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At least 199 records · Page 11Linked to original sources

Selected trace metals and organic compounds and bioavailability of selected organic compounds in soils, Hackberry Flat, Tillman County, Oklahoma, 1994-95

In 1995 the Oklahoma Department of Wildlife Conservation acquired a drained wetland in southwest Oklahoma known as Hackberry Flat. Following restoration by Wildlife Conservation the wetland will be used by migratory birds and waterfowl. If naturally occurring trace metals and residual organic compounds from agriculture and industry were present, they may have posed a potential biohazard and were a concern for Wildlife Conservation. The U. S. Geological Survey, in cooperation with Wildlife Conservation and the Oklahoma Geological Survey, examined the soils of Hackberry Flat to determine trace metal concentrations, presence of selected organic compounds, and the bioavailability of selected organic compounds in the soils. The purpose of this report is to present the data that establish the baseline concentrations of selected trace metals and organic compounds in the soils of Hackberry Flat prior to wetland restoration. Sampling and analysis were performed using two approaches. One was to collect soil samples and analyze the composition with standard laboratory practices. The second exposed composite soils samples to organic-free water and a semipermeable membrane device that mimics an organism and then analyzed the device. Ten soil samples were collected in 1994 to be analyzed for trace metals, organochlorine pesticides, and polychlorinated biphenyls. Soil samples tested for bioavailability of selected organic compounds were collected in 1995. Most of the 182 soil samples collected were from the center of every 40-acre quarter-quarter section owned by the Wildlife Conservation. The samples were grouped by geographical area with a maximum of 16 sample sites per group. Concentrations of most selected trace metals measured from soils in Hackberry Flat are within the range of mean concentrations measured in cultivated soils within the United States. Organochlorine pesticides, polychlorinated biphenyls, and polyaromatic hydrocarbons were not found at concentrations above the analytical detection levels and, if present, in the soil samples are at concentrations below the detection level of the analytical method used. Organochlorine pesticides, total polychlorinated biphenyls, and polyaromatic hydrocarbons were not detected in any of the semipermeable membrane devices at the analytical detection levels.

Oklahoma↗

Occurrence of selected pharmaceuticals, personal-care products, organic wastewater compounds, and pesticides in the lower Tallapoosa River watershed near Montgomery, Alabama, 2005

Synthetic and natural organic compounds derived from agricultural operations, residential development, and treated and untreated sanitary and industrial wastewater discharges can contribute contaminants to surface and ground waters. To determine the occurrence of these compounds in the lower Tallapoosa River watershed, Alabama, new laboratory methods were used that can detect human and veterinary antibiotics; pharmaceuticals; and compounds found in personal-care products, food additives, detergents and their metabolites, plasticizers, and other industrial and household products in the environment. Well-established methods for detecting 47 pesticides and 19 pesticide degradates also were used. In all, 186 different compounds were analyzed by using four analytical methods. The lower Tallapoosa River serves as the water-supply source for more than 100,000 customers of the Montgomery Water Works and Sanitary Sewer Board. Source-water protection is a high priority for the Board, which is responsible for providing safe drinking water. The U.S. Geological Survey, in cooperation with the Montgomery Water Works and Sanitary Sewer Board, conducted this study to provide baseline data that could be used to assess the effects of agriculture and residential development on the occurrence of selected organic compounds in the lower Tallapoosa River watershed. Twenty samples were collected at 10 sites on the Tallapoosa River and its tributaries. Ten samples were collected in April 2005 during high base streamflow, and 10 samples were collected in October 2005 when base streamflow was low. Thirty-two of 186 compounds were detected in the lower Tallapoosa River watershed. Thirteen compounds, including atrazine, 2-chloro-4-isopropylamino-6-amino-s-triazine (CIAT), hexazinone, metalaxyl, metolachlor, prometryn, prometon, simazine, azithromycin, oxytetracycline, sulfamethoxazole, trimethoprim, and tylosin, had measurable concentrations above their laboratory reporting levels. Concentrations were estimated for an additional 19 compounds that were detected below their laboratory reporting levels. The two most frequently detected compounds were the pesticides atrazine (19 of 20 samples) and simazine (13 of 20 samples). Tylosin, a veterinary antibiotic, was detected in 8 of 20 samples. Other compounds frequently detected at very low concentrations included CIAT and hexazinone (a degradate of atrazine and a pesticide, respectively); camphor (derived from personal-care products or flavorants), para-cresol (various uses including solvent, wood preservative, and in household cleaning products), and N,N-diethyl-m-toluamide (DEET, an insect repellent).

Alabama↗

Use of predictive models and rapid methods to nowcast bacteria levels at coastal beaches

The need for rapid assessments of recreational water quality to better protect public health is well accepted throughout the research and regulatory communities. Rapid analytical methods, such as quantitative polymerase chain reaction (qPCR) and immunomagnetic separation/adenosine triphosphate (ATP) analysis, are being tested but are not yet ready for widespread use. Another solution is the use of predictive models, wherein variable(s) that are easily and quickly measured are surrogates for concentrations of fecal-indicator bacteria. Rainfall-based alerts, the simplest type of model, have been used by several communities for a number of years. Deterministic models use mathematical representations of the processes that affect bacteria concentrations; this type of model is being used for beach-closure decisions at one location in the USA. Multivariable statistical models are being developed and tested in many areas of the USA; however, they are only used in three areas of the Great Lakes to aid in notifications of beach advisories or closings. These “operational” statistical models can result in more accurate assessments of recreational water quality than use of the previous day's Escherichia coli (E. coli) concentration as determined by traditional culture methods. The Ohio Nowcast, at Huntington Beach, Bay Village, Ohio, is described in this paper as an example of an operational statistical model. Because predictive modeling is a dynamic process, water-resource managers continue to collect additional data to improve the predictive ability of the nowcast and expand the nowcast to other Ohio beaches and a recreational river. Although predictive models have been shown to work well at some beaches and are becoming more widely accepted, implementation in many areas is limited by funding, lack of coordinated technical leadership, and lack of supporting epidemiological data.

Aquatic Ecosystem Health & Management↗

What is eDNA method standardization and why do we need it?

The rapid advancement of environmental DNA ( eDNA ) science in the past two decades has inspired a concomitant growth in the development of eDNA sampling and analytical methods. However, these methods are often developed by individual laboratories or institutions, which can isolate protocols within programmes, agencies or regions and prevent the beneficial exchange of data and ideas. Recent efforts to advance national and international coordination have resulted in a groundswell of standardisation efforts, but there is still considerable confusion around the role of formal standards for regulatory or research applications. With this commentary, we hope to provide clarity on the terminology used in standardisation discussions, including the differences between formal standards and best practice guidelines. Additionally, we discuss how eDNA method choice may be informed by environmental management scenarios and review examples of formal eDNA method standards being used to inform management action. The eDNA community now has an opportunity to develop a roadmap for method development to help close standardisation gaps, advance eDNA method adoption and accelerate our ability to monitor biological life at the scales our current environmental challenges demand.

Metabarcoding and Metagenomics↗

Methods of analysis by the U.S. Geological Survey Organic Geochemistry Research Group--Update and additions to the determination of chloroacetanilide herbicide degradation compounds in water using high-performance liquid chromatography/mass spectrometry

An analytical method using high-performance liquid chromatography/mass spectrometry (HPLC/MS) was developed by the U.S. Geological Survey in 1999 for the analysis of selected chloroacetanilide herbicide degradation compounds in water. These compounds were acetochlor ethane sulfonic acid (ESA), acetochlor oxanilic acid (OXA), alachlor ESA, alachlor OXA, metolachlor ESA, and metolachlor OXA. The HPLC/MS method was updated in 2000, and the method detection limits were modified accordingly. Four other degradation compounds also were added to the list of compounds that can be analyzed using HPLC/MS; these compounds were dimethenamid ESA, dimethenamid OXA, flufenacet ESA, and flufenacet OXA. Except for flufenacet OXA, good precision and accuracy were demonstrated for the updated HPLC/MS method in buffered reagent water, surface water, and ground water. The mean HPLC/MS recoveries of the degradation compounds from water samples spiked at 0.20 and 1.0 g/L (microgram per liter) ranged from 75 to 114 percent, with relative standard deviations of 15.8 percent or less for all compounds except flufenacet OXA, which had relative standard deviations ranging from 11.3 to 48.9 percent. Method detection levels (MDL's) using the updated HPLC/MS method varied from 0.009 to 0.045 ?g/L, with the flufenacet OXA MDL at 0.072 g/L. The updated HPLC/MS method is valuable for acquiring information about the fate and transport of the parent chloroacetanilide herbicides in water.

Open-File Report↗

Methods of analysis by the U.S. Geological Survey Organic Geochemistry Research Group: Determination of acetamide herbicides and their degradation products in water using online solid-phase extraction and liquid chromatography/mass spectrometry

An analytical method for the determination of 6 acetamide herbicides (acetochlor, alachlor, dimethenamid, flufenacet, metolachlor, and propachlor) and 16 of their degradation products in natural water samples using solid-phase extraction and liquid chromatography/mass spectrometry is described in this report. Special consideration was given during the development of the method to prevent the formation of degradation products during the analysis. Filtered water samples were analyzed using octadecylsilane as the solid-phase extraction media on online automated equipment followed by liquid chromatography/mass spectrometry. The method uses only 10 milliliters of sample per injection. Three different water-sample matrices, a reagent-water, a ground-water, and a surface-water sample spiked at 0.10 and 1.0 microgram per liter, were analyzed to determine method performance. Method detection limits ranged from 0.004 to 0.051 microgram per liter for the parent acetamide herbicides and their degradation products. Mean recoveries for the acetamide compounds in the ground- and surface-water samples ranged from 62.3 to 117.4 percent. The secondary amide of acetochlor/metolachlor ethanesulfonic acid (ESA) was recovered at an average rate of 43.5 percent. The mean recoveries for propachlor and propachlor oxanilic acid (OXA) were next lowest, ranging from 62.3 to 95.5 percent. Mean recoveries from reagent-water samples ranged from 90.3 to 118.3 percent for all compounds. Overall the mean of the mean recoveries of all compounds in the three matrices spiked at 0.10 and 1.0 microgram per liter ranged from 89.9 to 100.7 percent, including the secondary amide of acetochlor/metolachlor ESA and the propachlor compounds. The acetamide herbicides and their degradation products are reported in concentrations ranging from 0.05 to 2.0 micrograms per liter. The upper concentration limit is 2.0 micrograms per liter for all compounds without dilution. With the exception of the secondary amide of acetochlor/metolachlor ESA, good precision and accuracy for the chloroacetanalide herbicides and their degradation compounds were demonstrated for the method in buffered reagent water, ground water, and surface water. The extraction method as used did not optimize the recovery of the secondary amide of acetochlor/metolachlor ESA.

Open-File Report↗

Methods of analysis by the U.S. Geological Survey Organic Geochemistry Research Group--Determination of dissolved isoxaflutole and its sequential degradation products, diketonitrile and benzoic acid, in water using solid-phase extraction and liquid chromatography/tandem mass spectrometry

An analytical method for the determination of isoxaflutole and its sequential degradation products, diketonitrile and a benzoic acid analogue, in filtered water with varying matrices was developed by the U.S. Geological Survey Organic Geochemistry Research Group in Lawrence, Kansas. Four different water-sample matrices fortified at 0.02 and 0.10 ug/L (micrograms per liter) are extracted by vacuum manifold solid-phase extraction and analyzed by liquid chromatography/tandem mass spectrometry using electrospray ionization in negative-ion mode with multiple-reaction monitoring (MRM). Analytical conditions for mass spectrometry detection are optimized, and quantitation is carried out using the following MRM molecular-hydrogen (precursor) ion and product (p) ion transition pairs: 357.9 (precursor), 78.9 (p), and 277.6 (p) for isoxaflutole and diketonitrile, and 267.0 (precursor), 159.0 (p), and 223.1 (p) for benzoic acid. 2,4-dichlorophenoxyacetic acid-d3 is used as the internal standard, and alachlor ethanesulfonic acid-d5 is used as the surrogate standard. Compound detection limits and reporting levels are calculated using U.S. Environmental Protection Agency procedures. The mean solid-phase extraction recovery values ranged from 104 to 108 percent with relative standard deviation percentages ranging from 4.0 to 10.6 percent. The combined mean percentage concentration normalized to the theoretical spiked concentration of four water matrices analyzed eight times at 0.02 and 0.10 ug/L (seven times for the reagent-water matrix at 0.02 ug/L) ranged from approximately 75 to 101 percent with relative standard deviation percentages ranging from approximately 3 to 26 percent for isoxaflutole, diketonitrile, and benzoic acid. The method detection limit (MDL) for isoxaflutole and diketonitrile is 0.003 ug/L and 0.004 ug/L for benzoic acid. Method reporting levels (MRLs) are 0.011, 0.010, and 0.012 ug/L for isoxaflutole, diketonitrile, and benzoic acid, respectively. On the basis of the calculated MRLs and MDLs and evaluation of the signal-to-noise ratios for each compound, the MRLs and MDLs are set at 0.010 and 0.003 ug/L, respectively, for all three compounds.

Techniques and Methods↗

Multiple-method estimation of recharge rates at diverse locations in the North Carolina Coastal Plain, USA

Recharge rates determined at diverse study sites in a shallow, unconfined aquifer differed from one another depending on the analytical method used and on each method's applicability and limitations. Total recharge was quantified with saturated-zone methods using water-table fluctuations at seven sites in North Carolina, USA and using groundwater-age dating at three of the seven sites; at two of the sites, potential recharge was quantified with an unsaturated-zone method using Darcy's law; and at five of the sites, net recharge was quantified with a stream hydrograph-separation method using streamflow-recession curves. Historical mean net recharge was 25 to 69% of the historical total recharge rates. The large disparity is attributed to groundwater losses between recharge and discharge areas, primarily by evapotranspiration and seepage to underlying aquifers. The spatial distribution of historical mean annual total recharge did not vary between landscape units, as suggested in a previous study. Similarly, total recharge did not correlate significantly with mean annual rainfall, mean annual water table depth, or the surficial soil properties of percent clay and bulk density. Total recharge did correlate significantly with the surficial soil properties of percent sand and percent silt. ?? Springer-Verlag 2007.

North Carolina↗

Methods of analysis by the U.S. Geological Survey Organic Geochemistry Research Group: Determination of triazine and phenylurea herbicides and their degradation products in water using solid-phase extraction and liquid chromatography/mass spectrometry

An analytical method for the determination of 7 triazine and phenylurea herbicides and 12 of their degradation products in natural water samples using solid-phase extraction and liquid chromatography/mass spectrometry is presented in this report. Special consideration was given during the development of the method to prevent the formation of degradation products during the analysis. Filtered water samples were analyzed using 0.5 gram graphitized carbon as the solid-phase extraction media followed by liquid chromatography/mass spectrometry. Three different water-sample matrices ground-water, surface-water, and reagent-water samples?spiked at 0.2 and 2.0 micrograms per liter were analyzed. Method detection limits ranged from 0.013 to 0.168 microgram per liter for the parent triazine herbicides and the triazine degradation products. Method detection limits ranged from 0.042 to 0.141 microgram per liter for the parent phenylurea herbicides and their degradation products. Mean recoveries for the triazine compounds in the ground- and surface-water samples generally ranged from 72.6 to 117.5 percent, but deethyl-cyanazine amide was recovered at 140.5 percent. Mean recoveries from the ground- and surface-water samples for the phenylurea compounds spiked at the 2.0-micrograms-per-liter level ranged from 82.1 to 114.4 percent. The mean recoveries for the phenylureas spiked at 0.2-microgram per liter were less consistent, ranging from 87.0 to 136.0 percent. Mean recoveries from reagent-water samples ranged from 87.0 to 109.5 percent for all compounds. The triazine compounds and their degradation products are reported in concentrations ranging from 0.05 to 2.0 micrograms per liter, with the exception of deethylcyanazine and deethylcyanazine amide which are reported at 0.20 to 2.0 micrograms per liter. The phenylurea compounds and their degradation products are reported in concentrations ranging from 0.20 to 2.0 micrograms per liter. The upper concentration limit was 2.0 micrograms per liter for all compounds without dilution.

Open-File Report↗

Using sequential self-calibration method to identify conductivity distribution: Conditioning on tracer test data

An iterative inverse method, the sequential self-calibration method, is developed for mapping spatial distribution of a hydraulic conductivity field by conditioning on nonreactive tracer breakthrough curves. A streamline-based, semi-analytical simulator is adopted to simulate solute transport in a heterogeneous aquifer. The simulation is used as the forward modeling step. In this study, the hydraulic conductivity is assumed to be a deterministic or random variable. Within the framework of the streamline-based simulator, the efficient semi-analytical method is used to calculate sensitivity coefficients of the solute concentration with respect to the hydraulic conductivity variation. The calculated sensitivities account for spatial correlations between the solute concentration and parameters. The performance of the inverse method is assessed by two synthetic tracer tests conducted in an aquifer with a distinct spatial pattern of heterogeneity. The study results indicate that the developed iterative inverse method is able to identify and reproduce the large-scale heterogeneity pattern of the aquifer given appropriate observation wells in these synthetic cases. ?? International Association for Mathematical Geology 2008.

Mathematical Geosciences↗

Characteristics of zircons from volcanic ash-derived tonsteins in Late Permian coal fields of eastern Yunnan, China

Kaolinitic tonsteins of altered synsedimentary volcanic ash-fall origin are well developed in the Late Permian coal-bearing formations of eastern Yunnan Province. Because of their unique origin, wide lateral extent, relatively constant thickness and sharp contacts with enclosing strata, great importance has been attached to these isochronous petrographic markers. In order to compare tonsteins with co-existing, non-cineritic claystones and characterize the individuality of tonsteins from different horizons for coal bed correlation, a semi-quantitative method was developed that is based on statistical analyses of the concentration and morphology of zircons and their spatial distribution patterns. This zircon-based analytical method also serves as a means for reconstructing volcanic ash-fall dispersal patterns. The results demonstrate that zircons from claystones of two different origins (i.e., tonstein and non-cineritic claystone) differ greatly in their relative abundances, crystal morphologies and spatial distribution patterns. Tonsteins from the same area but from different horizons are characterized by their own unique statistical patterns in terms of zircon concentration values and morphologic parameters (crystal length, width and the ratio of these values), thus facilitating stratigraphic correlation. Zircons from the same tonstein horizon also show continuous variation in these statistical patterns as a function of areal distribution, making it possible to identify the main path and direction in which the volcanic source materials were transported by prevailing winds.

International Journal of Coal Geology↗

Methods of analysis by the U.S. Geological Survey Organic Geochemistry Research Group; determination of chloroacetanilide herbicide metabolites in water using high-performance liquid chromatography-diode array detection and high-performance liquid chromatography/mass spectrometry

Analytical methods using high-performance liquid chromatography-diode array detection (HPLC-DAD) and high-performance liquid chromatography/mass spectrometry (HPLC/MS) were developed for the analysis of the following chloroacetanilide herbicide metabolites in water: acetochlor ethanesulfonic acid (ESA), acetochlor oxanilic acid (OXA), alachlor ESA, alachlor OXA, metolachlor ESA, and metolachlor OXA. Good precision and accuracy were demonstrated for both the HPLC-DAD and HPLC/MS methods in reagent water, surface water, and ground water. The mean HPLC-DAD recoveries of the chloroacetanilide herbicide metabolites from water samples spiked at 0.25, 0.50, and 2.0 mg/L (micrograms per liter) ranged from 84 to 112 percent, with relative standard deviations of 18 percent or less. The mean HPLC/MS recoveries of the metabolites from water samples spiked at 0.05, 0.20, and 2.0 mg/L ranged from 81 to 125 percent, with relative standard deviations of 20 percent or less. The limit of quantitation (LOQ) for all metabolites using the HPLC-DAD method was 0.20 mg/L, whereas the LOQ using the HPLC/MS method was 0.05 mg/L. These metabolite-determination methods are valuable for acquiring information about water quality and the fate and transport of the parent chloroacetanilide herbicides in water.

Open-File Report↗

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-Determination of pesticides in water by Carbopak-B solid-phase extraction and high-preformance liquid chromatography

In accordance with the needs of the National Water-Quality Assessment Program (NAWQA), the U.S. Geological Survey has developed and implemented a graphitized carbon-based solid-phase extraction and high-performance liquid chromatographic analytical method. The method is used to determine 41 pesticides and pesticide metabolites that are not readily amenable to gas chromatography or other high-temperature analytical techniques. Pesticides are extracted from filtered environmental water samples using a 0.5-gram graphitized carbon-based solid-phase cartridge, eluted from the cartridge into two analytical fractions, and analyzed using high-performance liquid chromatography with photodiode-array detection. The upper concentration limit is 1.6 micrograms per liter (=B5g/L) for most compounds. Single-operator method detection limits in organic-free water samples ranged from 0.006 to 0.032 =B5g/L= Recoveries in organic-free water samples ranged from 37 to 88 percent. Recoveries in ground- and surface-water samples ranged from 29 to 94 percent. An optional on-site extraction procedure allows for samples to be collected and processed at remote sites where it is difficult to ship samples to the laboratory within the recommended pre-extraction holding time of 7 days.

Open-File Report↗

Analysis of pharmaceutical and other organic wastewater compounds in filtered and unfiltered water samples by gas chromatography/mass spectrometry

Research on the effects of exposure of stream biota to complex mixtures of pharmaceuticals and other organic compounds associated with wastewater requires the development of additional analytical capabilities for these compounds in water samples. Two gas chromatography/mass spectrometry (GC/MS) analytical methods used at the U.S. Geological Survey National Water Quality Laboratory (NWQL) to analyze organic compounds associated with wastewater were adapted to include additional pharmaceutical and other organic compounds beginning in 2009. This report includes a description of method performance for 42 additional compounds for the filtered-water method (hereafter referred to as the filtered method) and 46 additional compounds for the unfiltered-water method (hereafter referred to as the unfiltered method). The method performance for the filtered method described in this report has been published for seven of these compounds; however, the addition of several other compounds to the filtered method and the addition of the compounds to the unfiltered method resulted in the need to document method performance for both of the modified methods. Most of these added compounds are pharmaceuticals or pharmaceutical degradates, although two nonpharmaceutical compounds are included in each method. The main pharmaceutical compound classes added to the two modified methods include muscle relaxants, opiates, analgesics, and sedatives. These types of compounds were added to the original filtered and unfiltered methods largely in response to the tentative identification of a wide range of pharmaceutical and other organic compounds in samples collected from wastewater-treatment plants. Filtered water samples are extracted by vacuum through disposable solid-phase cartridges that contain modified polystyrene-divinylbenzene resin. Unfiltered samples are extracted by using continuous liquid-liquid extraction with dichloromethane. The compounds of interest for filtered and unfiltered sample types were determined by use of the capillary-column gas chromatography/mass spectrometry. The performance of each method was assessed by using data on recoveries of compounds in fortified surface-water, wastewater, and reagent-water samples. These experiments (referred to as spike experiments) consist of fortifying (or spiking) samples with known amounts of target analytes. Surface-water-spike experiments were performed by using samples obtained from a stream in Colorado (unfiltered method) and a stream in New York (filtered method). Wastewater spike experiments for both the filtered and unfiltered methods were performed by using a treated wastewater obtained from a single wastewater treatment plant in New York. Surface water and wastewater spike experiments were fortified at both low and high concentrations and termed low- and high-level spikes, respectively. Reagent water spikes were assessed in three ways: (1) set spikes, (2) a low-concentration fortification experiment, and (3) a high-concentration fortification experiment. Set spike samples have been determined since 2009, and consist of analysis of fortified reagent water for target compounds included for each group of 10 to18 environmental samples analyzed at the NWQL. The low-concentration and high-concentration reagent spike experiments, by contrast, represent a one-time assessment of method performance. For each spike experiment, mean recoveries ranging from 60 to 130 percent indicate low bias, and relative standard deviations (RSDs) less than (<) 30 percent indicate low variability. Of the compounds included in the filtered method, 21 had mean recoveries ranging from 63 to 129 percent for the low-level and high-level surface-water spikes, and had low (<15 percent) RSDs for these spikes. The remaining 21 compounds generally had high bias for the low-level or the high-level spike experiments for surface water [mean recoveries <58 percent or greater than (>)132 percent]. For wastewater spikes, 24 of the compounds included in the filtered method had recoveries ranging from 61 to 130 percent for the low-level and high-level spikes. RSDs were <29 percent for both of these spike experiments for the 24 compounds. The remaining 18 compounds in the filtered method generally had high recoveries (>130 percent) or variable recoveries (RSDs >30 percent) for low-level wastewater spikes, or low recoveries (<60 percent) for high-level wastewater spikes. Of the compounds included in the filtered method, 34 had mean set-spike recoveries between 61 and 126 percent, and RSDs <30 percent. Of the compounds included in the unfiltered method, 17 had mean spike recoveries ranging from 74 to 129 percent and RSDs ranging from 5 to 25 percent for low-level and high-level surface water spikes. The remaining compounds had poor mean recoveries (<60 or >130 percent), or high RSDs (>29 percent) for these spikes. For wastewater, 14 of the compounds included in the unfiltered method had mean recoveries ranging from 62 to 127 percent and RSDs <25 percent for the low-level and high-level spikes. Most of the remaining compounds had high mean recoveries for wastewater (>130 percent), or low mean recoveries (<20 percent) or high RSDs (>33 percent) for the low-level wastewater spikes. Of the compounds found in wastewater, 24 had mean set spike recoveries ranging from 64 to 104 percent and RSDs <30 percent. Separate method detection limits (MDLs) were computed for surface water and wastewater for both the filtered and unfiltered methods. Filtered method MDLs ranged from 0.007 to 0.14 microgram per liter (μg/L) for the surface water matrix and from 0.004 to 0.62 μg/L for the wastewater matrix. Unfiltered method MDLs ranged from 0.014 to 0.33 μg/L for the surface water matrix and from 0.008 to 0.36 μg/L for the wastewater matrix.

Open-File Report↗

Salinity and total dissolved solids measurements for natural waters: An overview and a new salinity method based on specific conductance and water type

The total concentration of dissolved constituents in water is routinely quantified by measurements of salinity or total dissolved solids (TDS). However, salinity and TDS are operationally defined by their analytical methods and are not equivalent for most waters. Furthermore, multiple methods are available to determine salinity and TDS, and these methods have inherent differences. TDS is defined as the mass of anhydrous residue remaining in a sample vessel after evaporation and subsequent oven drying at a defined temperature. Salinity is a measure of the mass of dissolved salts in a given mass of solution. In addition, there are approaches that quantify the total solute (TS) concentration, including gases. The purpose of this study is to develop a proxy method using specific conductance and major-ion water type to reliably predict salinity, TDS, and/or TS. Thus, we compared several methods to calculate salinity, TDS, and TS for 6391 surface water samples and conclude the following: TDS measurements are best suited for studies of anhydrous residue (e.g., evaporites); salinity determined by summing the speciated ion concentrations, termed S ∑spec , is the most comprehensive method to represent the concentration of dissolved constituents in natural waters; and TS determinations are useful if dissolved CO 2 and other gases are of interest. Thus, we utilized S ∑spec to compare differences between the various salinity, TDS, and TS methods, and to develop a new proxy method to predict salinity based on specific conductance (SC) and major ion water type, termed S SC_WT . For the surface waters used in this study, the median difference between TDS and S ∑Spec was between −19% and −24%, depending on the method. The median difference between S SC_WT and S ∑Spec was −2.4% for the samples in this study. The S SC_WT approach is cost effective, rapid, and capable of providing reliable real-time salinity determinations at surface water sites where SC data are available and water type is known.

Applied Geochemistry↗

Comparisons of likelihood and machine learning methods of individual classification

Classification methods used in machine learning (e.g., artificial neural networks, decision trees, and k -nearest neighbor clustering) are rarely used with population genetic data. We compare different nonparametric machine learning techniques with parametric likelihood estimations commonly employed in population genetics for purposes of assigning individuals to their population of origin (&ldquo;assignment tests&rdquo;). Classifier accuracy was compared across simulated data sets representing different levels of population differentiation (low and high F ST ), number of loci surveyed (5 and 10), and allelic diversity (average of three or eight alleles per locus). Empirical data for the lake trout ( Salvelinus namaycush ) exhibiting levels of population differentiation comparable to those used in simulations were examined to further evaluate and compare classification methods. Classification error rates associated with artificial neural networks and likelihood estimators were lower for simulated data sets compared to k -nearest neighbor and decision tree classifiers over the entire range of parameters considered. Artificial neural networks only marginally outperformed the likelihood method for simulated data (0&ndash;2.8% lower error rates). The relative performance of each machine learning classifier improved relative likelihood estimators for empirical data sets, suggesting an ability to &ldquo;learn&rdquo; and utilize properties of empirical genotypic arrays intrinsic to each population. Likelihood-based estimation methods provide a more accessible option for reliable assignment of individuals to the population of origin due to the intricacies in development and evaluation of artificial neural networks. In recent years, characterization of highly polymorphic molecular markers such as mini- and microsatellites and development of novel methods of analysis have enabled researchers to extend investigations of ecological and evolutionary processes below the population level to the level of individuals (e.g., Bowcock et al. 1994 ; Estoup and Angers 1998 ; Jarne and Lagoda 1996 ). Analyses of individual-based genotypic information could substantially improve our understanding of evolutionary phenomena and contribute to effective management of natural populations (review in Bernatchez and Duchesne 2000 ). The use of individual-based methods remained largely unexplored in animal populations until recently due to a lack of highly polymorphic markers ( Bernatchez and Duchesne 2000 ; Smouse and Chevillon 1998 ). Traditional analytical methods in population genetics rely almost exclusively on descriptors of genetic characterizations of populations ( Bernatchez and Duchesne 2000 ) and not on individual genotypes. &ldquo;Assignment tests&rdquo; are designed to determine population membership for individuals. One particular application based on a likelihood estimate (LE) was introduced by Paetkau et al. (1995 ; see also V&aacute;squez-Dom&iacute;nguez et al. 2001) to assign an individual to the population of origin on the basis of multilocus genotype and expectations of observing this genotype in each potential source population. The LE approach can be implemented statistically in a Bayesian framework as a convenient way to evaluate hypotheses of plausible genealogical relationships (e.g., that an individual possesses an ancestor in another population) ( Dawson and Belkhir 2001 ; Pritchard et al. 2000 ; Rannala and Mountain 1997 ). Other studies have evaluated the confidence of the assignment ( Almudevar 2000 ) and characteristics of genotypic data (e.g., degree of population divergence, number of loci, number of individuals, number of alleles) that lead to greater population assignment ( Bernatchez and Duchesne 2000 ; Cornuet et al. 1999 ; Haig et al. 1997 ; Shriver et al. 1997; Smouse and Chevillon 1998 ). Main statistical and conceptual differences between methods leading to the use of an assignment test are given in, for example, Cornuet et al. (1999) and Rosenberg et al. (2001) . However, the relative power of those tests has certainly not been fully appreciated and empirical comparisons are scarce ( Eldridge et al. 2001 ). Assignment tests can also be considered as surrogates at the individual level (sensu Hansen et al. 2001a ) for other statistical tools developed earlier, such as mixed-stock analysis (e.g., Pella and Masuda 2001 ; Pella and Milner 1987 ). Detailed theoretical comparison of the interests and limitations of both methods are still lacking, but empirical studies have revealed correlations between outputs of methods ( Knutsen et al. 2001 ; Potvin and Bernatchez 2001 ). Assignment tests have been widely used in different applications, including determination of degree of population differentiation or to establish the relationship among individuals within and among various taxonomic groupings (e.g., Bogdanowicz et al. 1997 ; Koskinen et al. 2001 ; Marshall et al. 2000 ; M&uuml;ller 2000 ; Neraas and Spruell 2001 ; Nielsen et al. 2001b ; Polzhien et al. 2000 ; Primmer et al. 1999 ; Roeder et al. 2001 ; Roques et al. 1999 ; Schulte-Hostedde et al. 2001 ; Sefc et al. 2000 ; Spidle et al. 2001 ; V&aacute;squez-Dom&iacute;nguez et al. 2001 ), including hybrids (e.g., Beaumont et al. 2001 ; Congiu et al. 2001 ; Randi et al. 2001 ), introgressed individuals (e.g., Martinez et al. 2001 ; Randi and Lucchini 2002 ), and ecotypes (e.g., Taylor et al. 2000 ). Applications of assignment tests also include [human] forensics (e.g., Evett and Weir 1998 ; Primmer et al. 2000 ), identification and/or source of dispersers (e.g., Davies et al. 1999 ; Eldridge et al. 2001 ; Galbusera et al. 2000 ; Petersson et al. 2001 ; Tsutsui et al. 2001 ; Vasem&auml;gi et al. 2001), phylogeographical analyses (e.g., King et al. 2001 ; Zeisset and Beebee 2001 ), and the evaluation of the contribution of stocked individuals to natural populations (e.g., Fritzner et al. 2001 ; Hansen et al. 2000 , 2001b ) and of supportive breeding programs ( Nielsen et al. 2001a ; Olsen et al. 2000 ). Fish are among the organisms that have received considerable attention using such tools (see Hansen et al. [2001a] for a review). Moreover, these techniques are now used for profiles of traits outside the limited scope of population genetics ( Thorrold et al. 2001 ). Methods of classification vary widely based on several criteria (e.g., Jain et al. 2000 ) ( Figure 1 ). Two basic classification processes are traditionally recognized in machine learning: supervised classifiers and unsupervised classifiers ( Figure 1 ; e.g., Duda et al. 2000 ; Jain et al. 2000 ). Supervised classifiers represent a group of methods whereby individual assignment is made to predefined classes (i.e., populations of origin). Unsupervised classification classes are unknown and are defined a posteriori on the basis of the degree of difference or similarity in attributes characterized from sampled individuals. Clustering methods (e.g., multidimensional scaling, principal component analysis) are examples of unsupervised classification. Applications of assignment testing in population genetics first used supervised parametric likelihood-based approaches ( Figure 1 ). Other machine learning classification methods are widely used in the physical and social sciences and in other biological disciplines (e.g. Boddy et al. 2000 ; Leung and Tran 2000 ; Manel et al. 1999 ; Raymer et al. 1997 ). Artificial neural networks (ANNs) are a popular technique used in machine learning (e.g., Boddy and Morris 1999 ; Duda et al. 2000 ; Lek and Gu&eacute;gan 2000 ; Ripley 1996 ). However, while recognized ( Hansen et al. 2001a ), ANN methods rarely have been employed for population genetics applications ( Aurelle 1999 ; Aurelle et al. 1999 ; Cornuet et al. 1996 ; Curtis et al. 2001 ; Giraudel et al. 2000 ; Grigull et al. 2001 ; Taylor et al. 1994 ; Whitler et al. 1994 ). Other popular classification methods in machine learning, such as decision trees (e.g., Bell 1996 , 1999 ; Duda et al. 2000 ; Mitchell 1997 ) and k -nearest neighbor analysis ( k -NN; e.g., Dasarathy 1991 ; Duda et al. 2000 ) have yet to be applied in population genetics ( Figure 1 ). Moreover, there has not been a directed effort to compare machine learning methodologies with the likelihood-based procedures widely used in population genetics. Cornuet et al. (1996) compared the relative merits of ANNs to discriminant analysis in an empirical study involving different populations and subspecies of honeybee ( Apis mellifera ). However, they did not compare LE and ANN supervised classifiers. Aurelle (1999) used the approach of Rannala and Mountain (1997) ( Figure 1 ) and ANN analysis using brown trout ( Salmo trutta ) microsatellite data; however, he did not provide a direct comparison of classification results or accuracies. Hansen et al. (2001a) briefly presented ANNs, but rejected their use without really testing their ability to classify individuals. The objective of this article is to describe several of the more widely used machine learning classifiers that may have utility when used with empirical population genetics data. We compare likelihood-based &ldquo;assignment tests&rdquo; ( Paetkau et al. 1995 ) with supervised machine learning classifiers including ANN, decision tree, and a k -NN clustering. Simulations were conducted which estimated and compared the assignment accuracy associated with different classifiers using ranges of parameter values (number of loci, allelic diversity, and interpopulation variance in allele frequency) typically encountered in natural populations. Comparative analyses were extended to empirical examples using lake trout ( Salvelinus namaycush ; Salmonidae).

Journal of Heredity↗

Per- and polyfluoroalkyl substances in groundwater from the Great Miami buried-valley aquifer, southwestern Ohio, 2019–20

Groundwater samples were collected during 2019 and 2020 from 23 wells in the Great Miami buried-valley aquifer (GM-BVA) in southwestern Ohio by the U.S. Geological Survey, in cooperation with the Miami Conservancy District, Dayton, Ohio, to determine concentrations of selected per- and polyfluoroalkyl substances (PFAS). The GM-BVA is a glacial outwash and alluvial fill aquifer that is the sole source of water supply for much of the region. Wells had total depths that ranged from 21 to 101 feet below land surface, and groundwater levels that ranged from 1.39 to 52.15 feet below land surface before sampling in 2019. Groundwater and related quality-control samples were sequentially collected from 22 of the 23 wells and analyzed for 24 different PFAS by 2 methods that used proprietary isotope-dilution based adaptations of U.S. Environmental Protection Agency (EPA) method 537.1, termed methods 1 and 2. Method 2 had smaller reporting limits (RL) for 22 of 24 PFAS analyzed and smaller detection limits (DLs) for all 24 PFAS analyzed compared with method 1, which made method 2 more sensitive to detect PFAS. Concentrations of perfluorooctanesulfonate (PFOS) in a groundwater (GW)-method 2 sample from well CL–275 of 1.9 nanograms per liter (ng/L) and perfluorooctanoate (PFOA) in a GW-method 2 sample from well BU–1106 of 2.1 ng/L were greater than their EPA interim health advisory guidances for drinking water (as of June 2022) by about 9,500 and 52,500 percent, respectively. The EPA interim health advisory guidances for PFOS (0.02 ng/L) and PFOA (0.004 ng/L) were also 65 and 215 times less, respectively, than the smallest method 2 DLs for PFOS (1.3 ng/L) and PFOA (0.86 ng/L). Other PFAS were either not detected in GM-BVA groundwater samples or were detected in concentrations less than Ohio action levels or Federal health-risk-based guidance. The most detected PFAS in groundwater was perfluorobutanesulfonate (PFBS), which had concentrations in samples from eight wells that ranged from 1.0 to 8.0 ng/L or from 0.05 to 0.4 percent of its EPA health advisory of 2,000 ng/L for drinking water. The similarity of PFBS (7.8 ng/L), perfluoropentanesulfonate (PFPeS; 8.1 ng/L), and perfluorohexanesulfonate (PFHxS; 14 ng/L) concentrations yielded from the GW-method 1 sample from well CL–275 on July 9, 2019, to those of PFBS (8.0 ng/L), PFPeS (7.8 ng/L), and PFHxS (16 ng/L) from the paired GW-method 2 sample demonstrated the capability of both methods to reproduce PFAS concentrations that were greater than their respective DLs. Non-detection of these PFAS in follow-up GW-method 1 and sequential replicate (Rep–GW-method 1) samples from CL–275 on April 21, 2020, indicated that the 2019 results represented a transient detection in groundwater. Eleven of twenty-three wells sampled in 2019 had from 1 to 4 PFAS detected in one or more groundwater samples or in a paired replicate sample: PFBS in 8 wells and 9 samples; PFHxS in 4 wells and 5 samples; and PFPeS, PFOS, perfluorobutanoate, perfluoropentanoate, PFOA, and perfluorooctanesulfonamide in 1 well and 1 sample each. More PFAS were detected in GW-method 2 samples than GW-method 1 samples because method 2 had smaller RLs and DLs. Results indicate benefits from the analysis of paired samples, sequential replicate samples, and other quality-control samples using analytical methods with sensitive RLs and DLs to verify PFAS concentrations in groundwater. Groundwater-age estimates indicate that water produced from all sampled wells had infiltrated to the water table within the 1947–present (2022) period of PFAS use or environmental presence. Eight wells with detectable PFBS in groundwater from 2019 samples also had groundwater-recharge dates that ranged from 1991 to 2016. Those ages coincided with the possible environmental presence of PFBS as a PFAS byproduct or use as an alternative to PFOS after about 2002. Two wells that had detections of PFHxS in 2019 groundwater samples also had post-2000 groundwater-recharge dates that coincided with the period of use of PFHxS as an alternative to PFOS. Six of nine wells with more than 66-percent of urban land use that was within 0.3 miles of each well, as of 2012, also had 1 to 4 PFAS detected in one of their groundwater samples. Seven of nine wells that produced groundwater in 2019 with an oxic redox category also had one or more PFAS detected in a sample.

Ohio↗

Design, analysis, and interpretation of field quality-control data for water-sampling projects

The process of obtaining and analyzing water samples from the environment includes a number of steps that can affect the reported result. The equipment used to collect and filter samples, the bottles used for specific subsamples, any added preservatives, sample storage in the field, and shipment to the laboratory have the potential to affect how accurately samples represent the environment from which they were collected. During the early 1990s, the U.S. Geological Survey implemented policies to include the routine collection of quality-control samples in order to evaluate these effects and to ensure that water-quality data were adequately representing environmental conditions. Since that time, the U.S. Geological Survey Office of Water Quality has provided training in how to design effective field quality-control sampling programs and how to evaluate the resultant quality-control data. This report documents that training material and provides a reference for methods used to analyze quality-control data. Quality-control data are those generated from the collection and analysis of quality-control samples, and are used to estimate the magnitude of errors in the process of obtaining environmental data. &ldquo;Bias&rdquo; and &ldquo;variability&rdquo; are the terms used in this report for the two types of errors in environmental data that are quantified by the data from quality-control samples. Bias is the systematic error inherent in a method or measurement system. Variability is the random error that occurs in independent measurements. The types of field quality-control samples discussed in this report include blanks, spikes, and replicates. Blanks are samples prepared with water that is intended to be free of measurable constituents that will be analyzed by the laboratory; blanks are used to estimate bias caused by contamination. Spiked samples are modified by addition of specific analytes; spikes are used to determine the performance of analytical methods and to estimate the potential bias due to matrix interference or analyte degradation. Replicate samples are two or more samples that are considered to be essentially identical in composition. Replicates are used to evaluate variability in analytical results. Various sub-types of these quality-control samples are defined and discussed in this report, and guidance is provided for incorporating the proper samples into the design for a project. The concept of inference space is introduced to help determine where and when quality-control samples should be collected as well as which environmental samples are related to a set of quality-control samples. The recommended basic quality-control design incorporates project-specific considerations, such as the objectives and scale of the study, and hydrologic and chemical conditions within the study area. The report provides extensive information about statistical methods used to analyze quality-control data in order to estimate potential bias and variability in environmental data. These methods include construction of confidence intervals on various statistical measures, such as the mean, percentiles and percentages, and standard deviation. The methods are used to compare quality-control results with the larger set of environmental data in order to determine whether the effects of bias and variability might interfere with interpretation of these data. Examples from published reports are presented to illustrate how the methods are applied, how bias and variability are reported, and how the interpretation of environmental data can be qualified based on the quality-control analysis.

Techniques and Methods↗