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An international code comparison study on coupled thermal, hydrologic and geomechanical processes of natural gas hydrate-bearing sediments

Geologic reservoirs containing gas hydrate occur beneath permafrost environments and within marine continental slope sediments, representing a potentially vast natural gas source. Numerical simulators provide scientists and engineers with tools for understanding how production efficiency depends on the numerous, interdependent (coupled) processes associated with potential production strategies for these gas hydrate reservoirs. Confidence in the modeling and forecasting abilities of these gas hydrate reservoir simulators (GHRSs) grows with successful comparisons against laboratory and field test results, but such results are rare, particularly in natural settings. The hydrate community recognized another approach to building confidence in the GHRS: comparing simulation results between independently developed and executed computer codes on structured problems specifically tailored to the interdependent processes relevant for gas hydrate-bearing systems. The United States Department of Energy, National Energy Technology Laboratory (DOE/NETL), sponsored the first international gas hydrate code comparison study, IGHCCS1, in the early 2000s. IGHCCS1 focused on coupled thermal and hydrologic processes associated with producing gas hydrates from geologic reservoirs via depressurization and thermal stimulation. Subsequently, GHRSs have advanced to model more complex production technologies and incorporate geomechanical processes into the existing framework of coupled thermal and hydrologic modeling. This paper contributes to the validation of these recent GHRS developments by providing results from a second GHRS code comparison study, IGHCCS2, also sponsored by DOE/NETL. IGHCCS2 includes participants from an international collection of universities, research institutes, industry, national laboratories, and national geologic surveys. Study participants developed a series of five benchmark problems principally involving gas hydrate processes with geomechanical components. The five problems range from simple geometries with analytical solutions to a representation of the world’s first offshore production test of methane hydrates, which was conducted with the depressurization method off the coast of Japan. To identify strengths and limitations in the various GHRSs, study participants submitted solutions for the benchmark problems and discussed differing results via teleconferences. The GHRSs evolved over the course of IGHCCS2 as researchers modified their simulators to reflect new insights, lessons learned, and suggested performance enhancements. The five benchmark problems, final sample solutions, and lessons learned that are presented here document the study outcomes and serve as a reference guide for developing and testing gas hydrate reservoir simulators.

Journal of Marine and Petroleum Geology↗

Adjustment of total suspended solids data for use in sediment studies

The U.S. Environmental Protection Agency identifies fluvial sediment as the single most widespread pollutant in the Nation's rivers and streams, affecting aquatic habitat, drinking water treatment processes, and recreational uses of rivers, lakes, and estuaries. A significant amount of suspended-sediment data has been produced using the total suspended solids (TSS) laboratory analysis method. An evaluation of data collected and analyzed by the U.S. Geological Survey and others has shown that the variation in TSS analytical results is considerably larger than that for traditional suspended-sediment concentration analyses (SSC) and that the TSS data show a negative bias when compared to SSC data. This paper presents the initial results of a continuing investigation into the differences between TSS and SSC results. It explores possible relations between these differences and other hydrologic data collected at the same stations. A general equation was developed to relate TSS data to SSC data. However, this general equation is not applicable for data from individual stations. Based on these analyses, there appears to be no simple, straightforward way to relate TSS and SSC data unless pairs of TSS and SSC results are available for a station.

Conference Paper↗

Geospatial standard operating procedures of the Chesapeake Bay Program

Introduction The Chesapeake Bay Program (CBP) has operated a geographic information system (GIS) program since the early 1990s to address the established and growing need for and use of geospatial data, maps, and analysis within the CBP Partnership. This report is intended to detail the standard operating procedures of the CBP GIS program and address the quality assurance, quality control, and other technical activities that CBP will implement to ensure the commitment of the CBP GIS Team to performance standards (U.S. Environmental Protection Agency, 2003). The report is intended as an update to the 2011 Quality Assurance Project Plan (QAPP). For specialized tasks or analytical projects beyond the scope of this QAPP, a separate specialized QAPP with details on quality control, assurance procedures, and the geospatial methods associated with all aspects of the project may be required.

Open-File Report↗

An evaluation of a reagentless method for the determination of total mercury in aquatic life

Multiple treatment (i.e., drying, chemical digestion, and oxidation) steps are often required during preparation of biological matrices for quantitative analysis of mercury; these multiple steps could potentially lead to systematic errors and poor recovery of the analyte. In this study, the Direct Mercury Analyzer (Milestone Inc., Monroe, CT) was utilized to measure total mercury in fish tissue by integrating steps of drying, sample combustion and gold sequestration with successive identification using atomic absorption spectrometry. We also evaluated the differences between the mercury concentrations found in samples that were homogenized and samples with no preparation. These results were confirmed with cold vapor atomic absorbance and fluorescence spectrometric methods of analysis. Finally, total mercury in wild captured largemouth bass (n = 20) were assessed using the Direct Mercury Analyzer to examine internal variability between mercury concentrations in muscle, liver and brain organs. Direct analysis of total mercury measured in muscle tissue was strongly correlated with muscle tissue that was homogenized before analysis (r = 0.81, p < 0.0001). Additionally, results using this integrated method compared favorably (p < 0.05) with conventional cold vapor spectrometry with atomic absorbance and fluorescence detection methods. Mercury concentrations in brain were significantly lower than concentrations in muscle (p < 0.001) and liver (p < 0.05) tissues. This integrated method can measure a wide range of mercury concentrations (0-500 ??g) using small sample sizes. Total mercury measurements in this study are comparative to the methods (cold vapor) commonly used for total mercury analysis and are devoid of laborious sample preparation and expensive hazardous waste. ?? Springer 2006.

Water, Air, & Soil Pollution↗

Methods of analysis—Determination of pesticides in filtered water and suspended sediment using liquid chromatography- and gas chromatography-tandem mass spectrometry

The widespread application of pesticides in agricultural and urban areas leads to their presence in surface waters. Presence of these biologically active chemicals in environmental waters potentially has adverse effects on nontarget organisms. To better understand the environmental fate of these contaminants, a robust method to capture chemicals with wide-ranging physicochemical properties has been developed. The method was developed by the U.S. Geological Survey’s Organic Chemistry Research Laboratory to monitor pesticides, pesticide degradates, and other agrochemicals in environmental surface waters throughout the country. The analysis involves a multiresidue method to determine 183 pesticides and pesticide degradates in filtered water samples and 178 pesticides and pesticide degradates in paired suspended sediment samples. After the filtration of whole water, contaminants are individually measured in the filtered water and the collected suspended sediment. Filtered water is extracted via solid-phase extraction, whereas suspended sediment is extracted using an ultrasonication, solid-liquid extraction. Samples are analyzed by liquid chromatography-tandem mass spectrometry using an electrospray ionization source in positive and negative modes and analyzed by gas chromatography-tandem mass spectrometry using an advanced electron ionization source in positive mode. Instrument parameters were optimized for the highest sensitivity, and at least two transitions (quantifier and qualifier) were monitored for each analyte. Recoveries in test filtered water ( n =9; 183 analytes) from the American River, California, and suspended sediment ( n =9; 178 analytes) samples fortified at 15 nanograms per liter (ng/L) ranged from 70.1 to 121.0 and 71.1 to 117.0 percent in water and suspended sediment filter samples, respectively. Method detection limits of pesticides and pesticide degradates ranged from 0.5 to 10.6 ng/L in water and 0.7 to 11.8 ng/L in suspended sediment filters. Reporting limits were 1.1–21.1 ng/L and 1.5–23.7 ng/L in water and filter samples, respectively. The developed method is applied to surface-water samples for the analysis of pesticides, pesticide degradates, and other agrochemicals.

Techniques and Methods↗

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-Determination of arsenic and selenium in water and sediment by graphite furnace atomic absorption spectrometry

Graphite furnace-atomic absorption spectrometry (GF-AAS) is a sensitive, precise, and accurate technique that can be used to determine arsenic and selenium in samples of water and sediment. The GF-AAS method has been developed to replace the hydride generation-atomic absorption spectrometry (HG-AAS) methods because the method detection limits are similar, bias and variability are comparable, and interferences are minimal. Advantages of the GF-AAS method include shorter sample preparation time, increased sample throughput from simultaneous multielement analysis, reduced amount of chemical waste, reduced sample volume requirements, increased linear concentration range, and the use of a more accurate digestion procedure. The linear concentration range for arsenic and selenium is 1 to 50 micrograms per liter in solution; the current method detection limit for arsenic in solution is 0.9 microgram per liter; the method detection limit for selenium in solution is 1 microgram per liter. This report describes results that were obtained using stop-flow and low-flow conditions during atomization. The bias and variability of the simultaneous determination of arsenic and selenium by GF-AAS under both conditions are supported with results from standard reference materials--water and sediment, real water samples, and spike recovery measurements. Arsenic and selenium results for all Standard Reference Water Samples analyzed were within one standard deviation of the most probable values. Long-term spike recoveries at 6.25, 25.0, 37.5 micrograms per liter in reagent-, ground-, and surface-water samples for arsenic averaged 103 plus or minus 2 percent using low-flow conditions and 104 plus or minus 4 percent using stop-flow conditions. Corresponding recoveries for selenium were 98 plus or minus 13 percent using low-flow conditions and 87 plus or minus 24 percent using stop-flow conditions. Spike recoveries at 25 micrograms per liter in 120 water samples ranged from 97 to 99 percent for arsenic and from 82 to 93 percent for selenium, depending on the flow conditions used. Statistical analysis of dissolved and whole-water recoverable analytical results for the same set of water samples indicated that there is no significant difference between the GF-AAS and HG-AAS methods. Interferences related to various chemical constituents were also identified. Although sulfate and chloride in association with various cations might interfere with the determination of arsenic and selenium by GF-AAS, the use of a magnesium nitrate/palladium matrix modifier and low-flow argon during atomization helped to minimize such interferences. When using stabilized temperature platform furnace conditions where stop flow is used during atomization, the addition of hydrogen (5 percent volume/volume) to the argon minimized chemical interferences. Nevertheless, stop flow during atomization was found to be less effective than low flow in reducing interference effects.

Open-File Report↗

A new ghost-node method for linking different models and initial investigations of heterogeneity and nonmatching grids

A flexible, robust method for linking parent (regional-scale) and child (local-scale) grids of locally refined models that use different numerical methods is developed based on a new, iterative ghost-node method. Tests are presented for two-dimensional and three-dimensional pumped systems that are homogeneous or that have simple heterogeneity. The parent and child grids are simulated using the block-centered finite-difference MODFLOW and control-volume finite-element FEHM models, respectively. The models are solved iteratively through head-dependent (child model) and specified-flow (parent model) boundary conditions. Boundary conditions for models with nonmatching grids or zones of different hydraulic conductivity are derived and tested against heads and flows from analytical or globally-refined models. Results indicate that for homogeneous two- and three-dimensional models with matched grids (integer number of child cells per parent cell), the new method is nearly as accurate as the coupling of two MODFLOW models using the shared-node method and, surprisingly, errors are slightly lower for nonmatching grids (noninteger number of child cells per parent cell). For heterogeneous three-dimensional systems, this paper compares two methods for each of the two sets of boundary conditions: external heads at head-dependent boundary conditions for the child model are calculated using bilinear interpolation or a Darcy-weighted interpolation; specified-flow boundary conditions for the parent model are calculated using model-grid or hydrogeologic-unit hydraulic conductivities. Results suggest that significantly more accurate heads and flows are produced when both Darcy-weighted interpolation and hydrogeologic-unit hydraulic conductivities are used, while the other methods produce larger errors at the boundary between the regional and local models. The tests suggest that, if posed correctly, the ghost-node method performs well. Additional testing is needed for highly heterogeneous systems. ?? 2007 Elsevier Ltd. All rights reserved.

Advances in Water Resources↗

Estimation of nonlinear water-quality trends in high-frequency monitoring data

Recent advances in high-frequency water-quality sensors have enabled direct measurements of physical and chemical attributes in rivers and streams nearly continuously. Water-quality trends can be used to identify important watershed-scale changes driven by natural and anthropogenic influences. Statistical methods to estimate trends using high-frequency data are lacking. To address this gap, an evaluation of the generalized additive model (GAM) approach to test for trends in high-frequency data was conducted. Our proposed framework includes methods for handling serial correlation, trend estimation and slope-change detection, and trend interpretation at arithmetic scale for log-transformed variables. Water-temperature and turbidity data, representing two analytes with different temporal patterns, collected from the James River at Cartersville, Virginia, USA, were chosen for this analysis. Results indicated that the model, including flow, season, time covariates, and interaction between flow and season performed well for both analytes. The same model structure was applied to specific conductance data, collected from a small highly urbanized watershed, with satisfactory model performance. The water temperature GAM results indicated that the significant decreasing-then-increasing patterns after 2012 were mainly driven by air temperature changes. The turbidity trend was not significant over time. The specific conductance results showed a consistently upward trend over the last decade due to ever-increasing urbanization in the small watershed. This study suggests that the GAM method has great potential as a useful tool for trend analysis on high-frequency data, and for informing watershed managers of hydro-climatic and human influences on water quality by detecting crucial signal variation over time.

Chesapeake Bay watershed↗

Gas chromatographic separation and quantitative estimation of barbiturate mixtures in solid dosage forms

A gas chromatographic method has been described for the analysis of mixed barbiturates in solid dosage forms. Analysis on a 10% SE-30 column gave good separations for butabarbital, amobarbital, secobarbital, pentobarbital, and/or phenobarbital; amobarbital is not separated adequately from pentobarbital. An internal standard, mephobarbital, is used to minimize injection errors. The method gives both good quantitative and qualitative results on the barbiturates investigated. Two synthetic tablet mixtures were analyzed by this procedure and recoveries were 98—103%. It is recommended that the method be subjected to collaborative study.

Journal of the Association of Official Analytical ↗

Polarographic determination of tungsten in rocks

This work was undertaken to develop a simpler and faster method than the classical gravimetric procedure for the determination of tungsten in rocks and ores. A new polarographic wave of tungsten is obtained in a supporting electrolyte of dilute hydrochloric acid containing tartrate ion. This permits the determination of tungsten both rapidly and accurately. No precipitation of the tungsten is necessary, and only the iron need be separated from the tungsten. The accuracy is within the limits of a polarographic procedure; comparison of polarographic and gravimetric results is given. The method reduces appreciably the amount of time ordinarily consumed in determination of tungsten.

Analytical Chemistry↗

Adaptive monitoring in support of adaptive management in rangelands

Monitoring supports iterative learning about the effectiveness of management actions, information that can help managers plan future actions, facilitate decision-making, and improve outcomes. Adaptive monitoring is the evolution of a monitoring program in response to new management questions; new or changing environmental or socioeconomic conditions, improved monitoring methods, models, and tools; and experience implementing the monitoring program. Adaptive monitoring is connected to research and management through the exchange of data; analytical, methodological, and technological developments; information; and understanding. We review recent advances in adaptive monitoring and discuss new opportunities for both the research and management communities to improve monitoring in the years ahead.

Rangelands↗

Minimum requirements for publishing hydrogen, carbon, nitrogen, oxygen and sulfur stable-isotope delta results (IUPAC Technical Report)

Stable hydrogen, carbon, nitrogen, oxygen and sulfur (HCNOS) isotope compositions expressed as isotope-delta values are typically reported relative to international standards such as Vienna Standard Mean Ocean Water (VSMOW), Vienna Peedee belemnite (VPDB) or Vienna Cañon Diablo Troilite (VCDT). These international standards are chosen by convention and the calibration methods used to realise them in practice undergo occasional changes. To ensure longevity and reusability of published data, a comprehensive description of (1) analytical procedure, (2) traceability, (3) data processing, and (4) uncertainty evaluation is required. Following earlier International Union of Pure and Applied Chemistry documents on terminology and notations, this paper proposes minimum requirements for publishing HCNOS stable-isotope delta results. Each of the requirements are presented with illustrative examples.

Pure and Applied Chemistry↗

A two-constituent solute-transport model for ground water having variable density

A numerical model has been developed to simulate solute transport and dispersion of either one or two constituents in groundwater where there is two-dimensional, density-dependent flow. The model is a modified version of the one documented by Konikow and Bredehoeft (1978), which uses finite-difference methods and the method of characteristics to solve the flow and transport equations. The model was tested on an idealized seawater intrusion problem for which an analytical solution has been developed. The results were nearly identical to those of other numerical models tested on the same problem. A description of the formats for the input data, a sample of input and output for a two-constituent example problem, and a listing of the Fortran program are presented. (Author 's abstract)

Water-Resources Investigations Report↗

Getting the message across: using ecological integrity to communicate with resource managers

This chapter describes and illustrates how concepts of ecological integrity, thresholds, and reference conditions can be integrated into a research and monitoring framework for natural resource management. Ecological integrity has been defined as a measure of the composition, structure, and function of an ecosystem in relation to the system’s natural or historical range of variation, as well as perturbations caused by natural or anthropogenic agents of change. Using ecological integrity to communicate with managers requires five steps, often implemented iteratively: (1) document the scale of the project and the current conceptual understanding and reference conditions of the ecosystem, (2) select appropriate metrics representing integrity, (3) define externally verified assessment points (metric values that signify an ecological change or need for management action) for the metrics, (4) collect data and calculate metric scores, and (5) summarize the status of the ecosystem using a variety of reporting methods. While we present the steps linearly for conceptual clarity, actual implementation of this approach may require addressing the steps in a different order or revisiting steps (such as metric selection) multiple times as data are collected. Knowledge of relevant ecological thresholds is important when metrics are selected, because thresholds identify where small changes in an environmental driver produce large responses in the ecosystem. Metrics with thresholds at or just beyond the limits of a system’s range of natural variability can be excellent, since moving beyond the normal range produces a marked change in their values. Alternatively, metrics with thresholds within but near the edge of the range of natural variability can serve as harbingers of potential change. Identifying thresholds also contributes to decisions about selection of assessment points. In particular, if there is a significant resistance to perturbation in an ecosystem, with threshold behavior not occurring until well beyond the historical range of variation, this may provide a scientific basis for shifting an ecological assessment point beyond the historical range. We present two case studies using ongoing monitoring by the US National Park Service Vital Signs program that illustrate the use of an ecological integrity approach to communicate ecosystem status to resource managers. The Wetland Ecological Integrity in Rocky Mountain National Park case study uses an analytical approach that specifically incorporates threshold detection into the process of establishing assessment points. The Forest Ecological Integrity of Northeastern National Parks case study describes a method for reporting ecological integrity to resource managers and other decision makers. We believe our approach has the potential for wide applicability for natural resource management.

Book chapter↗

Methodological refinements in the determination of 146 polychlorinated biphenyls, including non-ortho- and mono-ortho-substituted PCBs, and 26 organochlorine pesticides as demonstrated in heron eggs

A method for the determination of 146 polychlorinated biphenyls (PCBs), including four non-ortho- and eight mono-ortho-substituted congeners, and 26 chlorinated pesticides is described. The method consists of ultrasonic extraction, Florisil cleanup, HPLC fractionation over porous graphitic carbon (PGC), and final determination with GC/ECD, GC/MS, or both. Two PCB congeners (PCB 30 and PCB 161) and two polybromobiphenyls (2,4‘,5-tribromobiphenyl and 3,3‘,4,4‘-tetrabromobiphenyl) were used as surrogate standards to evaluate the analytical efficiency. Four PCB congeners, PCB 14 and PCB 159 for the first fraction, PCB 61 for the second fraction, and PCB 204 for the third fraction, were used as internal standards to monitor the GC performance. The retention behavior of PCBs and pesticides on the PGC column are discussed. The method was found to be reproducible, effective, and reliable under the operational conditions proposed and was applied successfully to the analysis of individual PCBs and chlorinated pesticides in black-crowned night heron ( Nycticorax nycticorax ) egg samples.

Maryland↗

Identifying sources of heterogeneity in capture probabilities: An example using the Great Tit Parus major

Heterogeneous capture probabilities are a common problem in many capture-recapture studies. Several methods of detecting the presence of such heterogeneity are currently available, and stratification of data has been suggested as the standard method to avoid its effects. However, few studies have tried to identify sources of heterogeneity, or whether there are interactions among sources. The aim of this paper is to suggest an analytical procedure to identify sources of capture heterogeneity. We use data on the sex and age of Great Tits captured in baited funnel traps, at two localities differing in average temperature. We additionally use 'recapture' data obtained by videotaping at feeder (with no associated trap), where the tits ringed with different colours were recorded. This allowed us to test whether individuals in different classes (age, sex and condition) are not trapped because of trap shyness or because o a reduced use of the bait. We used logistic regression analysis of the capture probabilities to test for the effects of age, sex, condition, location and 'recapture method. The results showed a higher recapture probability in the colder locality. Yearling birds (either males or females) had the highest recapture prob abilities, followed by adult males, while adult females had the lowest recapture probabilities. There was no effect of the method of 'recapture' (trap or video tape), which suggests that adult females are less often captured in traps no because of trap-shyness but because of less dependence on supplementary food. The potential use of this methodological approach in other studies is discussed.

Barcelona, Madrid↗

The effect of scent lures on detection is not equitable among sympatric species

Context: Camera trapping is an effective tool for cost-efficient monitoring of species over large temporal and spatial scales and it is becoming an increasingly popular method for investigating wildlife communities and trophic interactions. However, camera trapping targeting rare and elusive species can be hampered by low detection rates, which can decrease the accuracy and precision of results from common analytical approaches (e.g., occupancy modeling, capture-recapture). Consequently, researchers often employ attractants to increase detection without accounting for how attractants influence detection of species among trophic levels. Aims: We aimed to evaluate the influences of a commonly used non-species-specific olfactory lure (i.e. sardines) and sampling design on detection of four species (i.e. bobcat [ Lynx rufus ], coyote [ Canis latrans ], raccoon [ Procyon lotor ], and eastern cottontail [ Sylvilagus floridanus ]) that represented a range of foraging guilds in an agricultural landscape. Methods: We set 180 camera stations, each for ∼28 days, during the summer of 2019. We set cameras with one of three lure treatments: (1) olfactory lure, (2) no olfactory lure, or (3) olfactory lure only during the latter half of the survey. We evaluated the influence of the lure at three temporal scales of detection (i.e. daily probability of detection, independent sequences per daily detection, and triggers per independent sequence). Key results: The lure tended to positively influence detection of coyotes and raccoons but negatively influenced detection of bobcats and eastern cottontails. The influence of the lure varied among temporal scales of detection. Conclusions: Scent lures can differentially influence detection of species within or among tropic levels, and the influence of a scent lure may vary among temporal scales. Implications: Our results demonstrate the importance of evaluating the influence of an attractant for each focal species when using camera data to conduct multi-species or community analyses, accounting for variation in sampling strategies across cameras, and identifying the appropriate species-specific temporal resolution for assessing variation in detection data. Furthermore, we highlight that care should be taken when using camera data as an index of relative abundance (e.g. as is commonly done with prey species) when there is variation in the use of lures across cameras.

Wildlife Research↗