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GeoAI and the future of spatial analytics

This chapter discusses the challenges of traditional spatial analytical methods in their limited capacity to handle big and messy data, as well as mining unknown or latent patterns. It then introduces a new form of spatial analytics—geospatial artificial intelligence (GeoAI)—and describes the advantages of this new strategy in big data analytics and data-driven discovery. Finally, a convergent spatial analytical framework is suggested as a potential future pathway for spatial analysis.

Book chapter↗

Determination of pesticides associated with suspended sediments in the San Joaquin River, California, USA, using gas chromatography-ion trap mass spectrometry

An analytical method useful for the quantification of a range of pesticides and pesticide degradation products associated with suspended sediments was developed by testing a variety of extraction and cleanup schemes. The final extraction and cleanup methods chosen for use are suitable for the quantification of the listed pesticides using gas chromatography-ion trap mass spectrometry and the removal of interfering coextractable organic material found in suspended sediments. Methylene chloride extraction followed by Florisil cleanup proved most effective for separation of coextractives from the pesticide analytes. Removal of elemental sulfur was accomplished with tetrabutylammonium hydrogen sulfite. The suitability of the method for the analysis of a variety of pesticides was evaluated, and the method detection limits (MDLs) were determined (0.1-6.0 ng/g dry weight of sediment) for 21 compounds. Recovery of pesticides dried onto natural sediments averaged 63%. Analysis of duplicate San Joaquin River suspended-sediment samples demonstrated the utility of the method for environmental samples with variability between replicate analyses lower than between environmental samples. Eight of 21 pesticides measured were observed at concentrations ranging from the MDL to more than 80 ng/g dry weight of sediment and exhibited significant temporal variability. Sediment-associated pesticides, therefore, may contribute to the transport of pesticides through aquatic systems and should be studied separately from dissolved pesticides.

Toxicological and Environmental Chemistry↗

Flood-discharge profiles of selected streams in Rockland County, New York

Flood-discharge profiles of 10 streams in Rockland County at six recurrence intervals ranging from 2 to 100 years are presented. Synthetic flood-frequency estimates were derived for nine rainfall-runoff sites from calibrated models; observed flood-frequency estimates were derived for three sites having long-term discharge records. A variance-weighting technique was applied to compare the synthetic flood-frequency estimates with the observed (gaged) estimates and estimates computed at each site from regional regression equations. For ungaged locations on the 10 streams, flood-frequency relationships were derived from regional regression equations previously developed for New Jersey streams. Regional analysis indicated the most significant basin characteristics to be drainage area, streambed slope, storage, and amount of impervious cover. A method for refining (weighting) flood-frequency estimates at selected ungaged locations near rainfall-runoff and (or) long-term gaged sites is given. This report explains analytical methods and includes a list of basin characteristics at several locations along each stream and a table of peak discharges for the six recurrence intervals at 13 gaging stations. The profiles enable the determination of flood discharge at all locations having a drainage area greater than 1 square mile on the 10 streams. (USGS)

Water-Resources Investigations Report↗

U/Th dating by SHRIMP RG ion-microprobe mass spectrometry using single ion-exchange beads

We present a new analytical method for U-series isotopes using the SHRIMP RG (Sensitive High mass Resolution Ion MicroProbe) mass spectrometer that utilizes the preconcentration of the U-series isotopes from a sample onto a single ion-exchange bead. Ion-microprobe mass spectrometry is capable of producing Th ionization efficiencies in excess of 2%. Analytical precision is typically better than alpha spectroscopy, but not as good as thermal ionization mass spectroscopy (TIMS) and inductively coupled plasma multicollector mass spectrometry (ICP-MS). Like TIMS and ICP-MS the method allows analysis of small samples sizes, but also adds the advantage of rapidity of analysis. A major advantage of ion-microprobe analysis is that U and Th isotopes are analyzed in the same bead, simplifying the process of chemical separation. Analytical time on the instrument is ???60 min per sample, and a single instrument-loading can accommodate 15-20 samples to be analyzed in a 24-h day. An additional advantage is that the method allows multiple reanalyses of the same bead and that samples can be archived for reanalysis at a later time. Because the ion beam excavates a pit only a few ??m deep, the mount can later be repolished and reanalyzed numerous times. The method described of preconcentrating a low concentration sample onto a small conductive substrate to allow ion-microprobe mass spectrometry is potentially applicable to many other systems. Copyright ?? 2005 Elsevier Ltd.

Geochimica et Cosmochimica Acta↗

Ion microprobe measurement of strontium isotopes in calcium carbonate with application to salmon otoliths

The ion microprobe has the capability to generate high resolution, high precision isotopic measurements, but analysis of the isotopic composition of strontium, as measured by the 87 Sr/ 86 Sr ratio, has been hindered by isobaric interferences. Here we report the first high precision measurements of 87 Sr/ 86 Sr by ion microprobe in calcium carbonate samples with moderate Sr concentrations. We use the high mass resolving power (7000 to 9000 M.R.P.) of the SHRIMP-RG ion microprobe in combination with its high transmission to reduce the number of interfering species while maintaining sufficiently high count rates for precise isotopic measurements. The isobaric interferences are characterized by peak modeling and repeated analyses of standards. We demonstrate that by sample-standard bracketing, 87 Sr/ 86 Sr ratios can be measured in inorganic and biogenic carbonates with Sr concentrations between 400 and 1500 ppm with ∼2‰ external precision (2σ) for a single analysis, and subpermil external precision with repeated analyses. Explicit correction for isobaric interferences (peak-stripping) is found to be less accurate and precise than sample-standard bracketing. Spatial resolution is ∼25 μm laterally and 2 μm deep for a single analysis, consuming on the order of 2 ng of material. The method is tested on otoliths from salmon to demonstrate its accuracy and utility. In these growth-banded aragonitic structures, one-week temporal resolution can be achieved. The analytical method should be applicable to other calcium carbonate samples with similar Sr concentrations.

Geochimica et Cosmochimica Acta↗

Concentrations of platinum group elements in 122 U.S. coal samples

Analysis of more than 13,000 coal samples by semi-quantitative optical emission spectroscopy (OES) indicates that concentrations of the platinum group elements (iridium, palladium, platinum, osmium, rhodium, and ruthenium) are less than 1 ppm in the ash, the limit of detection for this method of analysis. In order to accurately determine the concentration of the platinum group elements (PGE) in coal, additional data were obtained by inductively coupled plasma mass spectroscopy, an analytical method having part-per-billion (ppb) detection limits for these elements. These data indicate that the PGE in coal occur in concentrations on the order of 1 ppb or less.

Open-File Report↗

Report of the U.S. Geological Survey's analytical evaluation program; standard reference water samples M-82 (major constituents), T-83 (trace constituents), N-8 (nutrients), and P-2 (precipitation snowmelt)

The U.S. Geological Survey began an interlaboratory testing program of reference water samples in 1962. Principal purposes of the program are to provide a means for participating water laboratories to: (1) identify analytical problem areas; (2) ascertain the accuracy and precision of common water analyses and analytical methods and; (3) provide reference samples for continuing quality assurance testing. Participation in this continuing quality assurance program is mandatory for all domestic laboratories providing water analysis data for Survey use. Analytical data submitted by the participating laboratories that analyzed the respective reference samples distributed in October 1982 are presented. Relative performance ratings achieved by the laboratories for each determination and statistical evaluation of the data are given in 14 tables. (Author 's abstract)

Open-File Report↗

Method of analysis and quality-assurance practices by the U. S. Geological Survey Organic Geochemistry Research Group—Determination of four selected mosquito insecticides and a synergist in water using liquid-liquid extraction and gas chromatography/mass spectrometry

A method of analysis and quality-assurance practices were developed for the determination of four mosquito insecticides (malathion, metho-prene, phenothrin, and resmethrin) and one synergist (piperonyl butoxide) in water. The analytical method uses liquid-liquid extraction (LLE) and gas chromatography/mass spectrometry (GC/MS). Good precision and accuracy were demonstrated in reagent water, urban surface water, and ground water. The mean accuracies as percentages of the true compound concentrations from water samples spiked at 10 and 50 nanograms per liter ranged from 68 to 171 percent, with standard deviations in concentrations of 27 nanograms per liter or less. The method detection limit for all compounds was 5.9 nanograms per liter or less for 247-milliliter samples. This method is valuable for acquiring information about the fate and transport of these mosquito insecticides and one synergist in water.

Kansas↗

Dissolved organic matter in the deep TALDICE ice core: A nano-UPLC-nano-ESI-HRMS method

Trace organic compounds in deep ice cores supply important paleoclimatic information. Untargeted analyses of dissolved organic matter provide an overview of molecular species in ice samples however, sample volumes usually required for these analyses are generally not available from deep ice cores. Here, we developed an analytical method using a nano-UPLC-nano-ESI-HRMS to detect major molecular species in ice cores. Samples (4 µL) from the TALos Dome Ice CorE (TALDICE), allowed investigating molecular species across a range of depths including during glacial and interglacial periods. We detected 317 chemical species that were tentatively assigned to fatty acids, hydroxy fatty acids and their degradation products (oxo-fatty acids and dicarboxylic acids), as well as oxidation byproducts of isoprene and monoterpenes. These compounds indicate that the main sources of the organic fraction are microbes as well as primary and secondary aerosols. Interglacial samples encompass a wide range of species including compounds from the oxidation of isoprene and monoterpenes as well as unsaturated fatty acids, while the glacial samples contained less diverse species. This difference may be due to decreased temperatures during the glacial period inhibiting terrestrial vegetation growth and increasing the sea ice extent, thereby weakening the emission sources.

Science of the Total Environment↗

Annual changes in seasonal river water temperatures in the eastern and western United States

Changes in river water temperatures are anticipated to have direct effects on thermal habitat and fish population vital rates, and therefore, understanding temporal trends in water temperatures may be necessary for predicting changes in thermal habitat and how species might respond to such changes. However, many investigations into trends in water temperatures use regression methods that assume long-term monotonic changes in temperature, when in fact changes are likely to be nonmonotonic. Therefore, our objective was to highlight the need and provide an example of an analytical method to better quantify the short-term, nonmonotonic temporal changes in thermal habitat that are likely necessary to determine the effects of changing thermal conditions on fish populations and communities. To achieve this objective, this study uses Bayesian dynamic linear models (DLMs) to examine seasonal trends in river water temperatures from sites located in the eastern and western United States, regions that have dramatically different riverine habitats and fish communities. We estimated the annual rate of change in water temperature and found little evidence of seasonal changes in water temperatures in the eastern U.S. We found more evidence of warming for river sites located in the western U.S., particularly during the fall and winter seasons. Use of DLMs provided a more detailed view of temporal dynamics in river thermal habitat compared to more traditional methods by quantifying year-to-year changes and associated uncertainty, providing managers with the information needed to adapt decision making to short-term changes in habitat conditions that may be necessary for conserving aquatic resources in the face of a changing climate.

Upper Colorado River Basin↗

Comparison of enzyme-linked immunosorbent assay and gas chromatography procedures for the detection of cyanazine and metolachlor in surface water samples

Enzyme-linked immunosorbent assay (ELISA) data from surface water reconnaissance were compared to data from samples analyzed by gas chromatography for the pesticide residues cyanazine (2-[[4-chloro-6-(ethylamino)-l,3,5-triazin-2-yl]amino]-2-methylpropanenitrile ) and metolachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide). When ELISA analyses were duplicated, cyanazine and metolachlor detection was found to have highly reproducible results; adjusted R2s were 0.97 and 0.94, respectively. When ELISA results for cyanazine were regressed against gas chromatography results, the models effectively predicted cyanazine concentrations from ELISA analyses (adjusted R2s ranging from 0.76 to 0.81). The intercepts and slopes for these models were not different from 0 and 1, respectively. This indicates that cyanazine analysis by ELISA is expected to give the same results as analysis by gas chromatography. However, regressing ELISA analyses for metolachlor against gas chromatography data provided more variable results (adjusted R2s ranged from 0.67 to 0.94). Regression models for metolachlor analyses had two of three intercepts that were not different from 0. Slopes for all metolachlor regression models were significantly different from 1. This indicates that as metolachlor concentrations increase, ELISA will over- or under-estimate metolachlor concentration, depending on the method of comparison. ELISA can be effectively used to detect cyanazine and metolachlor in surface water samples. However, when detections of metolachlor have significant consequences or implications it may be necessary to use other analytical methods.

Journal of Agricultural and Food Chemistry↗

Catalog of Mount St. Helens 2004 - 2005 tephra samples with major- and trace-element geochemistry

This open-file report presents a catalog of information about 135 ash samples along with geochemical analyses of bulk ash, glass and individual mineral grains from tephra deposited as a result of volcanic activity at Mount St. Helens, Washington, from October 1, 2004 until August 15, 2005. This data, in conjunction with that in a companion report on 2004-2007 Mount St. Helens dome samples by Thornber and others (2008a) are presented in support of the contents of the U.S. Geological Survey Professional Paper 1750 (Sherrod and others, ed., 2008). Readers are referred to appropriate chapters in USGS Professional Paper 1750 for detailed narratives of eruptive activity during this time period and for interpretations of sample characteristics and geochemical data presented here. All ash samples reported herein are currently archived at the David A. Johnston Cascades Volcano Observatory in Vancouver, Washington. The Mount St. Helens 2004?2005 Tephra Sample Catalogue along with bulk, glass and mineral geochemistry are tabulated in 6 worksheets of the accompanying Microsoft Excel file, of2008-1131.xls. Samples in all tables are organized by collection date. Table 1 is a detailed catalog of sample information for tephra deposited downwind of Mount St. Helens between October 1, 2004 and August 18, 2005. Table 2 provides major- and trace-element analyses of 8 bulk tephra samples collected throughout that interval. Major-element compositions of 82 groundmass glass fragments, 420 feldspar grains, and 213 mafic (clinopyroxene, amphibole, hypersthene, and olivine) mineral grains from 12 ash samples collected between October 1, 2004 and March 8, 2005 are presented in tables 3 through 5. In addition, trace-element abundances of 198 feldspars from 11 ash samples (same samples as major-element analyses) are provided in table 6. Additional mineral and bulk ash analyses from 2004 and 2005 ash samples are published in chapters 30 (oxide thermometry; Pallister and others, 2008), 32 (amphibole major elements; Thornber and others, 2008b) and 37 (210Pb; 210Pb/226Pa; Reagan and others, 2008) of U.S. Geological Survey Professional Paper 1750 (Sherrod and others, 2008). A brief overview of sample collection methods is given below as an aid to deciphering the tephra sample catalog. This is followed by an explanation of the categories of sample information (column headers) in table 1. A summary of the analytical methods used to obtain the geochemical data in this report introduces the presentation of major- and trace-element geochemistry of Mount St. Helens 2004-2005 tephra samples in tables 2-6. Rhyolite glass standard analyses are reported (Appendix 1) to demonstrate the accuracy and precision of similar glass analyses presented herein.

Washington↗

Sediment and chemical contaminant loads in tributaries to the Anacostia River, Washington, District of Columbia, 2016–17

A study was conducted by the U.S. Geological Survey (USGS) in cooperation with the Washington, D.C., Department of Energy & Environment to estimate the loads of suspended-sediment-bound chemical compounds in five gaged tributaries and four ungaged tributaries of the Anacostia River (known locally as “Lower Anacostia River”) in Washington, D.C. Tributaries whose discharge is measured by the USGS are the Northeast and Northwest Branches of the Anacostia River, referred to in this report as “Northeast Branch” (NEB) and “Northwest Branch” (NWB), respectively; Watts Branch (WB); and Hickey Run (HR). A USGS streamflow-gaging station was established in 2016 on Beaverdam Creek (known locally as “Lower Beaverdam Creek” [LBDC]) to support this study. The ungaged streams studied include Nash Run; Pope Branch; an unnamed stream at Fort DuPont, referred to in this report as “Fort DuPont Creek”; and an unnamed stream at Fort Stanton, referred to in this report as “Fort Stanton Creek.” The gaged streams were sampled during four to five storms and two low-flow events during January, March, May, and July 2017. The ungaged streams were sampled during one storm and one low-flow event during July 2017. Storm sampling involved collecting large-volume (60- to 70-liter) composite samples, then removing sediment by filtration in the laboratory. Low-flow samples were obtained by filtering streamwater directly in the field. Continuously recording data sondes were deployed throughout the study to measure turbidity and other water-quality characteristics. During sampling, multiple discrete samples of streamwater were collected to determine suspended-sediment concentration (SSC) and particulate organic carbon (POC) concentration. Shortly after each storm, bed sediment was collected for chemical analysis. Sediment samples were analyzed for 209 polychlorinated biphenyl (PCB) congeners; 35 polyaromatic hydrocarbon (PAH) compounds, including 20 nonalkylated and 15 alkylated species; and 20 organochlorine pesticide (OP) compounds. Sediment from one storm was analyzed for 23 metals. Relations were developed among turbidity, discharge, and measured SSC by using multiple linear regression of log-transformed data. These relations were used to estimate SSC from continuous records of discharge and turbidity and were subsequently used to estimate sediment loads for the 2017 calendar year. USGS continuous records of turbidity in NEB, NWB, Watts Branch, and Hickey Run were available for 2013–17, which allowed sediment loads to be calculated for these years. Sediment loads for the ungaged streams were estimated by using loads measured in Watts Branch adjusted on the basis of stream-basin areas. Sediment loads for 2017 total 3.10×10 7 kilograms (kg), with 1.02×107 kg (33 percent of total) from the NEB, 1.55×10 7 kg (50 percent) from the NWB, 4.45×10 6 kg (14 percent) from LBDC, 5.62×10 5 kg (2 percent) from Watts Branch, and 2.82×10 5 kg (1 percent) from Hickey Run. Sediment yields were highest from NWB and LBDC (3.13×10 5 kilograms per year per square mile [kg/yr/mi 2 ] and 3.01 kg/yr/mi 2 , respectively). As a result of gaps in turbidity and discharge data, the load for LBDC reported here was calculated from measurements representing only 88 percent of the year (2017), and thus underestimates the actual load. All other gaged tributaries had datasets covering 100 percent of the year and are considered to fully represent actual loads. Estimated sediment loads for the ungaged streams during 2017 total 3.5×10 5 kg, with 1.2×10 5 kg from Nash Run, 6.2×10 4 kg from Pope Branch, 1.1×10 5 kg from Fort DuPont Creek, and 5.6×10 4 kg from Fort Stanton Creek. Concentrations of PCBs, PAHs, and chlorinated pesticides in streamwater are presented for stormflow and low-flow conditions. Average concentrations (in stormflow and low-flow samples) of total PCBs (sum of all congeners, including coelutions) are 5.9 micrograms per kilogram (µg/kg) for NEB, 6.6 µg/kg for NWB, 130 µg/kg for LBDC, 34 µg/kg for Watts Branch, and 69 µg/kg for Hickey Run. Average concentrations of total PAHs (tPAH) (total of nonalkylated and alkylated species) are 2,000 µg/kg for NEB, 3,300 µg/kg for NWB, 2,200 µg/kg for LBDC, 2,400 µg/kg for Watts Branch, and 18,000 µg/kg for Hickey Run. tPAH concentrations among the ungaged streams were highest in Nash Run (5,500 µg/kg); concentrations in the other ungaged streams were less than (<) 700 µg/kg. The general magnitude of tPCB and tPAH concentrations in streamwater samples was low-flow samples greater than (>) stormflow samples greater than or equal to (≥) bed-sediment samples. PCB congener profiles in the three types of samples were nearly identical in each stream and were similar in all streams except for LBDC, where the dominant PCBs shifted to the lighter di- through tetra- homologs. LBDC showed higher tPCB concentrations and a distinct congener profile from the other streams. The similarity in congener makeup supported that averaging PCB concentrations in stormflow and low-flow samples was appropriate for calculating chemical loads. Loads of tPCB, tPAH (total of alkylated and nonalkylated forms), and pesticides were estimated for each stream by multiplying average contaminant concentrations by the respective sediment loads. Total PCB loads for 2017 were estimated to be 820 grams (g) with 8 percent (60 g) from NEB, 12 percent (95 g) from NWB, 75 percent (590 g) from LBDC, 3 percent (25 g) from Watts Branch, and 2.5 percent (19 g) from Hickey Run. PCB toxicity totaled 3.8×10 −3 µg/kg, with the largest contribution (47 percent) derived from LBDC. Total PAH loads (sum of alkylated and nonalkylated forms) for 2017 were estimated to be 89,000 g, with 23 percent (20,000 g) from NEB, 59 percent (52,000 g) from NWB, 11 percent (9,800 g) from LBDC, 2 percent (1,400 g) from Watts Branch, and 6 percent (5,200 g) from Hickey Run. These results indicate that the largest contributor (75 percent) of PCBs to the Anacostia River is LBDC, although it contributes only 15 percent of the sediment and its basin area represents only 10 percent of the area of the Anacostia River watershed. The majority of the PAH load originates from NWB (59 percent of total) and NEB (22 percent). The ungaged tributaries contribute extremely small loads of PCBs and PAHs, totaling 8.1 g and 765 kg, respectively. More than 94 percent of the total load from the ungaged tributaries is derived from the Nash Run Basin. Various organochlorine pesticides were present in suspended and bed sediment from all gaged and ungaged tributaries; however, elevated detection levels associated with the analytical methods resulted in numerous unquantifiable concentrations in the suspended-sediment samples. Only the pesticide chlordane was found in measurable concentrations in all gaged tributaries. As a result, in this report, a combination of analytical data from suspended-sediment and bed-sediment samples was used to estimate the maximum pesticide loading for each tributary. Chlordane was the principal compound present in the gaged tributaries; the highest average concentration (average of stormflow and low-flow samples from each stream) was 62 µg/kg in sediment from Watts Branch. Chlordane loads for 2017 totaled 1,100 g, of which 7 percent (430 g) was from NEB, 28 percent (320 g) was from NWB, 28 percent (310 g) was from LBDC, 5 percent (56 g) was from Watts Branch, and 1 percent (11 g) was from Hickey Run. Chlordane was not present in suspended or bed sediment from any of the ungaged tributaries. Loads of the other pesticides were estimated by using the highest concentration measured in the combined suspended-sediment and bed-sediment data for each stream. Notable loads include dieldrin (860 g from NWB), methoxychlor (205 g from LBDC), endrin aldehyde (150 g from NWB), and 4,4-DDT (79 g from Watts Branch). Compared with pesticide loads from the gaged streams, those from the ungaged streams were minimal, with only the Pope Branch contribution exceeding 1 gram per year for 4,4-DDE (1.05 g) and 4,4’-DDT (1.3 g). The results of this study show that the dominant source of PCBs and chlordane is LBDC, despite its relatively small basin area. PAHs are ubiquitous throughout the study area, with the largest sources being NEB and NWB; this finding is a result of the large sediment load originating from these basins. The small, ungaged streams supply only minimal PCB and PAH loads, with Nash Run being the largest contributor.

District of Columbia↗

Incorporating temporal variation in seabird telemetry data: time variant kernel density models

A key component of the Mid-Atlantic Baseline Studies project was tracking the individual movements of focal marine bird species (Red-throated Loon [Gavia stellata], Northern Gannet [Morus bassanus], and Surf Scoter [Melanitta perspicillata]) through the use of satellite telemetry. This element of the project was a collaborative effort with the Department of Energy (DOE), Bureau of Ocean Energy Management (BOEM), the U.S. Fish and Wildlife Service (USFWS), and Sea Duck Joint Venture (SDJV), among other organizations. Satellite telemetry is an effective and informative tool for understanding individual animal movement patterns, allowing researchers to mark an individual once, and thereafter follow the movements of the animal in space and time. Aggregating telemetry data from multiple individuals can provide information about the spatial use and temporal movements of populations. Tracking data is three dimensional, with the first two dimensions, X and Y, ordered along the third dimension, time. GIS software has many capabilities to store, analyze and visualize the location information, but little or no support for visualizing the temporal data, and tools for processing temporal data are lacking. We explored several ways of analyzing the movement patterns using the spatiotemporal data provided by satellite tags. Here, we present the results of one promising method: time-variant kernel density analysis (Keating and Cherry, 2009). The goal of this chapter is to demonstrate new methods in spatial analysis to visualize and interpret tracking data for a large number of individual birds across time in the mid-Atlantic study area and beyond. In this chapter, we placed greater emphasis on analytical methods than on the behavior and ecology of the animals tracked. For more detailed examinations of the ecology and wintering habitat use of the focal species in the midAtlantic, see Chapters 20-22.

Report↗

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-Comparison of a nitric acid in-bottle digestion procedure to other whole-water digestion procedures

A hydrochloric acid in-bottle digestion procedure is used to partially digest wholewater samples prior to determining recoverable elements by various analytical methods. The use of hydrochloric acid is problematic for some methods of analysis because of spectral interference. The inbottle digestion procedure has been modified to eliminate such interference by using nitric acid instead of hydrochloric acid in the digestion. Implications of this modification are evaluated by comparing results for a series of synthetic whole-water samples. Results are also compared with those obtained by using U.S. Environmental Protection Agency (1994) (USEPA) Method 200.2 total-recoverable digestion procedure. Percentage yields that use the nitric acid inbottle digestion procedure are within 10 percent of the hydrochloric acid in-bottle yields for 25 of the 26 elements determined in two of the three synthetic whole-water samples tested. Differences in percentage yields for the third synthetic whole-water sample were greater than 10 percent for 16 of the 26 elements determined. The USEPA method was the most rigorous for solubilizing elements from particulate matter in all three synthetic whole-water samples. Nevertheless, the variability in the percentage yield by using the USEPA digestion procedure was generally greater than the in-bottle digestion procedure, presumably because of the difficulty in controlling the digestion conditions accurately.

Open-File Report↗

Probabilistic methodology for estimation of undiscovered petroleum resources in play analysis of the United States

A geostochastic system called FASPF was developed by the U.S. Geological Survey for their 1989 assessment of undiscovered petroleum resources in the United States. FASPF is a fast appraisal system for petroleum play analysis using a field-size geological model and an analytic probabilistic methodology. The geological model is a particular type of probability model whereby the volumes of oil and gas accumulations are modeled as statistical distributions in the form of probability histograms, and the risk structure is bilevel (play and accumulation) in terms of conditional probability. The probabilistic methodology is an analytic method derived from probability theory rather than Monte Carlo simulation. The resource estimates of crude oil and natural gas are calculated and expressed in terms of probability distributions. The probabilistic methodology developed by the author is explained. The analytic system resulted in a probabilistic methodology for play analysis, subplay analysis, economic analysis, and aggregation analysis. Subplay analysis included the estimation of petroleum resources on non-Federal offshore areas. Economic analysis involved the truncation of the field size with a minimum economic cutoff value. Aggregation analysis was needed to aggregate individual play and subplay estimates of oil and gas, respectively, at the provincial, regional, and national levels. ?? 1992 Oxford University Press.

Nonrenewable Resources↗

Occurrence, distribution, and concentration of hydrocarbons in and near the Shell Valley Aquifer, North Dakota

Water samples from 27 wells completed in and near the Shell Valley aquifer were analyzed for benzene, toluene, ethylbenzene, and xylene (BTEX), polynuclear aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB), and pentachlorophenol (PCP) using the enzyme-linked immunoassay method. The analyses indicated the presence of PAH, PCB, and PCP in the study area. However, an individual compound at a high concentration or many compounds at low concentrations could cause the detections. Therefore, selected samples were analyzed using the gas chromatography (GC) method, which can detect individual compounds and determine the concentrations of those compounds. Concentrations for all compounds detected using the GC method were less than the minimum reporting levels (MRLs) for each constituent, indicating numerous compounds at low concentrations probably caused the immunoassay detections. The GC method also can detect compounds other than BTEX, PAH, PCB, and PCP. Concentrations for 81 of the additional compounds were determined and were less than the MRLs. Four compounds that could not be quantified accurately using the requested analytical methods also were detected. Acetone was detected in 4 of the 27 wells, 2-butanone was detected in 3 of the 27 wells, prometon was detected in 1 of the 27 wells, and tetrahydrofuran was detected in 9 of the 27 wells. Acetone, 2-butanone, and tetrahydrofuran probably leached from the polyvinyl chloride (PVC) pipe and joint glue and probably are not contaminants from the aquifer. Prometon is a herbicide that controls most annual and many perennial broadleaf weeds and primarily is used on roads and railroad tracks. The one occurrence of prometon could be caused by overspraying for weeds.

North Dakota↗

Determination of heat purgeable and ambient purgeable volatile organic compounds in water by gas chromatography/mass spectrometry

Two new analytical methods have been developed by the U.S. Geological Survey (USGS) National Water Quality Laboratory (NWQL) that allow the determination of 37 heat purgeable volatile organic compounds (VOCs) (USGS Method O-4437-16 [NWQL Laboratory Schedule (LS) 4437]) and 49 ambient purgeable VOCs (USGS Method O-4436-16 [NWQL LS 4436]) in unfiltered water. This report documents the procedures and initial performance of both methods. The compounds chosen for inclusion in the methods were determined as having high priority by the USGS National Water-Quality Assessment (NAWQA) Program. Both methods use a purge-and-trap technique with gas chromatography/mass spectrometry. The compounds are extracted from the sample by bubbling helium through a 25-milliliter sample. For the polar and less volatile compounds, the sample is heated at 60 degrees Celsius, whereas the less polar and more volatile compounds are purged using a separate analytical procedure at ambient temperature. The compounds are trapped on a sorbent trap, desorbed into a gas chromatograph/mass spectrometer for separation, and then identified and quantified. Sample preservation is recommended for both methods by adding a 1:1 solution of hydrochloric acid (HCl [1:1]) to water samples to adjust the pH to 2. Analysis within 14 days from sampling is recommended. The heat purgeable method (USGS Method O-4437-16) operates with the mass spectrometer in the simultaneous full scan/selected ion monitoring mode. This method supersedes USGS Method O-4024-03 (NWQL LS 4024). Method detection limits (MDLs) for fumigant compounds 1,2-dibromoethane, 1,2-dichloropropane, 1,2,3-trichloropropane, chloropicrin, and 1,2-dibromo-3-chloropropane range from 0.002 to 0.010 microgram per liter (µg/L). The MDLs for all remaining heat purgeable VOCs range from 0.006 µg/L for tert -butyl methyl ether to 3 µg/L for alpha -terpineol. Calculated holding times indicate that 36 of the 37 heat purgeable VOCs are stable for a minimum of 14 days preserved with HCl (1:1) to pH 2, and many are stable longer. Acrolein was retained in the method validation and initial method implementation and subsequently deleted because of instability and inconsistent performance. 2-Chloromethyl oxirane, methyl oxirane, and oxirane were tested using this method, but the compounds degraded quickly with the HCl (1:1) used for microbial preservation. The ambient purgeable method, USGS Method O-4436-16, operates with the mass spectrometer in the full scan mode. This method is a modification of USGS Method O-4127-96 (NWQL LS 2020). Several compounds were retained from Method O-4127-96 and will continue to be determined in Method O-4436-16. Eleven high priority compounds were added. MDLs for the high priority compounds range from 0.007 µg/L for 2,2-dichloro-1,1,1-trifluoroethane to 0.04 µg/L for 1,2,3,4-tetrahydronaphthalene and 1,3-butadiene. Historical MDLs for the compounds retained from Method O-4127-96 range from 0.009 µg/L for trans -1,2-dichloroethene to 0.1 µg/L for bromomethane. The calculated holding times for the compounds indicate the majority of the compounds are stable for a minimum of 14 days, or longer, at pH 2 with HCl (1:1) preservation. Four semivolatile compounds, 1,2-dimethylnaphthalene, 1,6-dimethylnaphthalene, 2,6-di- tert -butyl phenol, and 2-chloronapthalene, were tested and deleted from the method due to poor performance. Benzyl chloride was tested and deleted due to instability.

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