses in the qPCR method to reduce relative error. Further studies evaluating the relationship between culture and qPCR should take into account analytical uncertainty as well as potential differences in results of these methods that may arise from sample variability, different sources of pollution, and environmental factors.

Environmental Science & Technology↗

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↗

Increasing accuracy of dispersal kernels in grid-based population models

Dispersal kernels in grid-based population models specify the proportion, distance and direction of movements within the model landscape. Spatial errors in dispersal kernels can have large compounding effects on model accuracy. Circular Gaussian and Laplacian dispersal kernels at a range of spatial resolutions were investigated, and methods for minimizing errors caused by the discretizing process were explored. Kernels of progressively smaller sizes relative to the landscape grid size were calculated using cell-integration and cell-center methods. These kernels were convolved repeatedly, and the final distribution was compared with a reference analytical solution. For large Gaussian kernels ( σ > 10 cells), the total kernel error was <10 −11 compared to analytical results. Using an invasion model that tracked the time a population took to reach a defined goal, the discrete model results were comparable to the analytical reference. With Gaussian kernels that had σ ≤ 0.12 using the cell integration method, or σ ≤ 0.22 using the cell center method, the kernel error was greater than 10%, which resulted in invasion times that were orders of magnitude different than theoretical results. A goal-seeking routine was developed to adjust the kernels to minimize overall error. With this, corrections for small kernels were found that decreased overall kernel error to <10 −11 and invasion time error to <5%.

Ecological Modelling↗

Comparison of two methods for estimating base flow in selected reaches of the South Platte River, Colorado

The U.S. Geological Survey, in cooperation with the Colorado Water Conservation Board, compared two methods for estimating base flow in three reaches of the South Platte River between Denver and Kersey, Colorado. The two methods compared in this study are the Mass Balance and the Pilot Point methods. Base-flow estimates made with the two methods were based upon a 54-year period of record (1950 to 2003). The Mass Balance method for estimating base flow is based on a mass balance of all known inflows to and outflows from a given stream reach, with the equation being solved for groundwater flow into or out of the reach. A positive mass balance indicates a gaining reach (base flow) and a negative balance indicates a losing reach. The mass balance was calculated using daily mean streamflow, wastewater treatment plant discharge, and stream diversion data. Monthly mean base flow was calculated as the average of all daily mean mass-balance results for a given month. The Pilot Point method is based on a daily mean mass balance of all inflows to and outflows from a stream reach. The Pilot Point differs from the Mass Balance method in that extreme daily mass-balance results are constrained utilizing two analytical solutions that represent the maximum possible streamflow gain or loss. Additionally, the Pilot Point method utilizes a smoothing function, based on a moving average of the daily constrained mass-balance results. The moving average for this study utilized a moving-average period, called the bin width, of 61 days. The maximum and minimum base-flow constraints and the smoothing function are utilized to provide base-flow estimates that exhibit reasonable maximum values and temporal variability consistent with the concept of groundwater flow being gradual and slow. Both the Mass Balance and Pilot Point results provided similar patterns in annual and monthly base flow. All three reaches were indicated to be gaining reaches, particularly after about 1970, with the magnitude of base flow increasing downstream. This degree of similarity between the two methods was expected because both methods are based on a streamflow mass balance. The magnitude of estimates provided by the two methods was measurably different. The stream gains and losses estimated using the Mass Balance method were consistently more variable and of greater magnitude than those estimated using the Pilot Point method. In the Denver to Henderson reach, the median estimated annual mean base flow was 34.0 cubic feet per second (ft 3 /s) using the Mass Balance method and was 39.1 ft 3 /s using the Pilot Point method. In the Henderson to Fort Lupton reach, the median estimated annual mean base flow was 50.0 ft 3 /s using the Mass Balance method and was 40.0 ft 3 /s using the Pilot Point method. In the Fort Lupton to Kersey reach, the median estimated annual mean base flow was 234 ft 3 /s using the Mass Balance method and was 214 ft 3 /s using the Pilot Point method. The Mass Balance results were quite variable over time such that they appeared suspect with respect to the concept of groundwater flow as being gradual and slow. The large degree of variability in the day-to-day and month-to-month Mass Balance results is likely the result of many factors. These factors could include ungaged stream inflows or outflows, short-term streamflow losses to and gains from temporary bank storage, and any lag in streamflow accounting owing to streamflow lag time of flow within a reach. The Pilot Point time series results were much less variable than the Mass Balance results and extreme values were effectively constrained. Less day-to-day variability, smaller magnitude extreme values, and smoother transitions in base-flow estimates provided by the Pilot Point method are more consistent with a conceptual model of groundwater flow being gradual and slow. The Pilot Point method provided a better fit to the conceptual model of groundwater flow and appeared to provide reasonable estimates of base flow.

Colorado↗

Long-range hazard assessment of volcanic ash dispersal for a Plinian eruptive scenario at Popocatépetl volcano (Mexico): implications for civil aviation safety

Popocatépetl is one of Mexico’s most active volcanoes threatening a densely populated area that includes Mexico City with more than 20 million inhabitants. The destructive potential of this volcano is demonstrated by its Late Pleistocene–Holocene eruptive activity, which has been characterized by recurrent Plinian eruptions of large magnitude, the last two of which destroyed human settlements in pre-Hispanic times. Popocatépetl’s reawakening in 1994 produced a crisis that culminated with the evacuation of two villages on the northeastern flank of the volcano. Shortly after, a monitoring system and a civil protection contingency plan based on a hazard zone map were implemented. The current volcanic hazards map considers the potential occurrence of different volcanic phenomena, including pyroclastic density currents and lahars. However, no quantitative assessment of the tephra hazard, especially related to atmospheric dispersal, has been performed. The presence of airborne volcanic ash at low and jet-cruise atmospheric levels compromises the safety of aircraft operations and forces re-routing of aircraft to prevent encounters with volcanic ash clouds. Given the high number of important airports in the surroundings of Popocatépetl volcano and considering the potential threat posed to civil aviation in Mexico and adjacent regions in case of a Plinian eruption, a hazard assessment for tephra dispersal is required. In this work, we present the first probabilistic tephra dispersal hazard assessment for Popocatépetl volcano. We compute probabilistic hazard maps for critical thresholds of airborne ash concentrations at different flight levels, corresponding to the situation defined in Europe during 2010, and still under discussion. Tephra dispersal mode is performed using the FALL3D numerical model. Probabilistic hazard maps are built for a Plinian eruptive scenario defined on the basis of geological field data for the “Ochre Pumice” Plinian eruption (4965 14 C yr BP). FALL3D model input eruptive parameters are constrained through an inversion method carried out with the semi-analytical HAZMAP model and are varied by sampling them using probability density functions. We analyze the influence of seasonal variations on ash dispersal and estimate the average persistence of critical ash concentrations at relevant locations and airports. This study assesses the impact that a Plinian eruption similar to the Ochre Pumice eruption would have on the main airports of Mexico and adjacent areas. The hazard maps presented here can support long-term planning that would help minimize the impacts of such an eruption on civil aviation.

Popocatépetl Volcano↗

Detecting temporal trends in species assemblages with bootstrapping procedures and hierarchical models

Quantifying patterns of temporal trends in species assemblages is an important analytical challenge in community ecology. We describe methods of analysis that can be applied to a matrix of counts of individuals that is organized by species (rows) and time-ordered sampling periods (columns). We first developed a bootstrapping procedure to test the null hypothesis of random sampling from a stationary species abundance distribution with temporally varying sampling probabilities. This procedure can be modified to account for undetected species. We next developed a hierarchical model to estimate species-specific trends in abundance while accounting for species-specific probabilities of detection. We analysed two long-term datasets on stream fishes and grassland insects to demonstrate these methods. For both assemblages, the bootstrap test indicated that temporal trends in abundance were more heterogeneous than expected under the null model. We used the hierarchical model to estimate trends in abundance and identified sets of species in each assemblage that were steadily increasing, decreasing or remaining constant in abundance over more than a decade of standardized annual surveys. Our methods of analysis are broadly applicable to other ecological datasets, and they represent an advance over most existing procedures, which do not incorporate effects of incomplete sampling and imperfect detection.

Philosophical Transactions of the Royal Society B:↗

Methods for simulating solute breakthrough curves in pumping groundwater wells

In modeling there is always a trade-off between execution time and accuracy. For gradient-based parameter estimation methods, where a simulation model is run repeatedly to populate a Jacobian (sensitivity) matrix, there exists a need for rapid simulation methods of known accuracy that can decrease execution time, and thus make the model more useful without sacrificing accuracy. Convolution-based methods can be executed rapidly for any desired input function once the residence-time distribution is known. The residence-time distribution can be calculated efficiently using particle tracking, but particle tracking can be ambiguous near a pumping well if the grid is too coarse. We present several embedded analytical expressions for improving particle tracking near a pumping well and compare them with a finely gridded finite-difference solution in terms of accuracy and CPU usage. Even though the embedded analytical approach can improve particle tracking near a well, particle methods reduce, but do not eliminate, reliance on a grid because velocity fields typically are calculated on a grid, and additional error is incurred using linear interpolation of velocity. A dilution rate can be calculated for a given grid and pumping well to determine if the grid is sufficiently refined. Embedded analytical expressions increase accuracy but add significantly to CPU usage. Structural error introduced by the numerical solution method may affect parameter estimates.

Computers & Geosciences↗

A novel method to characterise levels of pharmaceutical pollution in large scale aquatic monitoring campaigns

Much of the current understanding of pharmaceutical pollution in the aquatic environment is based on research conducted in Europe, North America and other select high-income nations. One reason for this geographic disparity of data globally is the high cost and analytical intensity of the research, limiting accessibility to necessary equipment. To reduce the impact of such disparities, we present a novel method to support large-scale monitoring campaigns of pharmaceuticals at different geographical scales. The approach employs the use of a miniaturised sampling and shipping approach with a high throughput and fully validated direct-injection High-Performance Liquid Chromatography-Tandem Mass Spectrometry method for the quantification of 61 active pharmaceutical ingredients (APIs) and their metabolites in tap, surface, wastewater treatment plant (WWTP) influent and WWTP effluent water collected globally. A 7-day simulated shipping and sample stability assessment was undertaken demonstrating no significant degradation over the 1–3 days which is typical for global express shipping. Linearity (r 2 ) was consistently ≥0.93 (median = 0.99 ± 0.02), relative standard deviation of intra- and inter-day repeatability and precision was <20% for 75% and 68% of the determinations made at three concentrations, respectively, and recovery from Liquid Chromatography Mass Spectrometry grade water, tap water, surface water and WWTP effluent were within an acceptable range of 60–130% for 87%, 76%, 77% and 63% of determination made at three concentrations respectively. Limits of detection and quantification were determined in all validated matrices and were consistently in the ng/L level needed for environmentally relevant API research. Independent validation of method results was obtained via an interlaboratory comparison of three surface-water samples and one WWTP effluent sample collected in North Liberty, Iowa (USA). Samples used for the interlaboratory validation were analysed at the University of York Centre of Excellence in Mass Spectrometry (York, UK) and the U.S. Geological Survey National Water Quality Laboratory in Denver (Colorado, USA). These results document the robustness of using this method on a global scale. Such application of this method would essentially eliminate the interlaboratory analytical variability typical of such large-scale datasets where multiple methods were used.

Applied Sciences↗

Mapping polar bear maternal denning habitat in the National Petroleum Reserve -- Alaska with an IfSAR digital terrain model

The National Petroleum Reserve–Alaska (NPR-A) in northeastern Alaska provides winter maternal denning habitat for polar bears ( Ursus maritimus ) and also has high potential for recoverable hydrocarbons. Denning polar bears exposed to human activities may abandon their dens before their young are able to survive the severity of Arctic winter weather. To ensure that wintertime petroleum activities do not threaten polar bears, managers need to know the distribution of landscape features in which maternal dens are likely to occur. Here, we present a map of potential denning habitat within the NPR-A. We used a fine-grain digital elevation model derived from Interferometric Synthetic Aperture Radar (IfSAR) to generate a map of putative denning habitat. We then tested the map’s ability to identify polar bear denning habitat on the landscape. Our final map correctly identified 82% of denning habitat estimated to be within the NPR-A. Mapped denning habitat comprised 19.7 km2 (0.1% of the study area) and was widely dispersed. Though mapping denning habitat with IfSAR data was as effective as mapping with the photogrammetric methods used for other regions of the Alaskan Arctic coastal plain, the use of GIS to analyze IfSAR data allowed greater objectivity and flexibility with less manual labor. Analytical advantages and performance equivalent to that of manual cartographic methods suggest that the use of IfSAR data to identify polar bear maternal denning habitat is a better management tool in the NPR-A and wherever such data may be available.

Alaska↗

Bedrock morphology and structure, upper Santa Cruz Basin, south-central Arizona, with transient electromagnetic survey data

The upper Santa Cruz Basin is an important groundwater basin containing the regional aquifer for the city of Nogales, Arizona. This report provides data and interpretations of data aimed at better understanding the bedrock morphology and structure of the upper Santa Cruz Basin study area which encompasses the Rio Rico and Nogales 1:24,000-scale U.S. Geological Survey quadrangles. Data used in this report include the Arizona Aeromagnetic and Gravity Maps and Data referred to here as the 1996 Patagonia Aeromagnetic survey, Bouguer gravity anomaly data, and conductivity-depth transforms (CDTs) from the 1998 Santa Cruz transient electromagnetic survey (whose data are included in appendixes 1 and 2 of this report). Analyses based on magnetic gradients worked well to identify the range-front faults along the Mt. Benedict horst block, the location of possibly fault-controlled canyons to the west of Mt. Benedict, the edges of buried lava flows, and numerous other concealed faults and contacts. Applying the 1996 Patagonia aeromagnetic survey data using the horizontal gradient method produced results that were most closely correlated with the observed geology. The 1996 Patagonia aeromagnetic survey was used to estimate depth to bedrock in the upper Santa Cruz Basin study area. Three different depth estimation methods were applied to the data: Euler deconvolution, horizontal gradient magnitude, and analytic signal. The final depth to bedrock map was produced by choosing the maximum depth from each of the three methods at a given location and combining all maximum depths. In locations of rocks with a known reversed natural remanent magnetic field, gravity based depth estimates from Gettings and Houser (1997) were used. The depth to bedrock map was supported by modeling aeromagnetic anomaly data along six profiles. These cross sectional models demonstrated that by using the depth to bedrock map generated in this study, known and concealed faults, measured and estimated magnetic susceptibilities of rocks found in the study area, and estimated natural remanent magnetic intensities and directions, reasonable geologic models can be built. This indicates that the depth to bedrock map is reason-able and geologically possible. Finally, CDTs derived from the 1998 Santa Cruz Basin transient electromagnetic survey were used to help identify basin structure and some physical properties of the basin fill in the study area. The CDTs also helped to confirm depth to bedrock estimates in the Santa Cruz Basin, in particular a region of elevated bedrock in the area of Potrero Canyon, and a deep basin in the location of the Arizona State Highway 82 microbasin. The CDTs identified many concealed faults in the study area and possibly indicate deep water-saturated clay-rich sediments in the west-central portion of the study area. These sediments grade to more sand-rich saturated sediments to the south with relatively thick, possibly unsaturated, sediments at the surface. Also, the CDTs may indicate deep saturated clay-rich sediments in the Highway 82 microbasin and in the Mount Benedict horst block from Proto Canyon south to the international border.

Arizona↗

Quantification of 15 bile acids in lake charr feces by ultra-high performance liquid chromatography–tandem mass spectrometry

Many fishes are hypothesized to use bile acids (BAs) as chemical cues, yet quantification of BAs in biological samples and the required methods remain limited. Here, we present an UHPLC&ndash;MS/MS method for simultaneous, sensitive, and rapid quantification of 15 BAs, including free, taurine, and glycine conjugated BAs, and application of the method to fecal samples from lake charr ( Salvelinus namaycush ). The analytes were separated on a C 18 column with acetonitrile&ndash;water (containing 7.5 mM ammonium acetate and 0.1% formic acid) as mobile phase at a flow rate of 0.25 mL/min for 12 min. BAs were monitored with a negative electrospray triple quadrupole mass spectrometer (Xevo TQ-S&trade;). Calibration curves of 15 BAs were linear over the concentration range of 1.00&ndash;5,000 ng/mL. Validation revealed that the method was specific, accurate, and precise. The method was applied to quantitative analysis of feces extract of fry lake charr and the food they were eating. The concentrations of analytes CA, TCDCA, TCA, and CDCA were 242.3, 81.2, 60.7, and 36.2 ng/mg, respectively. However, other taurine conjugated BAs, TUDCA, TDCA, and THDCA, were not detected in feces of lake charr. Interestingly, TCA and TCDCA were detected at high concentrations in food pellets, at 71.9 and 38.2 ng/mg, respectively. Application of the method to feces samples from lake charr supported a role of BAs as chemical cues, and will enhance further investigation of BAs as chemical cues in other fish species.

Journal of Chromatography B: Analytical Technologi↗

A transient laboratory method for determining the hydraulic properties of 'tight' rocks-I. Theory

Transient pulse testing has been employed increasingly in the laboratory to measure the hydraulic properties of rock samples with low permeability. Several investigators have proposed a mathematical model in terms of an initial-boundary value problem to describe fluid flow in a transient pulse test. However, the solution of this problem has not been available. In analyzing data from the transient pulse test, previous investigators have either employed analytical solutions that are derived with the use of additional, restrictive assumptions, or have resorted to numerical methods. In Part I of this paper, a general, analytical solution for the transient pulse test is presented. This solution is graphically illustrated by plots of dimensionless variables for several cases of interest. The solution is shown to contain, as limiting cases, the more restrictive analytical solutions that the previous investigators have derived. A method of computing both the permeability and specific storage of the test sample from experimental data will be presented in Part II.

International Journal of Rock Mechanics and Mining↗