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Calibration of Nu-Instruments Noblesse multicollector mass spectrometers for argon isotopic measurements using a newly developed reference gas

The greatest challenge limiting 40 Ar/ 39 Ar multicollection measurements is the availability of appropriate standard gasses to intercalibrate detectors. In particular, use of zoom lens ion-optics to steer and focus ion beams into a fixed detector array (i.e., Nu Instruments Noblesse) makes intercalibration of multiple detectors challenging because different ion-optic tuning conditions are required for optimal peak shape and sensitivity at different mass stations. We have found that detector efficiency and mass discrimination are affected by changes in ion-optic tuning parameters. Reliance upon an atmospheric Ar standard to calibrate the Noblesse is problematic because there is no straightforward way to relate atmospheric 40 Ar and 36 Ar to measurements of 40 Ar and 39 Ar if they are measured on separate detectors. After exploring alternative calibration approaches, we have concluded that calibration of the Noblesse is best performed using exactly the same source, detector, and ion-optic tuning settings as those used in routine 40 Ar/ 39 Ar analysis. To accomplish this, we have developed synthetic reference gasses containing 40 Ar, 39 Ar and 38 Ar produced by mixing gasses derived from neutron-irradiated sanidine with an enriched 38 Ar spike. We present a new method for calibrating the Noblesse based on use of both atmospheric Ar and the synthetic reference gasses. By combining atmospheric Ar and synthetic reference gas in different ways, we can directly measure 40 Ar/ 39 Ar, 38 Ar/ 39 Ar, and 36 Ar/ 39 Ar correction factors over ratios that vary from 0.5 to 460. These correction factors are reproducible to better than ± 0.5‰ (2σ standard error) over intervals spanning ~ 24 h but can vary systematically by ~ 4% over 2 weeks of continuous use when electron multiplier settings are held constant. Monitoring this variation requires daily calibration of the instrument. Application of the calibration method to 40 Ar/ 39 Ar multicollection measurements of widely used sanidine reference materials ACs-2, FCs-2, and TCs-2 demonstrate that calculated 40 Ar*/ 39 Ar K can be accurately corrected to yield model 40 Ar/ 39 Ar ages consistent with those reported by Earthtime 40 Ar/ 39 Ar laboratories. Replicate analyses of 8–12 single-crystal sanidine ages are reproduced to within 1–2‰ (2σ standard error) under optimal analytical conditions. This calibration technique is applicable over a wide range of isotopic ratios and signal sizes. Finally, the reference gas has the added advantage of facilitating straightforward characterization of electron multiplier dead time over a wide dynamic range.

Chemical Geology↗

Lava fingerprinting using paleomagnetism and innovative X-ray fluorescence spectroscopy: A case study from the Coso volcanic field, California

[1] We demonstrate an efficient method of rigorously separating difficult-to-distinguish lavas into eruptive units based on paleomagnetic remanence direction and rapid X-ray fluorescence spectroscopy (XRF) for Rb, Sr, Y, Zr, and Nb of polished paleomagnetic core samples (called PC XRF). Combined use of paleomagnetic remanence and PC XRF for lava fingerprinting allows correlation of individual eruptive units from one locality to another, permitting compilation of composite stratigraphy and paleomagentic measurement of relative vertical axis rotation of fault-bounded blocks. We test this lava fingerprinting method on rocks from the Coso volcanic field, California, against similar fingerprinting using XRF analysis by established methods. Resulting unit definitions and correlations are the same by both XRF techniques when coupled with paleomagnetic data, but at great time and cost savings with PC XRF. PC XRF analysis is possible because (1) matrix and grain size effects are minimal for the element set analyzed, (2) moderately phyric to aphyric polished paleomagnetic cores are already homogenous on spatial scales of 2 cm, and (3) use of element ratios cancels out some analytical uncertainties as well as minimizes effects of concentration variations due to fractional crystallization. Paleomagnetic remanence direction is an indispensable part of fingerprinting because it distinguishes flows of similar chemistry and can also place constraints on the duration of emplacement of each eruptive unit.

California↗

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-Determination of low-level silver by graphite furnace atomic absorption spectrophotometry

Increased awareness of the quality of water in the United States has led to the development of a method for determining low levels (0.2-5.0 microg/L) of silver in water samples. Use of graphite furnace atomic absorption spectrophotometry provides a sensitive, precise, and accurate method for determining low-level silver in samples of low ionic-strength water, precipitation water, and natural water. The minimum detection limit determined for low-level silver is 0.2 microg/L. Precision data were collected on natural-water samples and SRWS (Standard Reference Water Samples). The overall percent relative standard deviation for natural-water samples with silver concentrations more than 0.2 microg/L was less than 40 percent throughout the analytical range. For the SRWS with concentrations more than 0.2 microg/L, the overall percent relative standard deviation was less than 25 percent throughout the analytical range. The accuracy of the results was determined by spiking 6 natural-water samples with different known concentrations of the silver standard. The recoveries ranged from 61 to 119 percent at the 0.5-microg/L spike level. At the 1.25-microg/L spike level, the recoveries ranged from 92 to 106 percent. For the high spike level at 3.0 microg/L, the recoveries ranged from 65 to 113 percent. The measured concentrations of silver obtained from known samples were within the Branch of Quality Assurance accepted limits of 1 1/2 standard deviations on the basis of the SRWS program for Inter-Laboratory studies.

Open-File Report↗

An update of hydrologic conditions and distribution of selected constituents in water, eastern Snake River aquifer and perched groundwater zones, Idaho National Laboratory, Idaho, emphasis 2019–21

Since 1952, wastewater discharged to infiltration ponds (also called “percolation ponds”) and disposal wells at the Idaho National Laboratory (INL) has affected water quality in the eastern Snake River Plain (ESRP) aquifer and perched groundwater zones underlying the INL. The U.S. Geological Survey (USGS), in cooperation with the U.S. Department of Energy (DOE), maintains groundwater-monitoring networks at the INL to determine hydrologic trends and to delineate the movement of radiochemical and chemical wastes in both the aquifer and perched groundwater zones. This report presents an analysis of water-level and water-quality data collected from the ESRP aquifer and perched groundwater wells from the USGS groundwater monitoring networks during 2019–21. From March–May 2018 to March–May 2021, water levels in wells completed in the ESRP aquifer increased in the northern part of the INL and decreased in the southwestern part. Water-level increases ranged from 0.02 to 1.04 feet in the northern part and decreases ranged from 0.03 to 2.94 feet in the southwestern part of the INL. Detectable concentrations of radiochemical constituents in water samples from wells in the ESRP aquifer at the INL generally decreased or remained constant during 2019–21. Decreases in concentrations were attributed to radioactive decay, changes in waste-disposal methods, and dilution from recharge and underflow. In 2021, tritium was detected above reporting levels in water samples collected from 46 of 105 aquifer wells and ranged from 150±50 to 4,280±150 picocuries per liter (pCi/L). Tritium concentrations from eight wells completed in deep perched groundwater near the Advanced Test Reactor Complex (ATRC) generally were greater than or equal to the reporting level during at least one sampling event during 2019–21, and concentrations ranged from 160±50 to 2,097±107 pCi/L. Concentrations of strontium-90 in water from 12 of 45 aquifer wells sampled in 2021 exceeded the reporting level, and concentrations ranged from 2.5±0.7 to 299±6 pCi/L. During 2021, concentrations of strontium-90 from five wells completed in deep perched groundwater at the ATRC equaled or exceeded the reporting levels, and concentrations ranged from 3±0.9 pCi/L to 27.8±1.3 pCi/L. Concentrations of cesium-137 were less than the reporting level in all but one aquifer well, and concentrations of plutonium-238, plutonium-239, -240 (undivided), and americium-241 were less than the reporting level in water samples from all aquifer wells sampled during this study period. Dissolved chromium concentrations in water samples from 64 ESRP aquifer wells ranged from less than (<) 0.5 to 76.4 micrograms per liter (μg/L). During 2019–21, dissolved chromium was detected in water from wells completed in deep perched groundwater above the ESRP aquifer at the ATRC, and concentrations ranged from <1 to 82.1 μg/L. In 2021, concentrations of dissolved sodium in water from most ESRP aquifer wells in the southern part of the INL were greater than the western tributary groundwater background concentration of 8.3 milligrams per liter (mg/L). During 2021, dissolved sodium concentrations in water from 15 wells completed in deep perched groundwater ranged from 11.7 to 122.5 mg/L. Variations in sodium concentrations in aquifer wells and perched groundwater zones are attributed to either migration of remnant water from the former chemical-waste ponds or disposal volume and composition variability in percolation ponds installed in 2008. In 2021, concentrations of chloride in most water samples from ESRP aquifer wells south of the Idaho Nuclear Technology and Engineering Center (INTEC) and at the Central Facilities Area (CFA) exceeded background concentrations. Chloride concentrations in water from wells south of the INTEC have generally decreased because of discontinued chloride disposal to the legacy percolation ponds since 2002 when the discharge of wastewater was discontinued. During 2019–21, dissolved chloride concentrations in deep perched groundwater above the ESRP aquifer from 18 wells at the ATRC ranged from 8.15 to 231 mg/L. In 2021, sulfate concentrations in water samples from ESRP aquifer wells in the south-central part of the INL that exceeded the background concentration of sulfate, ranged from 21 to 141 mg/L. The greater-than-background concentrations in water from these wells are attributed to sulfate disposal at the ATRC infiltration ponds or the legacy INTEC percolation ponds. In 2021, sulfate concentrations in water samples from aquifer wells near the Radioactive Waste Management Complex (RWMC) were mostly greater than background concentrations. The maximum dissolved sulfate concentration in shallow perched groundwater near the ATRC was 575 mg/L in 2021. During 2021, dissolved sulfate concentrations in water from wells completed in deep perched groundwater near the cold waste ponds at the ATRC ranged from 22.3 to 519 mg/L. In 2021, concentrations of nitrate in water from most ESRP aquifer wells at and near the INTEC exceeded the western tributary groundwater background concentration of 0.655 mg/L. Concentrations of nitrate in aquifer wells southwest of INTEC and farther away from the influence of disposal areas and the Big Lost River, in intermittent source of surface water recharge to the aquifer, show a general decrease in nitrate concentration over time. Two aquifer wells south of INTEC show increasing trends that could result from wastewater beneath the INTEC tank farm being mobilized to the aquifer. During 2019–21, water samples from several ESRP aquifer wells were collected and analyzed for volatile organic compounds (VOCs). Twelve VOCs were detected, and 1–4 VOCs were detected in water samples from 10 wells. The most frequently detected VOCs include carbon tetrachloride (tetrachloromethane), trichloromethane, tetrachloroethene, 1,1,1-trichloroethane, and trichloroethene. In 2019–21, concentrations for all VOCs were less than their respective maximum contaminant levels (MCLs) for drinking water, except carbon tetrachloride in one well, trichloroethene in two wells, and vinyl chloride in one well. During 2019–21, variability and bias were evaluated from 34 replicate and 14 blank quality-assurance samples. Results from replicate analyses were investigated to evaluate sample variability. Constituents with acceptable reproducibility were major ions, trace elements, nutrients, and VOCs. All radiochemical constituents including gross alpha- and beta- radioactivity, strontium-90, cesium-137, and tritium, had acceptable reproducibility. Bias from sample contamination was evaluated from equipment, field, and source-solution blanks. Chloride and sulfate were detected slightly above their respective method detection limits in equipment and field blanks, but at concentrations well below the co-collected sample for that well. These chloride and sulfate detections in the field and equipment blanks were inconsequential because they weren’t detected above the analysis-specific variability for those constituents as determined by replicate sample result evaluation. None of the detections of nutrients and trace inorganic constituents were high enough to indicate environmental sample or analytical procedure bias.

Idaho↗

The dynamics of coastal models

Coastal basins are defined as estuaries, lagoons, and embayments. This book deals with the science of coastal basins using simple models, many of which are presented in either analytical form or Microsoft Excel or MATLAB. The book introduces simple hydrodynamics and its applications, from the use of simple box and one-dimensional models to flow over coral reefs. The book also emphasizes models as a scientific tool in our understanding of coasts, and introduces the value of the most modern flexible mesh combined wave-current models. Examples from shallow basins around the world illustrate the wonders of the scientific method and the power of simple dynamics. This book is ideal for use as an advanced textbook for graduate students and as an introduction to the topic for researchers, especially those from other fields of science needing a basic understanding of the basic ideas of the dynamics of coastal basins.

Book↗

X-ray spectrographic determination of cesium and rubidium

An x-ray spectrographic method for the determination of rubidium and cesium was developed, using the internal-standard method and a four-channel flat-crystal spectrograph. The sensitivity is within 0.1% for cesia and 0.02% for rubidia; the precision is within 10% of the amount present. Results agree well with those obtained by flame photometry and by radio-activation.

Analytical Chemistry↗

Determination of the platinum - Group elements (PGE) and gold (Au) in manganese nodule reference samples by nickel sulfide fire-assay and Te coprecipitation with ICP-MS

Platinum group elements (PGE) and Au data in polymetallic oceanic ferromanganese nodule reference samples and crust samples obtained by inductively coupled plasma mass spectrometry (ICP-MS), after separation and pre-concentration by nickel sulfide fire-assay and Te coprecipitation, are presented. By optimizing several critical parameters such as flux composition, matrix matching calibration, etc., best experimental conditions were established to develop a method suitable for routine analysis of manganese nodule samples for PGE and Au. Calibrations were performed using international PGE reference materials, WMG-1 and WMS-1. This improved procedure offers extremely low detection limits in the range of 0.004 to 0.016 ng/g. The results obtained in this study for the reference materials compare well with previously published data wherever available. New PGE data arc also provided on some international manganese nodule reference materials. The analytical methodology described here can be used for the routine analysis of manganese nodule and crust samples in marine geochemical studies.

Indian Journal of Marine Sciences↗

Dithizone method for determination of lead in monazite

In the determination of lead in monazite-to be used as the basis for geologic age measurements-it was necessary to eliminate interferences due to the presence of phosphates of thorium and the rare earth metals. The method involves attacking the monazite samples with hot, concentrated sulfuric acid, then taking them up with dilute nitric acid. Lead is extracted as the dithizonate and determined spectrophotometrically at 520 mµ. Rapid determinations were made with good reproducibility on a series of monazite samples.

Analytical Chemistry↗

Expanding national-scale wildlife disease surveillance systems with research networks

Efficient learning about disease dynamics in free-ranging wildlife systems can benefit from active surveillance that is standardized across different ecological contexts. For example, active surveillance that targets specific individuals and populations with standardized sampling across ecological contexts (landscape-scale targeted surveillance) is important for developing a mechanistic understanding of disease emergence, which is the foundation for improving risk assessment of zoonotic or wildlife-livestock disease outbreaks and predicting hotspots of disease emergence. However, landscape-scale targeted surveillance systems are rare and challenging to implement. Increasing experience and infrastructure for landscape-scale targeted surveillance will improve readiness for rapid deployment of this type of surveillance in response to new disease emergence events. Here, we describe our experience developing and rapidly deploying a landscape-scale targeted surveillance system for severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) in two free-ranging deer species across their ranges in the United States. Our surveillance system was designed to collect data across individual, population, and landscape scales for future analyses aimed at understanding mechanisms and risk factors of SARS-CoV-2 transmission, evolution, and persistence. Our approach leveraged partnerships between state and federal public service sectors and academic researchers in a landscape-scale targeted surveillance research network. Methods describe our approach to developing the surveillance network and sampling design. Results report challenges with implementing our intended sampling design, specifically how the design was adapted as different challenges arose and summarize the sampling design that has been implemented thus far. In the discussion, we describe strategies that were important for the successful deployment of landscape-scale targeted surveillance, development and operation of the research network, construction of similar networks in the future, and analytical approaches for the data based on the sampling design.

Ecology and Evolution↗

Determination of trace levels of herbicides and their degradation products in surface and ground waters by gas chromatography/ion-trap mass spectrometry

A rapid, specific and highly sensitive method is described for the determination of several commonly used herbicides and their degradation products in surface and ground waters by using gas chromatography/ion-trap mass spectrometry. The compounds included atrazine, and its degradation products desethylatrazine and desisopropylatrazine; Simazine; Cyanazine; Metolachlor; and alachlor and its degradation products, 2-chloro-2', 6'-diethylacetanilide, 2-hydroxy-2', 6'-diethylacetanilide and 2,6-diethylaniline. The method was applied to surface-water samples collected from 16 different stations along the lower Mississippi River and its major tributaries, and ground-water samples beneath a cornfield in central Nebraska. Average recovery of a surrogate herbicide, terbuthylazine, was greater than 99%. Recoveries of the compounds of interest from river water spiked at environmental levels are also presented. Full-scan mass spectra of these compounds were obtained on 1 ng or less of analyte. Data were collected in the full-scan acquisition mode. Quantitation was based on a single characteristic ion for each compound. The detection limit was 60 pg with a signal-to-noise ratio of greater than 10:1.

Analytica Chimica Acta↗

The atmosphere can be a source of certain water soluble volatile organic compounds in urban streams

Surface water and air volatile organic compound (VOC) data from 10 U.S. Geological Survey monitoring sites were used to evaluate the potential for direct transport of VOCs from the atmosphere to urban streams. Analytical results of 87 VOC compounds were screened by evaluating the occurrence and detection levels in both water and air, and equilibrium concentrations in water (C w s ) based on the measured air concentrations. Four compounds (acetone, methyl tertiary butyl ether, toluene, and m - & p -xylene) were detected in more than 20% of water samples, in more than 10% of air samples, and more than 10% of detections in air were greater than long-term method detection levels (LTMDL) in water. Benzene was detected in more than 20% of water samples and in more than 10% of air samples. Two percent of benzene detections in air were greater than one-half the LTMDL in water. Six compounds (chloroform, p-isopropyltoluene, methylene chloride, perchloroethene, 1,1,1-trichloroethane, and trichloroethene) were detected in more than 20% of water samples and in more than 10% of air samples. Five VOCs, toluene, m - & p -xylene, methyl tert-butyl ether (MTBE), acetone, and benzene were identified as having sufficiently high concentrations in the atmosphere to be a source to urban streams. MTBE, acetone, and benzene exhibited behavior that was consistent with equilibrium concentrations in the atmosphere.

Journal of the American Water Resources Associatio↗

Relations between DNA- and RNA-based molecular methods for cyanobacteria and microcystin concentration at Maumee Bay State Park Lakeside Beach, Oregon, Ohio, 2012

Water samples were collected from Maumee Bay State Park Lakeside Beach, Oregon, Ohio, during the 2012 recreational season and analyzed for selected cyanobacteria gene sequences by DNA-based quantitative polymerase chain reaction (qPCR) and RNA-based quantitative reverse-transcription polymerase chain reaction (qRT-PCR). Results from the four DNA assays (for quantifying total cyanobacteria, total Microcystis , and Microcystis and Planktothrix strains that possess the microcystin synthetase E ( mcyE ) gene) and two RNA assays (for quantifying Microcystis and Planktothrix genera that are expressing the microcystin synthetase E ( mcyE ) gene) were compared to microcystin concentration results determined by an enzyme-linked immunosorbent assay (ELISA). Concentrations of the target in replicate analyses were log10 transformed. The average value of differences in log10 concentrations for the replicates that had at least one detection were found to range from 0.05 to >0.37 copy per 100 milliliters (copy/100 mL) for DNA-based methods and from >0.04 to >0.17 copy/100 mL for RNA-based methods. RNA has a shorter half-life than DNA; consequently, a 24-hour holding-time study was done to determine the effects of holding time on RNA concentrations. Holding-time comparisons for the RNA-based Microcystis toxin mcyE assay showed reductions in the number of copies per 100 milliliters over 24 hours. The log difference between time 2 hours and time 24 hours was >0.37 copy/100 mL, which was higher than the analytical variability (log difference of >0.17 copy/100 mL). Spearman’s correlation analysis indicated that microcystin toxin concentrations were moderately to highly related to DNA-based assay results for total cyanobacteria (rho=0.69), total Microcystis (rho=0.74), and Microcystis strains that possess the mcyE gene (rho=0.81). Microcystin toxin concentrations were strongly related with RNA-based assay results for Microcystis mcyE gene expression (rho=0.95). Correlation analysis could not be done for Planktothrix mcyE gene expression because of too few detections.

Ohio↗

Modeling crustal deformation near active faults and volcanic centers: a catalog of deformation models and modeling approaches

This manual provides the physical and mathematical concepts for selected models used to interpret deformation measurements near active faults and volcanic centers. The emphasis is on analytical models of deformation that can be compared with data from the Global Positioning System (GPS) receivers, Interferometric synthetic aperture radar (InSAR), leveling surveys, tiltmeters and strainmeters. Source models include pressurized spherical, ellipsoidal, and horizontal penny-shaped geometries in an elastic, homogeneous, flat half-space. Vertical dikes and faults are described following the mathematical notation for rectangular dislocations in an elastic, homogeneous, flat half-space. All the analytical expressions were verified against numerical models developed by use of COMSOL Multyphics, a Finite Element Analysis software (http://www.comsol.com). In this way, typographical errors present were identified and corrected. Matlab scripts are also provided to facilitate the application of these models.

Techniques and Methods↗

Preliminary assessment of a water-quality monitoring program for total maximum daily loads in Johnson County, Kansas, January 2015 through June 2016

Municipalities in Johnson County in northeastern Kansas are required to implement stormwater management programs to reduce pollutant discharges, protect water quality, and comply with applicable water-quality regulations in accordance with National Pollutant Discharge Elimination System permits for stormwater discharge. To this end, municipalities collect grab samples at streams entering and leaving their jurisdiction to determine levels of excessive nutrients, sediment, and fecal bacteria to characterize pollutants and understand the factors affecting them. In 2014, the U.S. Geological Survey and the Johnson County Stormwater Management Program, with input from the Kansas Department of Health and Environment, initiated a 5-year monitoring program to satisfy minimum sampling requirements for each municipality as described by new stormwater permits issued to Johnson County municipalities. The purpose of this report is to provide a preliminary assessment of the monitoring program. The monitoring program is described, a preliminary assessment of the monitoring program design is provided using water-quality data collected during the first 2 years of the program, and the ability of the current monitoring network and sampling plan to provide data sufficient to quantify improvements in water quality resulting from implemented and planned best management practices is evaluated. The information in this initial report may be used to evaluate changes in data collection methods while data collection is still ongoing that may lead to improved data utility. Discrete water-quality samples were collected at 27 sites and analyzed for nutrients, Escherichia coli ( E. coli ) bacteria, total suspended solids, and suspended-sediment concentration. In addition, continuous water-quality data (water temperature, pH, dissolved oxygen, specific conductance, turbidity, and nitrate plus nitrite) were collected at one site to characterize variability and provide a basis for comparison to discrete data. Base flow samples indicated that point sources are likely affecting nutrient concentrations and E. coli bacteria densities at several sites. Concentrations of all analytes in storm runoff samples were characterized by substantial variability among sites and samples. About one-half of the sites, representing different watersheds, had storm runoff samples with nitrogen concentrations greater than 10 milligrams per liter. About one-third of the sites, representing different watersheds, had storm runoff samples with total phosphorus concentrations greater than 3 milligrams per liter. Six sites had samples with E. coli densities greater than 100,000 colonies per 100 milliliters of water. Total suspended solids concentrations of about 12,000 milligrams per liter or greater occurred in samples from three sites. Data collected for this monitoring program may be useful for some general assessment purposes but may also be limited in potential to fully inform stormwater management activities. Valuable attributes of the monitoring program design included incorporating many sites across the county for comparisons among watersheds and municipalities, using fixed-stage samplers to collect multiple samples during single events, collection of base flow samples in addition to storm samples to isolate possible point sources from stormwater sources, and use of continuous monitors to characterize variability. Limiting attributes of the monitoring program design included location of monitoring sites along municipal boundaries to satisfy permit requirements rather than using watershed-based criteria such as locations of tributaries, potential pollutant sources, and implemented management practices. Additional limiting attributes include having a large number of widespread sampling locations, which presented logistical challenges for predicting localized rainfall and collecting and analyzing samples during short timeframes associated with storms, and collecting storm samples at fixed-stage elevations only during the rising limb of storms, which does not characterize conditions over the storm hydrograph. The small number of samples collected per site resulted in a sample size too small to be representative of site conditions, including seasonal and hydrologic variability, and insufficient for meaningful statistical analysis or site-specific modeling. Several measures could be taken to improve data utility and include redesigning the monitoring network according to watershed characteristics, incorporating a nested design in which data are collected at different scales (watershed, subwatershed, and best management practices), increasing sampling frequency, and combining different methods to allow for flexibility to focus on areas and conditions of particular interest. A monitoring design that would facilitate most of these improvements would be to focus efforts on a limited number of watersheds for several years, then cycle to the next set of watersheds for several years, eventually returning to previously monitored watersheds to document changes. Redesign of the water-quality monitoring program requires considerable effort and commitment from municipalities of Johnson County. However, the long-term benefit likely is a monitoring program that results in improved stream conditions and more effective management practices and efficient expenditure of resources.

Kansas↗

Evaluation of a portable automated serum chemistry analyzer for field assessment of harlequin ducks, Histrionicus histrionicus

A portable analytical chemistry analyzer was used to make field assessments of wild harlequin ducks ( Histrionicus histrionicus ) in association with telemetry studies of winter survival in Prince William Sound, Alaska. We compared serum chemistry results obtained on-site with results from a traditional laboratory. Particular attention was paid to serum glucose and potassium concentrations as potential indicators of high-risk surgical candidates based on evaluation of the field data. The median differential for glucose values ( 𝑁 = 8 2 ) between methods was 0.6 mmol/L (quartiles 0.3 and 0.9 mmol/L) with the median value higher when assayed on site. Analysis of potassium on site returned a median of 2.7 mmol/L ( 𝑁 = 8 8 ; quartiles 2.4 and 3.0 mmol/L). Serum potassium values were too low for quantitation by the traditional laboratory. Changes in several serum chemistry values following a three-day storm during the study support the value of on site evaluation of serum potassium to identify presurgical patients with increased anesthetic risk.

Alaska↗

Improving predictive power of physically based rainfall-induced shallow landslide models: a probablistic approach

Distributed models to forecast the spatial and temporal occurrence of rainfall-induced shallow landslides are deterministic. These models extend spatially the static stability models adopted in geotechnical engineering and adopt an infinite-slope geometry to balance the resisting and the driving forces acting on the sliding mass. An infiltration model is used to determine how rainfall changes pore-water conditions, modulating the local stability/instability conditions. A problem with the existing models is the difficulty in obtaining accurate values for the several variables that describe the material properties of the slopes. The problem is particularly severe when the models are applied over large areas, for which sufficient information on the geotechnical and hydrological conditions of the slopes is not generally available. To help solve the problem, we propose a probabilistic Monte Carlo approach to the distributed modeling of shallow rainfall-induced landslides. For the purpose, we have modified the Transient Rainfall Infiltration and Grid-Based Regional Slope-Stability Analysis (TRIGRS) code. The new code (TRIGRS-P) adopts a stochastic approach to compute, on a cell-by-cell basis, transient pore-pressure changes and related changes in the factor of safety due to rainfall infiltration. Infiltration is modeled using analytical solutions of partial differential equations describing one-dimensional vertical flow in isotropic, homogeneous materials. Both saturated and unsaturated soil conditions can be considered. TRIGRS-P copes with the natural variability inherent to the mechanical and hydrological properties of the slope materials by allowing values of the TRIGRS model input parameters to be sampled randomly from a given probability distribution. The range of variation and the mean value of the parameters can be determined by the usual methods used for preparing the TRIGRS input parameters. The outputs of several model runs obtained varying the input parameters are analyzed statistically, and compared to the original (deterministic) model output. The comparison suggests an improvement of the predictive power of the model of about 10% and 16% in two small test areas, i.e. the Frontignano (Italy) and the Mukilteo (USA) areas, respectively. We discuss the computational requirements of TRIGRS-P to determine the potential use of the numerical model to forecast the spatial and temporal occurrence of rainfall-induced shallow landslides in very large areas, extending for several hundreds or thousands of square kilometers. Parallel execution of the code using a simple process distribution and the Message Passing Interface (MPI) on multi-processor machines was successful, opening the possibly of testing the use of TRIGRS-P for the operational forecasting of rainfall-induced shallow landslides over large regions.

Geoscientific Model Development and Discussions↗

Simultaneous determination of Cr(iii) and Cr(vi) using reversed-phased ion-pairing liquid chromatography with dynamic reaction cell inductively coupled plasma mass spectrometry

A method for the simultaneous determination of Cr(iii) and Cr(vi) species in waters, soil leachates and synthetic bio-fluids is described. The method uses reversed-phase ion-pairing liquid chromatography to separate the chromium species and a dynamic reaction cell (DRC??) equipped ICP-MS for detection of chromium. Separation of the chromium species is carried out in less than 2 min. Cr(iii) is complexed with ethylenediaminetetraacetic acid (EDTA) prior to separation by mixing samples with the mobile phase containing 2.0 mM tetrabutylammonium hydroxide (TBAOH), 0.5 mM EDTA (dipotassium salt), and 5% (vol/vol) methanol, adjusted to pH 7.6. The interfering 40Ar 12C+ background peak at mass 52 was reduced by over four orders of magnitude to less than 200 cps by using 0.65 mL min-1 ammonia as a reaction gas and an RPq setting on the DRC of 0.75. Method detection limits (MDLs) of 0.09 ??g L-1 for Cr(iii) and 0.06 ??g L-1 for Cr(vi) were obtained based on peak areas at mass 52 for 50 ??L injections of low level spikes. Reproducibility at 2 ??g L-1 was 3% RSD for 5 replicate injections. The tolerance of the method to various levels of common cations and anions found in natural waters and to matrix constituents found in soil leachates and simulated gastric and lung fluids was tested by performing spike recovery calculations for a variety of samples. ?? The Royal Society of Chemistry.

Journal of Analytical Atomic Spectrometry↗

Determination of selected azaarenes in water by bonded-phase extraction and liquid chromatography

A method for the rapid and simple quantitative determination of quinoline, isoquinoline, and five selected three-ring azaarenes in water has been developed. The azaarene fraction is separated from its carbon analogues on n-octadecyl packing material by edition with acidified water/acetonitrile. Concentration as great as 1000-fold is achieved readily. Instrumental analysis involves high-speed liquid chromatography on flexible-walled, wide-bore columns with fluorescence and ultraviolet detection at several wavelengths employing filter photometers in series. Method-validation data is provided as azaarene recovery efficiency from fortified samples. Distilled water, river water, contaminated ground water, and secondary-treatment effluent have been tested. Recoveries at part-per-billion levels are nearly quantitative for the three-ring compounds, but they decrease for quinoline and isoquinoline.

Analytical Chemistry↗