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The potential for citizen science to produce reliable and useful information in ecology

We examined features of citizen science that influence data quality, inferential power, and usefulness in ecology. As background context for our examination, we considered topics such as ecological sampling (probability based, purposive, opportunistic), linkage between sampling technique and statistical inference(designbased,modelbased),andscientificparadigms(confirmatory,exploratory).Wedistinguished several types of citizen science investigations, from intensive research with rigorous protocols targeting clearly articulated questions to mass-participation internet-based projects with opportunistic data collection lacking samplingdesign,andexaminedoverarchingobjectives,design,analysis,volunteertraining,andperformance. We identified key features that influence data quality: project objectives, design and analysis, and volunteer training and performance. Projects with good designs, trained volunteers, and professional oversight can meet statistical criteria to produce high-quality data with strong inferential power and therefore are well suited for ecological research objectives. Projects with opportunistic data collection, little or no sampling design, and minimal volunteer training are better suited for general objectives related to public education or data exploration because reliable statistical estimation can be difficult or impossible. In some cases, statistically robust analytical methods, external data, or both may increase the inferential power of certain opportunistically collected data. Ecological management, especially by government agencies, frequently requires data suitable for reliable inference. With standardized protocols, state-of-the-art analytical methods, and well-supervised programs, citizen science can make valuable contributions to conservation by increasing the scope of species monitoring efforts. Data quality can be improved by adhering to basic principles of data collection and analysis, designing studies to provide the data quality required, and including suitable statistical expertise, thereby strengthening the science aspect of citizen science and enhancing acceptance by the scientific community and decision makers.

Conservation Biology

Alaska Geochemical Database Version 3.0 (AGDB3)—Including “Best Value” Data Compilations for Rock, Sediment, Soil, Mineral, and Concentrate Sample Media

The Alaska Geochemical Database Version 3.0 (AGDB3) contains new geochemical data compilations in which each geologic material sample has one “best value” determination for each analyzed species, greatly improving speed and efficiency of use. Like the Alaska Geochemical Database Version 2.0 before it, the AGDB3 was created and designed to compile and integrate geochemical data from Alaska to facilitate geologic mapping, petrologic studies, mineral resource assessments, definition of geochemical baseline values and statistics, element concentrations and associations, environmental impact assessments, and studies in public health associated with geology. This relational database, created from data-bases and published datasets of the U.S. Geological Survey (USGS), Atomic Energy Commission National Uranium Resource Evaluation (NURE), Alaska Division of Geological & Geophysical Surveys (DGGS), U.S. Bureau of Mines, and U.S. Bureau of Land Management serves as a data archive in support of Alaskan geologic and geochemical projects and contains data tables in several different formats describing historical and new quantitative and qualitative geochemical analyses. The analytical results were determined by 112 laboratory and field analytical methods on 396,343 rock, sediment, soil, mineral, heavy-mineral concentrate, and oxalic acid leachate samples. Most samples were collected by personnel of these agencies and analyzed in agency laboratories or, under contracts, in commercial analytical laboratories. These data represent analyses of samples collected as part of various agency programs and projects from 1938 through 2017. In addition, mineralogical data from 18,138 nonmagnetic heavy-mineral concentrate samples are included in this database. The AGDB3 includes historical geochemical data archived in the USGS National Geochemical Database (NGDB) and NURE National Uranium Resource Evaluation-Hydrogeochemical and Stream Sediment Reconnaissance databases, and in the DGGS Geochemistry database. Retrievals from these data-bases were used to generate most of the AGDB data set. These data were checked for accuracy regarding sample location, sample media type, and analytical methods used. In other words, the data of AGDB3 supersedes data in the AGDB and the AGDB2, but the background about the data in these two earlier versions are needed by users of the current AGDB3 to understand what has been done to amend, clean up, correct and format this data. Corrections were entered, resulting in a significantly improved Alaska geochemical dataset, the AGDB3. Data that were not previously in these databases because the data predate the earliest agency geochemical data-bases, or were once excluded for programmatic reasons, are included here in the AGDB3 and will be added to the NGDB and Alaska Geochemistry. The AGDB3 data provided here are the most accurate and complete to date and should be useful for a wide variety of geochemical studies. The AGDB3 data provided in the online version of the database may be updated or changed periodically.

Alaska

Quality-assurance results for routine water analyses in U.S. Geological Survey laboratories, water year 1998

The U.S. Geological Survey operates a quality-assurance program based on the analyses of reference samples for two laboratories: the National Water Quality Laboratory and the Quality of Water Service Unit. Reference samples that contain selected inorganic, nutrient, and low-level constituents are prepared and submitted to the laboratory as disguised routine samples. The program goal is to estimate precision and bias for as many analytical methods offered by the participating laboratories as possible. Blind reference samples typically are submitted at a rate of 2 to 5 percent of the annual environmental-sample load for each constituent. The samples are distributed to the laboratories throughout the year. The reference samples are subject to the identical laboratory handling, processing, and analytical procedures as those applied to environmental samples and, therefore, have been used as an independent source to verify bias and precision of laboratory analytical methods and ambient water-quality measurements. The results are stored permanently in the National Water Information System and the Blind Sample Project's data base. During water year 1998, 95 analytical procedures were evaluated at the National Water Quality Laboratory and 63 analytical procedures were evaluated at the Quality of Water Service Unit. An overall evaluation of the inorganic and low-level constituent data for water year 1998 indicated 77 of 78 analytical procedures at the National Water Quality Laboratory met the criteria for precision. Silver (dissolved, inductively coupled plasma-mass spectrometry) was determined to be imprecise. Five of 78 analytical procedures showed bias throughout the range of reference samples: chromium (dissolved, inductively coupled plasma-atomic emission spectrometry), dissolved solids (dissolved, gravimetric), lithium (dissolved, inductively coupled plasma-atomic emission spectrometry), silver (dissolved, inductively coupled plasma-mass spectrometry), and zinc (dissolved, inductively coupled plasma-mass spectrometry). At the National Water Quality Laboratory during water year 1998, lack of precision was indicated for 2 of 17 nutrient procedures: ammonia as nitrogen (dissolved, colorimetric) and orthophosphate as phosphorus (dissolved, colorimetric). Bias was indicated throughout the reference sample range for ammonia as nitrogen (dissolved, colorimetric, low level) and nitrate plus nitrite as nitrogen (dissolved, colorimetric, low level). All analytical procedures tested at the Quality of Water Service Unit during water year 1998 met the criteria for precision. One of the 63 analytical procedures indicated a bias throughout the range of reference samples: aluminum (whole-water recoverable, inductively coupled plasma-atomic emission spectrometry, trace).

Water-Resources Investigations Report

Dealing with incomplete and variable detectability in multi-year, multi-site monitoring of ecological populations

An ecological monitoring program should be viewed as a component of a larger framework designed to advance science and/or management, rather than as a stand-alone activity. Monitoring targets (the ecological variables of interest; e.g. abundance or occurrence of a species) should be set based on the needs of that framework (Nichols and Williams 2006; e.g. Chapters 2&ndash;4). Once such monitoring targets are set, the subsequent step in monitoring design involves consideration of the field and analytical methods that will be used to measure monitoring targets with adequate accuracy and precision. Long-term monitoring programs will involve replication of measurements over time, and possibly over space; that is, one location or each of multiple locations will be monitored multiple times, producing a collection of site visits (replicates). Clearly this replication is important for addressing spatial and temporal variability in the ecological resources of interest (Chapters 7&ndash;10), but it is worth considering how this replication can further be exploited to increase the effectiveness of monitoring. In particular, defensible monitoring of the majority of animal, and to a lesser degree plant, populations and communities will generally require investigators to account for imperfect detection (Chapters 4, 18). Raw indices of population state variables, such as abundance or occupancy (sensu MacKenzie et al. 2002), are rarely defensible when detection probabilities are < 1, because in those cases detection may vary over time and space in unpredictable ways. Myriad authors have discussed the risks inherent in making inference from monitoring data while failing to correct for differences in detection, resulting in indices that have an unknown relationship to the parameters of interest (e.g. Nichols 1992, Anderson 2001, MacKenzie et al. 2002, Williams et al. 2002, Anderson 2003, White 2005, K&eacute;ry and Schmidt 2008). While others have argued that indices may be preferable in some cases due to the challenges associated with estimating detection probabilities (e.g. McKelvey and Pearson 2001, Johnson 2008), we do not attempt to resolve this debate here. Rather, we are more apt to agree with MacKenzie and Kendall (2002) that the burden of proof ought to be on the assertion that detection probabilities are constant. Furthermore, given the wide variety of field methods available for estimating detection probabilities and the inability for an investigator to know, a priori, if detection probabilities will be constant over time and space, we believe that development of monitoring programs ought to include field and analytical methods to account for the imperfect detection of organisms.

Book chapter

Quality-control results for ground-water and surface-water data, Sacramento River Basin, California, National Water-Quality Assessment, 1996-1998

Evaluating the extent that bias and variability affect the interpretation of ground- and surface-water data is necessary to meet the objectives of the National Water-Quality Assessment (NAWQA) Program. Quality-control samples used to evaluate the bias and variability include annual equipment blanks, field blanks, field matrix spikes, surrogates, and replicates. This report contains quality-control results for the constituents critical to the ground- and surface-water components of the Sacramento River Basin study unit of the NAWQA Program. A critical constituent is one that was detected frequently (more than 50 percent of the time in blank samples), was detected at amounts exceeding water-quality standards or goals, or was important for the interpretation of water-quality data. Quality-control samples were collected along with ground- and surface-water samples during the high intensity phase (cycle 1) of the Sacramento River Basin NAWQA beginning early in 1996 and ending in 1998. Ground-water field blanks indicated contamination of varying levels of significance when compared with concentrations detected in environmental ground-water samples for ammonia, dissolved organic carbon, aluminum, and copper. Concentrations of aluminum in surface-water field blanks were significant when compared with environmental samples. Field blank samples collected for pesticide and volatile organic compound analyses revealed no contamination in either ground- or surface-water samples that would effect the interpretation of environmental data, with the possible exception of the volatile organic compound trichloromethane (chloroform) in ground water. Replicate samples for ground water and surface water indicate that variability resulting from sample collection, processing, and analysis was generally low. Some of the larger maximum relative percentage differences calculated for replicate samples occurred between samples having lowest absolute concentration differences and(or) values near the reporting limit. Surrogate recoveries for pesticides analyzed by gas chromatography/mass spectrometry (GC/MS), pesticides analyzed by high performance liquid chromatography (HPLC), and volatile organic compounds in ground- and surface-water samples were within the acceptable limits of 70 to 130 percent and median recovery values between 82 and 113 percent. The recovery percentages for surrogate compounds analyzed by HPLC had the highest standard deviation, 20 percent for ground-water samples and 16 percent for surface-water samples, and the lowest median values, 82 percent for ground-water samples and 91 percent for surface-water samples. Results were consistent with the recovery results described for the analytical methods. Field matrix spike recoveries for pesticide compounds analyzed using GC/MS in ground- and surface-water samples were comparable with published recovery data. Recoveries of carbofuran, a critical constituent in ground- and surface-water studies, and desethyl atrazine, a critical constituent in the ground-water study, could not be calculated because of problems with the analytical method. Recoveries of pesticides analyzed using HPLC in ground- and surface-water samples were generally low and comparable with published recovery data. Other methodological problems for HPLC analytes included nondetection of the spike compounds and estimated values of spike concentrations. Recovery of field matrix spikes for volatile organic compounds generally were within the acceptable range, 70 and 130 percent for both ground- and surface-water samples, and median recoveries from 62 to 127 percent. High or low recoveries could be related to errors in the field, such as double spiking or using spike solution past its expiration date, rather than problems during analysis. The methodological changes in the field spike protocol during the course of the Sacramento River Basin study, which included decreasing the amount of spike solu

Water-Resources Investigations Report

Hydrogeology, Ground-Water-Age Dating, Water Quality, and Vulnerability of Ground Water to Contamination in a Part of the Whitewater Valley Aquifer System near Richmond, Indiana, 2002-2003

Assessments of the vulnerability to contamination of ground-water sources used by public-water systems, as mandated by the Federal Safe Drinking Water Act Amendments of 1996, commonly have involved qualitative evaluations based on existing information on the geologic and hydrologic setting. The U.S. Geological Survey National Water-Quality Assessment Program has identified ground-water-age dating; detailed water-quality analyses of nitrate, pesticides, trace elements, and wastewater-related organic compounds; and assessed natural processes that affect those constituents as potential, unique improvements to existing methods of qualitative vulnerability assessment. To evaluate the improvement from use of these methods, in 2002 and 2003, the U.S. Geological Survey, in cooperation with the City of Richmond, Indiana, compiled and interpreted hydrogeologic data and chemical analyses of water samples from seven wells in a part of the Whitewater Valley aquifer system in a former glacial valley near Richmond. This study investigated the application of ground-water-age dating, dissolved-gas analyses, and detailed water-quality analyses to quantitatively evaluate the vulnerability of ground water to contamination and to identify processes that affect the vulnerability to specific contaminants in an area of post-1972 greenfield development. The aquifer system in the study area includes an unconfined sand and gravel aquifer used for public-water supply (upper aquifer) and a confined sand and gravel aquifer (lower aquifer) separated by a till confining unit. Several hydrogeologic and cultural measures indicate that the upper aquifer is qualitatively vulnerable to contamination: the upper aquifer is unconfined and has a shallow depth to the water table (from about 4.75 to 14 feet below land surface), low-permeability sediments in the unsaturated zone are thin (less than 10 feet thick), estimated ground-water-flow rates through the upper aquifer are relatively rapid (the highest estimated rates ranged from 0.44 to about 5.0 feet per day), and potential contaminant sources were present. Ground-water-age dates indicate that ground-water samples represented recharge from about the time greenfield development began south of the ground-water-flow divide and that changes in water quality would lag changes in contaminant inputs. Estimates of ground-water age, computed with dichlorodifluoromethane (CFC-12) and trichlorotrifluoroethane (CFC-113) concentrations in water samples collected from seven observation wells in February and March 2003, indicated that water in the upper aquifer had recharged within about 13 to 30 years before sampling. Ground-water ages were youngest (from about 13 to 15 years since recharge) in water from the shallow wells along the glacial-valley margin and oldest (30 years) in water from a well at the base of the aquifer in the valley center. Ground-water ages determined for the shallow wells may be affected by mixing of recent recharge with older ground water from deeper in the aquifer, as indicated by upward hydraulic gradients between paired shallow and deep wells in the upper aquifer. Other parts of the Whitewater Valley aquifer system with similar hydrogeologic characteristics could be expected to have similarly young ground-water ages and residence times. Analyses of water samples collected from the seven observation wells in August and September 2002 indicated that concentrations of chloride, sodium, and nitrate generally were larger in ground water from the upper aquifer than in other parts of the Whitewater Valley aquifer system. Drinking-water-quality standards for Indiana were exceeded in water samples from one well for chloride concentrations, from four wells for dissolved-solids concentrations, and from one well for nitrate concentrations. Application of low-level methods for trace-element analyses determined that concentrations of aluminum, cobalt, iron, lithium, molybdenum, nickel, selenium, uranium, vanadium, and zinc were less than or equal to 8 micrograms per liter; concentrations of arsenic, cadmium, chromium, and copper were less than or equal to 1 microgram per liter. Application of low-level analytical methods to water samples enabled the detection of several pesticides and volatile, semivolatile, and wastewater-related organic compounds; concentrations of individual pesticides and volatile organic compounds were less than 0.1 microgram per liter and concentrations of individual wastewater organic compounds were less than 0.5 microgram per liter. The low-level analytical methods will provide useful data with which to compare future changes in water quality. Results of detailed water-quality analyses, ground-waterage dating, and dissolved-gas analyses indicated the vulnerability of ground water to specific types of contamination, the sequence of contaminant introduction to the aquifer relative to greenfield development, and processes that may mitigate the contamination. Concentrations of chloride and sodium and chloride/bromide weight ratios in sampled water from five wells indicated the vulnerability of the upper aquifer to roaddeicer contamination. Ground-water-age estimates from these wells indicated the onset of upgradient road-deicer use within the previous 25 years. Nitrate in the upper aquifer predates the post-1972 development, based on a ground-water-age date (30 years) and the nitrate concentration (5.12 milligrams per liter as nitrogen) in water from a deep well. Vulnerability of the aquifer to nitrate contamination is limited partially by denitrification. Detection of one to four atrazine transformation products in water samples from the upper aquifer indicated biological and hydrochemical processes that may limit the vulnerability of the ground water to atrazine contamination. Microbial processes also may limit the aquifer vulnerability to small inputs of halogenated aliphatic compounds, as indicated by microbial transformations of trichlorofluoromethane and trichlorotrifluoroethane relative to dichlorodifluoromethane. The vulnerability of ground water to contamination in other parts of the aquifer system also may be mitigated by hydrodynamic dispersion and biologically mediated transformations of nitrate, pesticides, and some organic compounds. Identification of the sequence of contamination and processes affecting the vulnerability of ground water to contamination would have been unlikely with conventional assessment methods.

Indiana, Ohio

Descriptions of anisotropy and heterogeneity and their effect on ground-water flow and areas of contribution to public supply wells in a karst carbonate aquifer system

Delineation of areas of contribution to wells tapping a karst carbonate aquifer system can be extremely difficult using conventional approaches designed for isotropic and homogeneous aquifers, because ground-water flow tends to be through solution-enhanced conduits. Nonradial flow along preferential zones can result in inaccurate estimates of flow paths and traveltimes. Because of the large variability in factors affecting contributing areas and an imperfect understanding of how these factors can vary, the estimation of contributing areas is an approximation at best. To better understand the effects of aquifer anisotropy and heterogeneity on areas of contribution, an exploratory modeling approach was used. MODFLOW, a numerical flow model, and MODPATH, a particle tracking program, were used to generate time-related areas of contribution for six hypothetical carbonate aquifer system types. The six types were conceptualized to approximate different types of aquifer anisotropy and heterogeneity. These include: (1) an isotropic and homogeneous single-layer system; (2) an anisotropic in a horizontal plane single layer system; (3) a discrete vertically fractured single-layer system; (4) a multilayered system; (5) a doubly porous single-layer system; and (6) a vertically and horizontally interconnected heterogeneous system. The simulated aquifer anisotropy was 5:1 (Kxx/Kyy) determined from TENSOR2D results. The simulated discrete vertical fracture network represents locations inferred from mapped photolineaments. The simulated enhanced flow zones were determined from borehole video and geophysical logs. Areas of contribution were simulated for two prototype regions. The two prototypes were selected to be representative of the hydrologic diversity within the study area and were designated the Central Swamp and Lake Terrace regions. Localized conditions in pumping, production well distribution, and aquifer transmissivity affect the size, shape, and orientation of areas of contribution to public supply wells. The simulated areas of contribution are 60 percent larger in the Central Swamp region where pumpage is more than double and transmissivity is about half that of the Lake Terrace region. Although these factors are important, this study focused on the effects from hydrogeologic factors common to karst carbonate aquifer systems. This study indicates that the distribution and type of aquifer anisotropy and heterogeneity will affect the size, shape, and orientation of areas of contribution in a karst carbonate aquifer system. The size of the 50-year time-related areas of contribution ranged from 8.2 to 39.1 square miles in the Central Swamp region and from 4.0 to 18.3 square miles in the Lake Terrace region. Simulations showed that the size of areas of contribution is primarily affected by simulated withdrawal rates, effective porosity of the carbonate rock, and transmissivity. The shape and orientation of the simulated areas of contribution primarily result from aquifer anisotropy, well distribution, flow along solution-enhanced zones, and short-circuiting of flow through fracture networks. Comparisons also were made between protection zones delineated using analytical models and areas of contribution delineated using numerical models. The size of the 5-year time-related protection zone in the Central Swamp region using an analytical model was almost twice as large as the numerically simulated area of contribution, and more than eight times larger than the numerically simulated area of contribution in the Lake Terrace region. The differences in size are primarily the result of how the flow field is approximated. The analytical method assumes only lateral flow to wells but numerical methods allow particles to move laterally and vertically. Additionally, multiple-well-interference effects resulting from the close proximity of several pumping wells cause individual capture zones to converge or diverge, depending on the difference in pumping rates and orientation among the wells. Such an interpretation is not available from analytical methods. The simulated distributions of aquifer anisotropy and heterogeneity, in this study, were highly conceptualized, but were based on plausible occurrences of anisotropy and heterogeneity inherent in carbonate aquifer systems.

Florida

Assessment of Energetic Compounds, Semi-volatile Organic Compounds, and Trace Elements in Streambed Sediment and Stream Water from Streams Draining Munitions Firing Points and Impact Areas, Fort Riley, Kansas, 2007-08

An assessment of energetic compounds (explosive and propellant residues) and associated semi-volatile organic compounds (SVOCs) and trace elements in streambed sediment and stream water from streams draining munitions firing points and impact areas at Fort Riley, northeast Kansas, was performed during 2007-08 by the U.S. Geological Survey (USGS) in cooperation with the U.S. Army. Streambed sediment from 16 sampling sites and stream-water samples from 5 sites were collected at or near Fort Riley and analyzed for as many as 17 energetic compounds, 65 SVOCs, and 27 trace elements. None of the energetic compounds or SVOCs were detected in streambed sediment collected from sites within the Fort Riley Military Reservation. This may indicate that these compounds either are not transported from dispersal areas or that analytical methods are not sensitive enough to detect the small concentrations that may be transported. Concentrations of munitions-associated trace elements did not exceed sediment-quality guidelines recommended by the U.S. Environmental Protection Agency (USEPA) and are not indicative of contamination of streambed sediment at selected streambed sampling sites, at least in regards to movement from dispersal areas. Analytical results of stream-water samples provided little evidence of contamination by energetic compounds, SVOCs, or associated trace elements. Perchlorate was detected in 19 of 20 stream-water samples at concentrations ranging from an estimated 0.057 to an estimated 0.236 ug/L (micrograms per liter) with a median concentration of an estimated 0.114 ug/L, substantially less than the USEPA Interim Health Advisory criterion (15 ug/L), and is in the range of documented background concentrations. Because of these small concentrations and possible natural sources (precipitation and groundwater), it is likely that the occurrence of perchlorate in stream water is naturally occurring, although a definitive identification of the source of perchlorate in stream water at Fort Riley is difficult. The only SVOCs detected in stream-water samples were bis(2-ethylhexyl) phthalate and di-n-butyl phthalate but at concentrations substantially less than the most stringent aquatic-life criteria established by the Kansas Department of Health and Environment. All trace element concentrations in stream-water samples were less than the most stringent aquatic-life criteria. The implication of these stream-water results is that contamination arising from firing-range activities, if it exists, is so small as to be nondetectable with current analytical methods or is not distinguishable from background concentrations for constituents that also are naturally occurring. Overall, the munitions-related constituents analyzed in streambed sediment and stream water, when detected, were at concentrations that were less than regulatory criteria

Scientific Investigations Report

Water- and air-quality monitoring of Sweetwater Reservoir watershed, San Diego County, California — Phase one results continued, 2001-2003

In 1998, the U.S. Geological Survey, in cooperation with the Sweetwater Authority, began a study to monitor water, air, and sediment at the Sweetwater and Loveland Reservoirs in San Diego County, California. The study includes regular sampling of water and air at Sweetwater Reservoir for chemical constituents, including volatile organic compounds (VOC), polynuclear aromatic hydrocarbons (PAH), pesticides, and major and trace elements. The purpose of this study is to monitor changes in contaminant composition and concentration during the construction and operation of State Route 125. To accomplish this, the study was divided into two phases. Phase One sampling (water years 1998–2004) determined baseline conditions for the detection frequency and the concentrations of target compounds in air and water. Phase Two sampling (starting water year 2005) continues at selected monitoring sites during and after construction of State Route 125 to assess the chemical impact this roadway alignment may have on water quality in the reservoir. Water samples were collected for VOCs and pesticides at Loveland Reservoir during Phase One and will be collected during Phase Two for comparison purposes. Air samples collected to monitor changes in VOCs, PAHs, and pesticides were analyzed by adapting methods used to analyze water samples. Bed-sediment samples have been and will be collected three times during the study; at the beginning of Phase One, at the start of Phase Two, and near the end of the study. In addition to the ongoing data collection, several special studies were initiated to assess the occurrence of specific chemicals of concern, such as trace metals, anthropogenic indicator compounds, and pharmaceuticals. This report describes the study design, and the sampling and analytical methods, and presents data from water and air samples collected during the fourth and fifth years of Phase One of the study (October 2001 to September 2003). Data collected during the first three years has been previously published. Three types of quality-control samples were used in this study: blanks, spikes, and replicates. Blanks and spikes are used to estimate result bias, and replicates are used to estimate result variability. Additionally, surrogate compounds were added at the laboratory to samples of VOCs, PAHs, pesticides, anthropogenic indicator compounds, and pharmaceuticals to monitor sample-specific performance of the analytical method.

California

Volatile organic compound matrix spike recoveries for ground- and surface-water samples, 1997-2001

The U.S. Geological Survey's National Water-Quality Assessment (NAWQA) Program used field matrix spikes (FMSs), field matrix spike replicates (FMSRs), laboratory matrix spikes (LMSs), and laboratory reagent spikes (LRSs), in part, to assess the quality of volatile organic compound (VOC) data from water samples collected and analyzed in more than 50 of the Nation's largest river basins and aquifers (Study Units). The data-quality objectives of the NAWQA Program include estimating the extent to which variability, degradation, and matrix effects, if any, may affect the interpretation of chemical analyses of ground- and surface-water samples. In order to help meet these objectives, a known mass of VOCs was added (spiked) to water samples collected in 25 Study Units. Data within this report include recoveries from 276 ground- and surface-water samples spiked with a 25-microliter syringe with a spike solution containing 85 VOCs to achieve a concentration of 0.5 microgram per liter. Combined recoveries for 85 VOCs from spiked ground- and surface-water samples and reagent water were used to broadly characterize the overall recovery of VOCs. Median recoveries for 149 FMSs, 107 FMSRs, 20 LMSs, and 152 LRSs were 79.9, 83.3, 113.1, and 103.5 percent, respectively. Spike recoveries for 85 VOCs also were calculated individually. With the exception of a few VOCs, the median percent recoveries determined from each spike type for individual VOCs followed the same pattern as for all VOC recoveries combined, that is, listed from least to greatest recovery-FMSs, FMSRs, LRSs, and LMSs. The median recoveries for individual VOCs ranged from 63.7 percent to 101.5 percent in FMSs; 63.1 percent to 101.4 percent in FMSRs; 101.7 percent to 135.0 percent in LMSs; and 91.0 percent to 118.7 percent in LRSs. Additionally, individual VOC recoveries were compared among paired spike types, and these recoveries were used to evaluate potential bias in the method. Variability associated with field spiking, field handling, transport, and analysis was assessed by comparing recoveries between 107 pairs of FMR and FMSR samples. For most VOCs, FMSR recoveries were greater than the paired FMS recoveries. This may result from routinely processing the FMS sample first, allowing a more fluid and efficient technique when processing the FMSR. Degradation was examined by comparing VOC recoveries between 20 pairs of FMS and LMS samples. For all VOCs, the LMS recoveries were greater than FMS recoveries. However, data presented in a previously published VOC stability study were interpreted, and recoveries indicated that VOC degradation should not affect the recovery for most VOCs monitored by the NAWQA Program. Matrix effects were examined by comparing VOC recoveries from 20 pairs of LMS and LRS samples. With the exception of two VOCs, individual recoveries were not significantly different between LMSs and LRSs, indicating that most VOC recoveries are not affected by matrix effects. Additionally, matrix effects should be negligible due to the analytical technique (purge and trap capillary column gas chromatography/mass spectrometry) used for VOC analysis at the U.S. Geological Survey National Water Quality Laboratory (NWQL). The reason for the lower VOC recoveries from FMSs and FMSRs than from LMSs and LRSs may be associated with differences in spiking technique and experience, and to varying environmental conditions at the time of spiking. However, for all spike types, 87 percent of the individual VOC recoveries were within the range of 60 to 140 percent, a range that is considered acceptable by the U.S. Environmental Protection Agency's established analytical method. Additionally, the median recovery for each spike type was within the range of 60 to 140 percent. The excellent VOC recoveries from LMSs and LRSs demonstrate that low VOC concentrations can routinely and accurately be measured by the analytical methods used by the NWQL.

Scientific Investigations Report

New-generation pesticides are prevalent in California's Central Coast streams

Pesticides are widely recognized as important biological stressors in streams, especially in heavily developed urban and agricultural areas like the Central California Coast region. We assessed occurrence and potential toxicity of pesticides in small streams in the region using two analytical methods: a broad-spectrum (223 compounds) method in use since 2012 and a newly developed method for 30 additional new-generation fungicides and insecticides. At least one pesticide compound was identified in 83 of the 85 streams sampled. About one-half (48%) of the 253 pesticides measured were detected at least once and 27 were detected in 10% or more of samples. Three of the top 4, and 6 of the top 10 most frequently detected compounds (chlorantraniliprole, dinotefuran, boscalid, thiamethoxam, clothianidin and the fluopicolide degradate 2,6-dichlorobenzamide) were analyzed by the new method. Pesticide mixtures were common, with two or more pesticide compounds detected in 81% of samples and 10 or more in 32% of samples. The pesticide count at a site was relatively consistent over the 6-week study. Four sites with mixed land-use in the lower basin (<5 km from the sampling site) tended to have the highest pesticide counts and the highest concentrations. Potential toxicity (assessed by comparison to benchmarks) to invertebrates was much more common than potential toxicity to fish or plants and was associated with a wide array of insecticides. The common occurrence of new-generation pesticides highlights the need to continuously update analytical methods to keep pace with changing pesticide use for a fuller assessment of pesticide occurrence and effects on the environment.

California

Water- and air-quality and surficial bed-sediment monitoring of the Sweetwater Reservoir watershed, San Diego County, California, 2003-09

In 1998, the U.S. Geological Survey, in cooperation with the Sweetwater Authority, began a study to assess the overall health of the Sweetwater watershed in San Diego County, California. This study was designed to provide a data set that could be used to evaluate potential effects from the construction and operation of State Route 125 within the broader context of the water quality and air quality in the watershed. The study included regular sampling of water, air, and surficial bed sediment at Sweetwater Reservoir (SWR) for chemical constituents, including volatile organic compounds (VOCs), base-neutral and acid- extractable organic compounds (BNAs) that include polycyclic aromatic hydrocarbons (PAHs), pesticides, and metals. Additionally, water samples were collected for anthropogenic organic indicator compounds in and around SWR. Background water samples were collected at Loveland Reservoir for VOCs, BNAs, pesticides, and metals. Surficial bed-sediment samples were collected for PAHs, organochlorine pesticides, and metals at Sweetwater and Loveland Reservoirs. To monitor changes in contaminant concentration in water and air at SWR during the construction and operation of State Route 125, this study was divided into three phases. Phase One sampling (September 1998 to September 2004) was designed to establish baseline conditions for target compounds in terms of detection frequency and concentration in air and water. Phase Two (October 2004 to September 2007) continued sampling at selected monitoring sites during construction of State Route 125 to assess any effect from the construction process and the use of heavy equipment to build the roadway. Phase Three (October 2007 to August 2009) continued sampling for 2 years after the opening of State Route 125 to assess the potential changes in water quality related to vehicle emissions from the roadway alignment. Surficial bed-sediment samples were collected three times during the study&mdash;at the beginning of the study, at the start of Phase Two, and at the end of the study. This report describes the study design and the sampling and analytical methods and presents data from water, air, and surficial bed-sediment samples collected from the sixth to eleventh years of the study (October 2003&ndash;August 2009), spanning the last year of Phase one and all of Phases Two and Three. Data collected during the first 5 years of sampling have been previously published. Three types of quality-control samples were used in this study&mdash;matrix spikes, blanks, and replicates. Matrix-spike data are considered to be adequate if the recovery concentration is within 30 percent of the matrix concentration. Replicate data are considered to be adequate if the replicate sample concentration is within 30 percent of the environmental sample concentration. Additionally, surrogate compounds were added to most samples to monitor sample-specific performance of the analytical method. Most VOC matrix-spike recovery data associated with water samples are within acceptable criteria, but three VOCs had recoveries below the acceptable criteria; these compounds may not have been detected in water samples if they were present at low concentrations. Data for blanks associated with water samples for VOCs and metals showed no detections above their laboratory reporting levels. Most replicate data are within acceptable criteria. Quality-control data for VOC air samples resulted in flagging several reported concentrations for acetone, benzene, ethenylbenzene, and naphthalene because they may be biased high. Acetone, benzene, and toluene were detected at low concentrations in almost every VOC air blank. Some PAH and pesticide concentrations in air samples were designated as estimated because of method performance limitations. PAHs in surficial bed sediment had 83 percent of surrogates below the acceptable criteria. No matrix-spike data for metals in surficial bed sediment were outside the acceptable criteria; only beryllium had a replicate comparison outside the acceptable criteria. Sampling results show concentrations of the gasoline oxygenate methyl tert -butyl ether in water and air samples declined after it was phased out by the State of California in January 2004. The largest concentrations of gasoline hydrocarbons benzene and toluene in water were detected at or near the surface of the SWR. Isophorone and phenol were the two most frequently detected BNA compounds in water. Diuron, prometon, and simazine were the most frequently detected pesticide compounds in water. Concentrations of benzene and toluene in air samples were highest during the cooler months and had a consistent seasonal pattern over time. Ten PAH compounds were detected frequently in air samples. Twelve pesticide compounds were also detected in air samples. Surficial bed-sediment samples were analyzed for 53 PAHs; 22 of the compounds had one or more detections. Surficial bed-sediment samples were analyzed for 22 organic compounds; only 6 compounds had one or more detections. Surficial bed-sediment samples were analyzed for 37 metals.

California

Nutrient loadings to streams of the continental United States from municipal and industrial effluent?

Data from the United States Environmental Protection Agency Permit Compliance System national database were used to calculate annual total nitrogen (TN) and total phosphorus (TP) loads to surface waters from municipal and industrial facilities in six major regions of the United States for 1992, 1997, and 2002. Concentration and effluent flow data were examined for approximately 118,250 facilities in 45 states and the District of Columbia. Inconsistent and incomplete discharge locations, effluent flows, and effluent nutrient concentrations limited the use of these data for calculating nutrient loads. More concentrations were reported for major facilities, those discharging more than 1 million gallons per day, than for minor facilities, and more concentrations were reported for TP than for TN. Analytical methods to check and improve the quality of the Permit Compliance System data were used. Annual loads were calculated using "typical pollutant concentrations" to supplement missing concentrations based on the type and size of facilities. Annual nutrient loads for over 26,600 facilities were calculated for at least one of the three years. Sewage systems represented 74% of all TN loads and 58% of all TP loads. This work represents an initial set of data to develop a comprehensive and consistent national database of point-source nutrient loads. These loads can be used to inform a wide range of water-quality management, watershed modeling, and research efforts at multiple scales.

Journal of the American Water Resources Associatio

Occurrence of organic wastewater compounds in selected surface-water supplies, Triangle area of North Carolina, 2002-2005

Selected organic wastewater compounds, such as household, industrial, and agricultural-use compounds, sterols, pharmaceuticals, and antibiotics, were measured at eight sites classified as drinking-water supplies in the Triangle Area of North Carolina. From October 2002 through July 2005, seven of the sites were sampled twice, and one site was sampled 28 times, for a total of 42 sets of environmental samples. Samples were analyzed for as many as 126 compounds using three laboratory analytical methods. These methods were developed by the U.S. Geological Survey to detect low levels (generally less than or equal to 1.0 microgram per liter) of the target compounds in filtered water. Because analyses were conducted on filtered samples, the results presented in this report may not reflect the total concentration of organic wastewater compounds in the waters that were sampled. Various quality-control samples were used to quality assure the results in terms of method performance and possible laboratory or field contamination. Of the 108 organic wastewater compounds that met method performance criteria, 24 were detected in at least one sample during the study. These 24 compounds included 3 pharmaceutical compounds, 6 fire retardants and plasticizers, 3 antibiotics, 3 pesticides, 6 fragrances and flavorants, 1 disinfectant, and 2 miscellaneous-use compounds, all of which likely originated from a variety of domestic, industrial, and agricultural sources. The 10 most frequently detected compounds included acetyl-hexamethyl tetrahydronaphthalene and hexahydro-hexamethyl cyclopentabenzopyran (synthetic musks that are widely used in personal-care products and are known endocrine disruptors); tri(2-chloroethyl) phosphate, tri(dichloroisopropyl) phosphate, and tributyl phosphate (fire retardants); metolachlor (herbicide); caffeine (nonprescription stimulant); cotinine (metabolite of nicotine); acetaminophen (nonprescription analgesic); and sulfamethoxazole (prescription antibiotic). The occurrence and distribution of organic wastewater compounds varied considerably among sampling sites, but at least one compound was detected at every location. The most organic wastewater compounds (19) were detected at the Neuse River above U.S. 70 at Smithfield, where two-thirds of the total number of samples were collected. The fewest organic wastewater compounds (1) were detected at the Eno River at Hillsborough. The detection of multiple organic wastewater compounds was common, with a median of 3.5 and as many as 12 compounds observed in individual samples. Some compounds, including acetaminophen, cotinine, tri(2-chloroethyl) phosphate, and metolachlor, were detected at numerous sites and in numerous samples, indicating that they are widely distributed in the environment. Other organic wastewater compounds, including acetyl-hexamethyl tetrahydronaphthalene and hexahydro-hexamethyl cyclopentabenzopyran, were detected in numerous samples but at only one location, indicating that sources of these compounds are more site specific. Results indicate that municipal wastewater may be a source of antibiotics and synthetic musks; however, the three sites in this study that are located downstream from wastewater discharges also receive runoff from agricultural, urban, and rural residential lands. Source identification was not an objective of this study. Concentrations of individual compounds generally were less than 0.5 microgram per liter. No concentrations exceeded Federal drinking-water standards or health advisories, nor water-quality criteria established by the State of North Carolina; however, such criteria are available for only a few of the compounds that were studied. Compared with other surface waters that have been sampled across the United States, the Triangle Area water-supply sites had fewer detections of organic wastewater compounds; however, differences in study design and analytical methods used among studies must be considered when mak

North Carolina

Statistical analysis of major ion and trace element geochemistry of water, 1986-2006, at seven wells transecting the freshwater/saline-water interface of the Edwards aquifer, San Antonio, Texas

This report by the U.S. Geological Survey, in cooperation with the San Antonio Water System, describes the results of a statistical analysis of major ion and trace element geochemistry of water at seven wells transecting the freshwater/saline-water interface of the Edwards aquifer in San Antonio, Texas, either over time or in response to variations in hydrologic conditions. The data used in this report were collected during 1986&ndash;2006. The seven monitoring wells are screened at different depths in the aquifer at three sites that form a generally north-to-south transect. The three wells of the southern site and the deeper of the two middle-site wells are open to the freshwater/saline-water transition zone, which contains saline water. The shallower well of the middle site and the two wells of the northern site are open to the freshwater zone. Mean specific conductance (SC) values were greater at transition-zone wells than at freshwater-zone wells, but SC did not vary systematically with depth. Concentrations of all major ions except bicarbonate were greater at transition-zone wells than at freshwater-zone wells, but concentrations tended to be more variable at freshwater-zone wells. Mean molar ratios of magnesium:calcium, sulfate:chloride, and sodium:chloride were similar at transition-zone wells and freshwater-zone wells. Concentrations of trace elements for many water samples at the seven transect wells were below the laboratory analytical reporting level. Detections of trace elements were more frequent at transition-zone wells, and mean concentrations of cadmium, chromium, copper, lead, and silver were elevated at transition-zone wells relative to freshwater-zone wells. All strong correlations between SC and major ions were positive, and in general there were more and stronger correlations between SC and major ions in the water from the freshwater-zone wells than from the transition-zone wells. Except for the shallowest transition-zone well, the transition-zone wells had relatively few strong correlations overall. The lack of a strong correlation indicates that much of the variability in the major ion concentrations at these wells might be a result of analytical variability caused by the multiple laboratory analytical methods used. In most cases, strong correlations between concentrations of trace elements were positive, and transition-zone wells and freshwater-zone wells had water with a similar number of significant correlations. Principal components analysis indicates dilution of ground water by low-ionic-strength meteoric water at the three freshwater-zone wells and at the shallowest transition-zone well. At the two deeper transition-zone wells at the southern site, principal components analysis indicates that there is no systematic variation in major ion concentrations. At three transition-zone wells, there was a general trend toward less salinity over the 21-year period of sampling. Trends in SC at the freshwater-zone wells were less consistent. There is no systematic change in the direction of trend in SC by water type (saline or fresh), between sites, or with depth. In general, trends in major ion concentrations corresponded to those in SC. For each trace element over the 21-year sampling period, there was either no trend or a downward trend. Relations between SC, major ions, and major ion molar ratios and hydrologic indicators (concurrent or prior time-averaged measures of water level and effective rainfall) were investigated. Correlations between geochemical variables and measures of water level in the freshwater-zone wells were much more frequent than correlations between geochemical variables and measures of water level in the transition-zone wells. There were correlations between SC and all measures of water level at the two freshwater-zone wells at the northern site, but there were no correlations between SC and any measures of water level at any transition-zone wells. SC was correlated with effective rainfall at all freshwater-zone wells and at one transition-zone well. The statistical analyses taken together indicate that the geochemistry at the freshwater-zone wells is more variable than that at the transition-zone wells. The geochemical variability at the freshwater-zone wells might result from dilution of ground water by meteoric water. This is indicated by relatively constant major ion molar ratios; a preponderance of positive correlations between SC, major ions, and trace elements; and a principal components analysis in which the major ions are strongly loaded on the first principal component. Much of the variability at three of the four transition-zone wells might result from the use of different laboratory analytical methods or reporting procedures during the period of sampling. This is reflected by a lack of correlation between SC and major ion concentrations at the transition-zone wells and by a principal components analysis in which the variability is fairly evenly distributed across several principal components. The statistical analyses further indicate that, although the transition-zone wells are less well connected to surficial hydrologic conditions than the freshwater-zone wells, there is some connection but the response time is longer.

Texas

Comparison of seven DNA metabarcoding sampling methods to assess diet in a large avian predator

DNA metabarcoding is a rapidly advancing tool for diet assessment in wildlife ecology. Studies have used a variety of field collection methods to evaluate diet; however, there is a pressing need to understand the differences among sampling methods and the downstream inferential consequences they may have on our ability to document diet accurately and efficiently. We evaluated seven DNA metabarcoding sampling methods to assess the diet of a large avian predator: Buteo lagopus (rough-legged hawk). We collected beak swabs, talon swabs, cheek (buccal) swabs, cloacal swabs, and cloacal loops from captured birds, and collected fecal samples from both captured and uncaptured birds. We described and compared variation in prey recovery within and among the seven sampling methods and identified appropriate analytical methods to compare diet among individuals sampled via different methods. Beak and talon swabs produced the highest prey detection rates, yielded the greatest prey richness per sample, and contributed the most to an individual's total prey richness per sampling occasion compared to other sampling methods. Within individuals sampled using five methods during a single capture occasion, cloacal swabs and cheek swabs positively predicted prey richness and average prey mass, respectively, from fecal samples. While all methods identified similar dominant prey taxa that were consistent with prior diet studies, beak and talon swabs detected greater prey richness at both the individual and population levels. We propose a food residue duration hypothesis whereby methods which sample areas containing food DNA consumed from longer and more continuous pre-sampling time intervals explain variation among sampling methods in observed prey richness. Choice of sampling method can influence predator diet characterization and is particularly important if researchers wish to quantify uncommon diet items or compare diet metrics using samples collected via different methods.

Environmental DNA

Linking geology and health sciences to assess childhood lead poisoning from artisanal gold mining in Nigeria

Background: In 2010, Médecins Sans Frontières discovered a lead poisoning outbreak linked to artisanal gold processing in northwestern Nigeria. The outbreak has killed approximately 400 young children and affected thousands more. Objectives: Our aim was to undertake an interdisciplinary geological- and health-science assessment to clarify lead sources and exposure pathways, identify additional toxicants of concern and populations at risk, and examine potential for similar lead poisoning globally. Methods: We applied diverse analytical methods to ore samples, soil and sweep samples from villages and family compounds, and plant foodstuff samples. Results: Natural weathering of lead-rich gold ores before mining formed abundant, highly gastric-bioaccessible lead carbonates. The same fingerprint of lead minerals found in all sample types confirms that ore processing caused extreme contamination, with up to 185,000 ppm lead in soils/sweep samples and up to 145 ppm lead in plant foodstuffs. Incidental ingestion of soils via hand-to-mouth transmission and of dusts cleared from the respiratory tract is the dominant exposure pathway. Consumption of water and foodstuffs contaminated by the processing is likely lesser, but these are still significant exposure pathways. Although young children suffered the most immediate and severe consequences, results indicate that older children, adult workers, pregnant women, and breastfed infants are also at risk for lead poisoning. Mercury, arsenic, manganese, antimony, and crystalline silica exposures pose additional health threats. Conclusions: Results inform ongoing efforts in Nigeria to assess lead contamination and poisoning, treat victims, mitigate exposures, and remediate contamination. Ore deposit geology, pre-mining weathering, and burgeoning artisanal mining may combine to cause similar lead poisoning disasters elsewhere globally.

Environmental Health Perspectives