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Preliminary preview for a geographic and monitoring program project; a review of point source-nonpoint source effluent trading/offset systems in watersheds

Watershed-based trading and offset systems are being developed to improve policy-maker?s and regulator?s ability to assess nonpoint source impacts in watersheds and to evaluate the efficacy of using market-incentive programs for preserving environmental quality. An overview of the history of successful and failed trading programs throughout the United States suggests that certain political, economic, and scientific conditions within a temporal and spatial setting help meet water quality standards. The current lack of spontaneous trading among dischargers does not mean that a marketable permit trading system is an inherently inefficient regulatory approach. Rather, its infrequent use is the result of institutional and informational barriers. Improving and refining the earth science information and technologies may help determine whether trading is a suitable policy for improving water quality. However, it is debatable whether or not environmental information is the limiting factor. This paper reviews additional factors affecting the potential for instituting a trading policy. The motivation for investigating and reviewing the history of offsets and trading was inspired by a project in the preliminary stages being developed by U.S. Geological Survey Western Geographic Science Center and the Environmental Protection Agency Region IX. An offset feasibility study will be an integrated, map-based approach that incorporates environmental, economic, and statistical information to investigate the potential for using offsets to meet mercury Total Maximum Daily Loads in the Sacramento River watershed. A regional water-quality offset program is being studied that may help known point sources reduce mercury loading more cost effectively by the remediation of abandoned mines or other diffuse sources as opposed to more costly treatment at their own sites. An efficient offset program requires both a scientific basis and methods to translate that science into a regulatory decision framework.

Open-File Report

Assessing water quality from highway runoff at selected sites in North Carolina with the Stochastic Empirical Loading and Dilution Model (SELDM)

In 2015, the U.S. Geological Survey (USGS) entered into a cooperative agreement with the North Carolina Department of Transportation (NCDOT) to develop a North Carolina-enhanced variation of the national Stochastic Empirical Loading and Dilution Model (SELDM) with available North Carolina-specific streamflow and water-quality data and to demonstrate use of the model by documenting selected simulation scenarios. The USGS developed the national SELDM in cooperation with the Federal Highway Administration (FHWA) to provide the tools and techniques necessary for performing stormwater-quality simulations. SELDM uses a stochastic mass-balance approach to estimate combinations of flows, concentrations, and loads of stormwater constituents from the site of interest (often a highway catchment; nonhighway areas, such as a large impervious area at a shopping center complex, also can be used) and the basin upstream from the stormwater outfall to assess the risk for adverse effects of runoff. SELDM also can be used to simulate the effectiveness of volume reduction, hydrograph extension, and water-quality concentration reductions by stormwater best management practices (BMPs), which are designed to help mitigate the effects of runoff on receiving water bodies. Some of the statistical inputs needed for the North Carolina-enhanced SELDM were either calculated or augmented using local or regional data from North Carolina. Streamflow statistics used by SELDM were determined for 266 streamgages across North Carolina on the basis of data available through the 2015 water year. Recession ratio statistics used for triangular hydrographs were also developed for 30 streamgages across the State. The NCDOT identified previous research reports on highway-runoff and BMP studies in North Carolina for review of potential data addition to the national FHWA Highway-Runoff Database (HRDB). Following USGS review of these data, a total of 25,087 event mean concentration values and 1,140 storm events for 39 highway-runoff sites and 195 analytes were uploaded to the national HRDB from six North Carolina highway-runoff research reports and a recent USGS bridge deck runoff study. Using data for 27 streamgages in North Carolina, a total of 57 water-quality transport curves were developed for seven constituents for use in simulating water-quality conditions in the upstream basin. Performance data for three BMPs (bioretention, grass strip or swale, and wetland channel) from NCDOT research data were incorporated into the North Carolina-enhanced SELDM for volume-reduction statistics, including the effectiveness of treating four water-quality constituents (total suspended solids, total nitrogen, total phosphorus, nitrate plus nitrite) and turbidity. Simulations using the North Carolina-enhanced SELDM are presented for two hypothetical upstream basins in the Piedmont ecoregion and one hypothetical highway site to demonstrate how simulations can be used to provide risk-based information about potential effects of stormwater runoff on downstream water quality and the potential for mitigating those risks by using BMPs. The first group of simulations explores the stochastic variability in dilution factors (the ratio of the highway runoff to the total downstream stormflow) for a hypothetical Piedmont rural creek having drainage areas ranging from 1 to 100 square miles. The second group of simulations examines dilution factors based on variations in precipitation, streamflow, and recession ratios for two hypothetical Piedmont upstream basins (rural and urban) where the drainage area was held constant at 25 square miles. These simulations indicate the sensitivity of results to variations in each of the three variables. The third group of simulations examines the effects of varied concentrations in the upstream basin on water-quality conditions downstream from the highway crossing. Variations in upstream water-quality conditions for three constituents (suspended sediment concentration, total nitrogen, and total phosphorus) are based on water-quality transport curves selected from among the 57 curves developed as part of this study to represent low-, medium-, and high-concentration statistics. Simulations completed for this third group also examine the potential effects of grass swale and bioretention BMP treatment on total nitrogen and total phosphorus concentrations in highway runoff. The BMP performance data from the NCDOT research reports were applied in this group of simulations. The stochastic mass-balance approach used in SELDM analyses and simulations provides a strong tool for engineers and water-resource managers to use in exploring a wide range of possible hydrologic and water-quality inputs and their effects on downstream water quality. The results of this study can not only aid engineers and managers in planning for potential adverse effects of runoff at site-specific locations, they can also help the USGS and other Federal and State agencies with oversight responsibilities in stormwater-quality issues to continue gathering data on potential water-quality effects in receiving streams.

North Carolina

Preliminary effects of streambank fencing of pasture land on the quality of surface water in a small watershed in Lancaster County, Pennsylvania

The use of fencing to exclude pastured animals from streams has been recognized as an agricultural best-management practice. Streambank fencing was installed in a small basin within the Mill Creek Watershed of Lancaster County, Pa., during summer 1997 to evaluate the effectiveness of fencing on surface-water quality. A preliminary review of data collected during a pre-treatment, or calibration period (October 1993 through June 1997), and part of the post-treatment period (July 1997 through November 1998) has identified a varied instream nutrient response to streambank fencing. Concentrations of total nitrogen (N) during low-flow periods were significantly reduced by 20 to 31 percent at treated relative to untreated sites, but the yield of total N during low-flow conditions did not change significantly. Low-flow concentrations and yields of total phosphorus (P) did not change significantly at the outlet of the treatment basin, but data from a tributary site (T-2) in the treatment basin showed a 19- to 79-percent increase in the concentration and yield of total P relative to those at untreated sites. The total-P increase was due to increased concentrations of dissolved P. The processes causing the decrease in the concentration of total N and an increase in the concentration of total P were related to stream discharge, which declined after fencing to about one-third lower than the period-of-record mean. Declines in stream discharge after fence installation were caused by lower than normal precipitation. As concentrations of dissolved oxygen decreased in the stream channel as flows decreased, there was increased potential for instream denitrification and solubilization of P from sediments in the stream channel. Vegetative uptake of nitrate could also have contributed to decreased N concentrations. There were few significant changes in concentrations and yields of nutrients during stormflow except for significant reductions of 16 percent for total-N concentrations and 26 percent for total-P concentrations at site T-2 relative to the site at the outlet of the control basin. Suspended-sediment concentrations in the stream were significantly reduced by fencing. These reductions were partially caused by reduced cow access to the stream and hence reduced potential for the cows to destabilize streambanks through trampling. Development of a vegetative buffer along the stream channel after fence installation also helped to retain soil eroding from upgradient land. Reductions in suspended sediment during low flow ranged from 17 to 26 percent; stormflow reductions in suspended sediment ranged from 21 to 54 percent at treated relative to untreated sites. Suspended-sediment yields, however, were significantly reduced only at site T-2, where low-flow and stormflow yields were reduced by about 25 and 10 percent, respectively, relative to untreated sites. Benthic-macroinvertebrate sampling has identified increased number of taxa in the treatment basin after fence installation. Relative to the control basin, there was about a 30-percent increase in the total number of taxa. This increase was most likely related to improved instream habitat as a result of channel revegetation.

Water-Resources Investigations Report

Total dissolved gas, barometric pressure, and water temperature data, lower Columbia River, Oregon and Washington, 1996

Increased levels of total dissolved gas pressure can cause gas-bubble trauma in fish downstream from dams on the Columbia River. In cooperation with the U.S. Army Corps of Engineers, the U.S. Geological Survey collected data on total dissolved gas pressure, barometric pressure, water temperature, and dissolved oxygen pressure at 11 stations on the lower Columbia River from the John Day forebay (river mile 215.6) to Wauna Mill (river mile 41.9) from March to September 1996. Methods of data collection, review, and processing are described in this report. Summaries of daily minimum, maximum, and mean hourly values are presented for total dissolved gas pressure, barometric pressure, and water temperature. Hourly values for these parameters are presented graphically. Dissolved oxygen data are not presented in this report because the quality-control data show that the data have poor precision and high bias. Suggested changes to monitoring procedures for future studies include (1) improved calibration procedures for total dissolved gas and dissolved oxygen to better define accuracy at elevated levels of supersaturation and (2) equipping dissolved oxygen sensors with stirrers because river velocities at the shoreline monitoring stations probably cannot maintain an adequate flow of water across the membrane surface of the dissolved oxygen sensor.

Oregon, Washington

The chemical quality of self-supplied domestic well water in the United States

Existing water quality data collected from domestic wells were summarized to develop the first national‐scale retrospective of self‐supplied drinking water sources. The contaminants evaluated represent a range of inorganic and organic compounds, and although the data set was not originally designed to be a statistical representation of national occurrence, it encompasses large parts of the United States including at least some wells sampled in every state and Puerto Rico. Inorganic contaminants were detected in many of the wells, and concentrations exceeded the U.S. EPA maximum contaminant levels (MCLs; federal drinking water standards used to regulate public drinking water quality) more often than organic contaminants. Of the inorganic constituents evaluated, arsenic concentrations exceeded the MCL (10 μg/L) in ∼11% of the 7580 wells evaluated, nitrate exceeded the MCL (10 mg/L) in ∼8% of the 3465 wells evaluated, uranium‐238 exceeded the MCL (30 μg/L) in ∼4% of the wells, and radon‐222 exceeded 300 and 4000 pCi/L (potential drinking water standards currently under review by the U.S. EPA) in ∼75% and 9% of the wells, respectively. The MCLs for total mercury and fluoride were each exceeded in <1% of the wells evaluated. The MCL was exceeded in <1% of all wells for all anthropogenically derived organic contaminants evaluated and was not exceeded for many contaminants. In addition, 10 contaminants evaluated do not currently have an MCL. Atrazine, however, was detected in 24% of the wells evaluated and was the most frequently detected organic contaminant of the 28 organic contaminants evaluated in this study. Simazine and metolachlor each were detected in ∼9% of all wells and tied for second in frequency of detection for organic contaminants. The third and fourth most frequently detected organic contaminants were methyl tert ‐butyl ether (MTBE) (6%) and chloroform (5%), respectively. Because the water quality of domestic wells is not federally regulated or nationally monitored, this study provides a unique, previously nonexistent, perspective on the quality of the self‐supplied drinking water resources used by ∼45 million Americans in the United States.

Ground Water Monitoring and Remediation

Pilot studies for the North American Soil Geochemical Landscapes Project - Site selection, sampling protocols, analytical methods, and quality control protocols

In 2004, the US Geological Survey (USGS) and the Geological Survey of Canada sampled and chemically analyzed soils along two transects across Canada and the USA in preparation for a planned soil geochemical survey of North America. This effort was a pilot study to test and refine sampling protocols, analytical methods, quality control protocols, and field logistics for the continental survey. A total of 220 sample sites were selected at approximately 40-km intervals along the two transects. The ideal sampling protocol at each site called for a sample from a depth of 0-5 cm and a composite of each of the O, A, and C horizons. The <2-mm fraction of each sample was analyzed for Al, Ca, Fe, K, Mg, Na, S, Ti, Ag, As, Ba, Be, Bi, Cd, Ce, Co, Cr, Cs, Cu, Ga, In, La, Li, Mn, Mo, Nb, Ni, P, Pb, Rb, Sb, Sc, Sn, Sr, Te, Th, Tl, U, V, W, Y, and Zn by inductively coupled plasma-mass spectrometry and inductively coupled plasma-atomic emission spectrometry following a near-total digestion in a mixture of HCl, HNO 3 , HClO 4 , and HF. Separate methods were used for Hg, Se, total C, and carbonate-C on this same size fraction. Only Ag, In, and Te had a large percentage of concentrations below the detection limit. Quality control (QC) of the analyses was monitored at three levels: the laboratory performing the analysis, the USGS QC officer, and the principal investigator for the study. This level of review resulted in an average of one QC sample for every 20 field samples, which proved to be minimally adequate for such a large-scale survey. Additional QC samples should be added to monitor within-batch quality to the extent that no more than 10 samples are analyzed between a QC sample. Only Cr (77%), Y (82%), and Sb (80%) fell outside the acceptable limits of accuracy (% recovery between 85 and 115%) because of likely residence in mineral phases resistant to the acid digestion. A separate sample of 0-5-cm material was collected at each site for determination of organic compounds. A subset of 73 of these samples was analyzed for a suite of 19 organochlorine pesticides by gas chromatography. Only three of these samples had detectable pesticide concentrations. A separate sample of A-horizon soil was collected for microbial characterization by phospholipid fatty acid analysis (PLFA), soil enzyme assays, and determination of selected human and agricultural pathogens. Collection, preservation and analysis of samples for both organic compounds and microbial characterization add a great degree of complication to the sampling and preservation protocols and a significant increase to the cost for a continental-scale survey. Both these issues must be considered carefully prior to adopting these parameters as part of the soil geochemical survey of North America.

Applied Geochemistry

Assessment of interim flow water-quality data of the San Joaquin River restoration program and implications for fishes, California, 2009-11

After more than 50 years of extensive water diversion for urban and agriculture use, a major settlement was reached among the U.S. Departments of the Interior and Commerce, the Natural Resources Defense Council, and the Friant Water Users Authority in an effort to restore the San Joaquin River. The settlement received Federal court approval in October 2006 and established the San Joaquin River Restoration Program, a multi-agency collaboration between State and Federal agencies to restore and maintain fish populations, including Chinook salmon, in the main stem of the river between Friant Dam and the confluence with the Merced River. This is to be done while avoiding or minimizing adverse water supply effects to all of the Friant Division contractors that could result from restoration flows required by the settlement. The settlement stipulates that water- and sediment-quality data be collected to help assess the restoration goals. This report summarizes and evaluates water-quality data collected in the main stem of the San Joaquin River between Friant Dam and the Merced River by the U.S. Bureau of Reclamation for the San Joaquin River Restoration Program during 2009-11. This summary and assessment consider sampling frequency for adequate characterization of variability, sampling locations for sufficient characterization of the San Joaquin River Restoration Program restoration reach, sampling methods for appropriate media (water and sediment), and constituent reporting limits. After reviewing the water- and sediment-quality results for the San Joaquin River Restoration Program, several suggestions were made to the Fisheries Management Work Group, a division of the San Joaquin River Restoration Program that focuses solely on the reintroduction strategies and health of salmon and other native fishes in the river. Water-quality results for lead and total organic carbon exceeded the Surface Water Ambient Monitoring Program Basin Plan Objectives for the San Joaquin Basin, and results for copper exceeded the U.S. Environmental Protection Agency Office of Pesticide Programs' aquatic-life chronic and acute benchmarks for invertebrates. One sediment sample contained detections of pyrethroid pesticides bifenthrin, lambda-cyhalothrin, and total permethrin at concentrations above published chronic toxicity thresholds.

California

Water quality in alluvial aquifers of the southern Rocky Mountains Physiographic Province, upper Colorado River basin, Colorado, 1997

Water-quality samples were collected in the summer of 1997 from 45 sites (43 wells and 2 springs) in selected alluvial aquifers throughout the Southern Rocky Mountains physiographic province of the Upper Colorado River Basin study unit as part of the U.S. Geological Survey National Water-Quality Assessment Program. The objective of this study was to assess the water-quality conditions in selected alluvial aquifers in the Southern Rocky Mountains physiographic province. Alluvial aquifers are productive aquifers in the Southern Rocky Mountains physiographic province and provide for easily developed wells. Water-quality samples were collected from areas where ground water is used predominantly for domestic or public water supply. Twenty-three of the 45 sites sampled were located in or near mining districts. No statistical differences were observed between the mining sites and sites not associated with mining activities for the majority of the constituents analyzed. Water samples were analyzed for major ions, nutrients, dissolved organic carbon, trace elements, radon-222, pesticides, volatile organic compounds, bacteria, and methylene blue active substances. In addition, field parameters consisting of water temperature, specific conductance, dissolved oxygen, pH, turbidity, and alkalinity were measured at all sites. Specific conductance for the ground-water sites ranged from 57 to 6,650 microsiemens per centimeter and had higher concentrations measured in areas such as the northwestern part of the study unit. Dissolved oxygen ranged from 0.1 to 6.0 mg/L (milligrams per liter) and had a median concentration of 2.9 mg/L. The pH field values ranged from 6.1 to 8.1; about 4 percent of the sites (2 of 45) had pH values outside the range of 6.5 to 8.5 and so did not meet the U.S. Environmental Protection Agency secondary maximum contaminant level standard for drinking water. About 5 percent (2 of 43) of the samples exceeded the U.S. Environmental Protection Agency recommended turbidity value of 5 nephelometric turbidity units; one of these samples was from a monitoring well. The U.S. Environmental Protection Agency secondary maximum contaminant levels for dissolved solids, sulfate, iron, and manganese were exceeded at some of the sites. Higher dissolved-solids concentrations were detected where sedimentary rocks are exposed, such as in the northwestern part of the Southern Rocky Mountains physiographic province. The dominant water compositions for the sites sampled are calcium, magnesium, and bicarbonate. However, sites in areas where sedimentary rocks are exposed and sites located in or near mining areas show more sulfate-dominated waters. Nutrient concentrations were less than the U.S. Environmental Protection Agency drinking-water standards. Only one site had a nitrate concentration greater than 3.0 mg/L, a level indicating possible influence from human activities. No significant differences among land-use/land-cover classifications (forest, rangeland, and urban) for drinking-water wells (42 sites) were identified for dissolved-solids, sulfate, nitrate, iron or manganese concentrations. Radon concentrations were higher in parts of the study unit where Precambrian rocks are exposed. All radon concentrations in ground water exceeded the previous U.S. Environmental Protection Agency proposed maximum contaminant level for drinking water, which has been withdrawn pending further review. Pesticide detections were at concentrations below the reporting limits and were too few to allow for comparison of the data. Eight volatile organic compounds were detected at six sites; all concentrations complied with U.S. Environmental Protection Agency drinking-water standards. Total coliform bacteria were detected at six sites, but no Escherichia coli ( E. coli ) was detected. Methylene blue active substances were detected at three sites at concentrations just above the reporting limit. Overall, the water quality in the Southern Rocky Mountains physiographic province is suitable for most uses, but natural and human factors affect the water quality.

Colorado

Water quality and aquatic toxicity data of 2002 spring thaw conditions in the upper Animas River watershed, Silverton, Colorado

This report presents hydrologic, water-quality, and biologic toxicity data collected during the annual spring thaw of 2002 in the upper Animas River watershed near Silverton, Colorado. The spring-thaw runoff is a concern because elevated concentrations of iron oxyhydroxides can contain sorbed trace metals that are potentially toxic to aquatic life. Water chemistry of streams draining the San Juan Mountains is affected by natural acid drainage and weathering of hydrothermal altered volcanic rocks and by more than a century of mining activities. The timing of the spring-thaw sampling effort was determined by reviewing historical climate and stream-flow hydrographs and current weather conditions. Twenty-one water-quality samples were collected between 11:00 AM March 27, 2002 and 6:00 PM March 30, 2002 to characterize water chemistry at the A-72 gage on the upper Animas River below Silverton. Analyses of unfiltered water at the A-72 gage showed a relation between turbidity and total-recoverable iron concentrations, and showed diurnal patterns. Copper and lead concentrations were related to iron concentrations, indicating that these elements are probably sorbed to colloidal iron material. Calcium, strontium, and sulfate concentrations showed overall decreasing trends due to dilution, but the loads of those constituents increased over the sampling period. Nine water-quality samples were collected near the confluence of Mineral Creek with the Animas River, the confluence of Cement Creek with the Animas River, and on the upper Animas River above the confluence with Cement Creek (three samples at each site). A total of six bulk water-toxicity samples were collected before, during, and after the spring thaw from the Animas River at the A-72 gage site. Toxicity tests conducted with the bulk water samples on amphipods did not show strong differences in toxicity among the three sampling periods; however, toxicity of river water to fathead minnows showed a decreasing trend during the course of the study.

Colorado

Science summary in support of Manatee Protection Area (MPA) design in Puerto Rico

The Antillean manatee (Trichechus manatus manatus), a subspecies of the West Indian manatee, is listed as endangered by the US Department of Interior. In accordance with its listing, the U.S. Fish and Wildlife Service’s Caribbean Field Office (USFWS) is mandated to create one or more Manatee Protection Areas (MPAs) for Puerto Rico. Designation of these areas must comply with the legal definition of an MPA’s purpose: to prevent or reduce take of manatees (CFR 50: 44 FR 60964, Oct. 22, 1979). To meet this goal, we pursued two objectives: 1) identify areas which include the specific ecological attributes necessary to support manatee populations, and 2) identify areas where take can be reduced through approved MPA regulatory frameworks. We achieved these objectives through literature review, expert elicitation, and geospatial modeling. This report delivers to USFWS a set of nine potential MPA regions. These regions represent the spatial realization of experts’ hypotheses regarding manatee requirements and threats, and the potential to implement MPA strategies (e.g. watercraft access, speed regulations, signage and boater education). The nine regions are compared based on a number of factors, including their potential to reduce take, quality of the habitat encompassed, and total area. These maps and statistics serve as suitable starting points to select one or more MPA sites, but we recommend that the mapped attributes and threats (i.e., boating activity) of MPAs be ground-truthed to visually confirm the local presence of resources, threats, and manatees before any area is selected. Once established, the effectiveness of MPAs can be monitored and updated through processes of adaptive monitoring and management. Aerial surveys, radio tracking studies, and public surveys are all valuable tools to assess the success of an MPA. Establishing MPAs is a management action that, integrated within the species Recovery Plan, should enhance the conservation of manatees.

Cooperator Science Series

Characterization of the water resources of the Pamunkey River watershed in Virginia—A review of water science, management, and traditional ecological knowledge

In central Virginia, the Pamunkey Indian Tribe and Reservation are facing increasingly complex water resource issues related to quantity and quality. Documentation of surface-water, groundwater, water quality, land subsidence, sea-level rise, and river ecology issues in the Pamunkey River watershed and incorporation of traditional ecological knowledge into these research topics may improve understanding of the water resources broadly. This report summarizes the relevant traditional ecological knowledge and scientific literature to elucidate gaps in the total combined knowledge of a suite of water science topics concerning the Pamunkey River watershed. This suite of water science topics includes some of the issues that the Pamunkey Indian Tribe and Reservation are facing within the watershed: fragmentation of streams and management of streamflow, flooding, degrading water quality, groundwater extraction, relative sea-level rise, rapid changes in ecosystems, loss of ecological and biological diversity, and climate change. Gaps in total combined knowledge are pervasive throughout each of these water resource topics. Identifying these knowledge gaps can help inform future research and management strategies.

Virginia

Use of set blanks in reporting pesticide results at the U.S. Geological Survey National Water Quality Laboratory, 2001-15

Executive Summary Background .—Pesticide results from the U.S. Geological Survey (USGS) National Water Quality Laboratory (NWQL) are used for water-quality assessments by many agencies and organizations. The USGS is committed to providing data of the highest possible quality to the consumers of its data. A cooperator’s inquiries about specific pesticide detections in water revealed potential laboratory contamination issues for some results. Consequently, the USGS conducted an extensive evaluation of potential low-level contamination related to processing or analysis of water-quality samples at NWQL for 21 pesticide compounds of interest to the cooperator. This is the most comprehensive study of NWQL pesticide quality-control (QC) results to date. Purpose and scope .—The purpose of this study was to document protocols used by the NWQL to censor pesticide results and to determine the effects of laboratory contamination—as determined from detections in laboratory set blanks—on pesticide detections in groundwater and surface-water samples. More than 30,000 pesticide results from 113 selected batches of samples (2 percent or less of total batches) analyzed by the NWQL during the 15 years from 2001 to 2015 were reviewed. All laboratory results from the selected batches, including results from environmental (surface water and groundwater) and QC (set-blank, blind-blank, and blind-spike) samples, were evaluated. The study includes results for 21 pesticide compounds analyzed in groundwater and surface-water samples collected across the United States. Eleven pesticide compounds were analyzed by a gas chromatography/mass spectrometry method and 10 compounds by a liquid chromatography/mass spectrometry method. Objectives and methods .—The objectives of this study were to (1) determine the characteristics of laboratory contamination over time, (2) compare distributions of pesticide results in set blanks with distributions in environmental samples, (3) evaluate the potential for false-positive and false-negative reporting of results, and (4) evaluate the effects of reevaluating historical pesticide results using 2017 compound identification protocols on detections of pesticides in groundwater and surface-water samples. The 113 instrument batches selected for this study contained detections of one or more of the 21 pesticide compounds in set blanks or were among those batches with the highest pesticide detection frequencies in set blanks. As a result, the dataset for this study was targeted toward pesticides and batches with laboratory contamination. The objectives were addressed by statistically comparing environmental and set-blank results; computing moving averages of set-blank detection frequencies to identify periods of episodic contamination; and using summary statistics, tabular summaries, and graphical approaches, such as time-series plots and cumulative distribution functions. Results .— Objective 1 : Laboratory contamination, as determined by pesticide detections in set blanks, was found in 13 percent of set-blank results from the 113 targeted batches included in this study (as compared to 6 percent of set-blank results from all 7,620 batches analyzed during the study period). It is estimated that 92 percent of the laboratory contamination during the study period was episodic, meaning that it occurred during discrete periods of time. All 21 of the targeted pesticide compounds had periods of episodic contamination, with most episodes ranging in duration from about 1 to 8 months. The remaining 8 percent of laboratory contamination was random or from a known source (deterministic). Objective 2 : For some compounds, graphs of cumulative distribution functions of the entire distributions of set-blank and environmental samples overlap, suggesting that there is no difference in the distributions of the two types of samples. However, time-series graphs show that detections in set blanks often occur at different times (sometimes separated by years) than detections in environmental samples, indicating clear differences in those distributions, and indicating the importance of evaluating the timing of detections in all sample types. For most compounds detected in set-blank and environmental samples, detection frequencies were significantly greater in set blanks than in groundwater or surface-water samples ( p <0.05). There are several explanations for this finding, including that the 113 batches of samples chosen for this study targeted batches with detections in set blanks or that detections in set-blank samples were historically determined with less stringent identification criteria than for environmental samples (groundwater and surface-water samples). Objective 3 : The false-positive and false-negative rates from blind samples submitted during the study period by the USGS Quality Systems Branch generally were less than 1 and 5 percent, respectively, for the 21 pesticides. The only compound with a false-positive rate greater than 1 percent was flumetsulam (2.6 percent), indicating that there is a higher likelihood of flumetsulam being reported as a detection when it is not present in an environmental sample compared with the reporting of other compounds. Objective 4 : Altogether, for data in targeted batches, NWQL would have reported 0.1 percent of results from groundwater samples and 1.4 percent of results from surface-water samples differently if 2017 identification protocols were applied to historical pesticide results. In most of these cases, detections observed in historical results would change to nondetections. The small percentages of changes that would occur if historical data were reevaluated indicate that historical protocols used by the NWQL to identify detections in environmental samples were robust and produced results that are predominantly consistent with current [2017] practices. Conclusions .—The NWQL produces high-quality pesticide results at environmentally relevant concentrations. NWQL identification protocols and censoring practices are largely effective at minimizing the reporting of false-positive and false-negative results. Laboratory contamination, when it occurred, tended to occur in episodes; thus, evaluating the timing and magnitude of detections in set blanks relative to detections in environmental samples was determined to be an important consideration for analysis of environmental results. Because NWQL censoring practices do not address all types and occurrences of laboratory contamination, options for additional censoring practices are provided for data users with more specific or stringent data-quality objectives. The methods used to analyze the 21 compounds for this report can similarly be applied to all 173 pesticide compounds that were analyzed by the NWQL during the same time period. This study also has helped to identify potential improvements in reporting USGS data, such as conducting more frequent review of set-blank datasets.

Scientific Investigations Report

Quality-Assurance Data for Routine Water Analyses by the U.S. Geological Survey Laboratory in Troy, New York - July 2005 through June 2007

The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance and quality-control data were stored in the laboratory's Lab Master data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality control samples analyzed from July 2005 through June 2007. Results for the quality-control samples for 19 analytical procedures were evaluated for bias and precision. Control charts indicate that data for eight of the analytical procedures were occasionally biased for either high-concentration or low-concentration samples but were within control limits; these procedures were: total aluminum, calcium, magnesium, nitrate (colorimetric method), potassium, silicon, sodium, and sulfate. Eight of the analytical procedures were biased throughout the analysis period for the high-concentration sample, but were within control limits; these procedures were: total aluminum, calcium, dissolved organic carbon, chloride, nitrate (ion chromatograph), potassium, silicon, and sulfate. The magnesium and pH procedures were biased throughout the analysis period for the low-concentration sample, but were within control limits. The acid-neutralizing capacity, total monomeric aluminum, nitrite, and specific conductance procedures were biased for the high-concentration and low-concentration samples, but were within control limits. Results from the filter-blank and analytical-blank analyses indicated that the procedures for 16 of 17 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. The data-quality objective was not met for dissolved organic carbon. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 18 of the 21 analytes. At least 93 percent of the samples met data-quality objectives for all analytes except acid-neutralizing capacity (85 percent of samples met objectives), total monomeric aluminum (83 percent of samples met objectives), total aluminum (85 percent of samples met objectives), and chloride (85 percent of samples met objectives). The ammonium and total dissolved nitrogen did not meet the data-quality objectives. Results of the USGS interlaboratory Standard Reference Sample (SRS) Project met the Troy Laboratory data-quality objectives for 87 percent of the samples analyzed. The P-sample (low-ionic-strength constituents) analysis had two outliers each in two studies. The T-sample (trace constituents) analysis and the N-sample (nutrient constituents) analysis had one outlier each in two studies. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 85 percent of the samples met data-quality objectives for 11 of the 14 analytes; the exceptions were acid-neutralizing capacity, total aluminum and ammonium. Data-quality objectives were not met in 41 percent of samples analyzed for acid-neutralizing capacity, 50 percent of samples analyzed for total aluminum, and 44 percent of samples analyzed for ammonium. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 86 percent of the samples analyzed for calcium, magnesium, pH, potassium, and sodium. Data-quality objectives were met by 76 percent of the samples analyzed for chloride, 80 percent of the samples analyzed for specific conductance, and 77 percent of the samples analyzed for sulfate.

Open-File Report

Quality-assurance data for routine water analyses by the U.S. Geological Survey Laboratory in Troy, New York—July 1995 through June 1997

The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) office in Troy, N.Y. analyzes samples collected by USGS projects in the Northeast. The laboratory&rsquo;s quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures developed to ensure proper sample collection, processing, and analysis. For the time period addressed in this report, the quality-assurance/quality-control data were stored in the laboratory&rsquo;s SAS data-management system, which provides efficient review, compilation, and plotting of quality-assurance/quality-control data. This report presents and discusses samples analyzed from July 1995 through June 1997. Quality-control results for 19 analytical procedures were evaluated for bias and precision. Control charts show that data from ten of the analytical procedures were biased throughout the analysis period for either high-concentration or low-concentration samples but were within control limits; these procedures were: acid-neutralizing capacity, total monomeric aluminum, ammonium, calcium, chloride, dissolved organic carbon, magnesium, nitrate (ion chromatography), nitrate (colorimetric method), and sulfate. Four of the analytical procedures were occasionally biased but were within control limits; they were: fluoride, pH, silicon, and sodium. Results from the filter-blank and analytical-blank analyses indicate that all analytical procedures in which blanks were run were within control limits, although values for a few blanks were outside the control limits. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in 14 of the 19 procedures. Data-quality objectives (DQO&rsquo;s) were met by at least 92 percent of the samples analyzed in all procedures except acid neutralizing capacity (80 percent of samples met objectives), total monomeric aluminum (87 percent of samples met objectives), organic monomeric aluminum (89 percent of samples met objectives), and chloride (89 percent of samples met objectives). The data are insufficient to evaluate the DQO&rsquo;s for total aluminum. Results of the USGS interlaboratory Standard Reference Sample Program indicated acceptable data quality for most constituents over the time period. The results of the P-sample (low-ionic strength constituent) analysis indicated high data quality with good ratings in all studies. The T-sample (trace constituent) had unacceptable ratings in two studies, but received satisfactory ratings in the others. The N-sample (nutrient constituent) studies had an unacceptable rating in one and an excellent rating in the other. Environment Canada&rsquo;s NWRI program results indicated that at least 90 percent of the samples met data-quality objectives in 9 of the 12 analyses; exceptions were calcium, chloride, and silicon. Data-quality objectives were not met for calcium samples in two NWRI studies, but all of the samples analyzed were within control limits for the remaining studies. Data-quality objectives were not met for 32 percent of samples analyzed for chloride and 27 percent of samples analyzed for silicon. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 90 percent of the calcium, pH, potassium, and sodium samples. Data-quality objectives were met by 77 percent of the chloride samples, 83 percent of the magnesium samples, and 80 percent of the sulfate samples. There is insufficient data to evaluate the specific conductance samples.

Open-File Report

Annual water-resources review, White Sands Missile Range, New Mexico, 1978

Ground-water data were collected in 1978 at White Sands Missile Range in south-central New Mexico. Total ground-water pumpage in 1978 was 692,045,700 gallons or 7,248,300 less than in 1977. Wells at the Post Headquarters produced 98 percent of the total volume. Water levels in test wells around the Post Headquarters well field show seasonal declines ranging from 14.78 feet to 0.71 feet. The water samples collected from the supply wells show that the chemical quality of the water is slightly better during the period of greatest declines. (Woodard-USGS)

Open-File Report

Quality-assurance data for routine water analyses by the U.S. Geological Survey laboratory in Troy, New York - July 2003 through June 2005

The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance and quality-control data were stored in the laboratory's Lab Master data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality control samples analyzed from July 2003 through June 2005. Results for the quality-control samples for 20 analytical procedures were evaluated for bias and precision. Control charts indicate that data for five of the analytical procedures were occasionally biased for either high-concentration or low-concentration samples but were within control limits; these procedures were: acid-neutralizing capacity, total monomeric aluminum, pH, silicon, and sodium. Seven of the analytical procedures were biased throughout the analysis period for the high-concentration sample, but were within control limits; these procedures were: dissolved organic carbon, chloride, nitrate (ion chromatograph), nitrite, silicon, sodium, and sulfate. The calcium and magnesium procedures were biased throughout the analysis period for the low-concentration sample, but were within control limits. The total aluminum and specific conductance procedures were biased for the high-concentration and low-concentration samples, but were within control limits. Results from the filter-blank and analytical-blank analyses indicate that the procedures for 17 of 18 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. The data-quality objective was not met for dissolved organic carbon. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 18 of the 22 analytes. At least 85 percent of the samples met data-quality objectives for all analytes except total monomeric aluminum (82 percent of samples met objectives), total aluminum (77 percent of samples met objectives), chloride (80 percent of samples met objectives), fluoride (76 percent of samples met objectives), and nitrate (ion chromatograph) (79 percent of samples met objectives). The ammonium and total dissolved nitrogen did not meet the data-quality objectives. Results of the USGS interlaboratory Standard Reference Sample (SRS) Project indicated good data quality over the time period, with ratings for each sample in the satisfactory, good, and excellent ranges or less than 10 percent error. The P-sample (low-ionic-strength constituents) analysis had one marginal and two unsatisfactory ratings for the chloride procedure. The T-sample (trace constituents)analysis had two unsatisfactory ratings and one high range percent error for the aluminum procedure. The N-sample (nutrient constituents) analysis had one marginal rating for the nitrate procedure. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 84 percent of the samples met data-quality objectives for 11 of the 14 analytes; the exceptions were ammonium, total aluminum, and acid-neutralizing capacity. The ammonium procedure did not meet data quality objectives in all studies. Data-quality objectives were not met in 23 percent of samples analyzed for total aluminum and 45 percent of samples analyzed acid-neutralizing capacity. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 86 percent of the samples analyzed for calcium, chloride, fluoride, magnesium, pH, potassium, sodium, and sulfate. Data-quality objectives were not met by samples analyzed for fluoride.

Open-File Report

Quality-Assurance Data for Routine Water Analyses by the U.S. Geological Survey Laboratory in Troy, New York-July 1997 through June 1999

The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance/quality-control data for the time period addressed in this report were stored in the laboratory's SAS data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality- control samples analyzed from July 1997 through June 1999. Results for the quality-control samples for 18 analytical procedures were evaluated for bias and precision. Control charts indicate that data for eight of the analytical procedures were occasionally biased for either high-concentration and (or) low-concentration samples but were within control limits; these procedures were: acid-neutralizing capacity, total monomeric aluminum, total aluminum, ammonium, calcium, chloride, specific conductance, and sulfate. The data from the potassium and sodium analytical procedures are insufficient for evaluation. Results from the filter-blank and analytical-blank analyses indicate that the procedures for 11 of 13 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. Blank analysis results for chloride showed that 22 percent of blanks did not meet data-quality objectives and results for dissolved organic carbon showed that 31 percent of the blanks did not meet data-quality objectives. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 14 of the 18 analytes. At least 90 percent of the samples met data-quality objectives for all analytes except total aluminum (70 percent of samples met objectives) and potassium (83 percent of samples met objectives). Results of the USGS interlaboratory Standard Reference Sample (SRS) Project indicated good data quality for most constituents over the time period. The P-sample (low-ionic-strength constituents) analysis had good ratings in two of these studies and a satisfactory rating in the third. The results of the T-sample (trace constituents) analysis indicated high data quality with good ratings in all three studies. The N-sample (nutrient constituents) studies had one each of excellent, good, and satisfactory ratings. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 80 percent of the samples met data-quality objectives for 9 of the 13 analytes; the exceptions were dissolved organic carbon, ammonium, chloride, and specific conductance. Data-quality objectives were not met for dissolved organic carbon in two NWRI studies, but all of the samples were within control limits for the last study. Data-quality objectives were not met in 41 percent of samples analyzed for ammonium, 25 percent of samples analyzed for chloride, and 30 percent of samples analyzed for specific conductance. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 84 percent of the samples analyzed for calcium, chloride, magnesium, pH, and potassium. Data-quality objectives were met by 73 percent of those analyzed for sulfate. The data-quality objective was not met for sodium. The data are insufficient for evaluation of the specific conductance results.

Open-File Report

Quality-Assurance Data for Routine Water Analyses by the U.S. Geological Survey Laboratory in Troy, New York--July 1999 through June 2001

The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance and quality-control data were stored in the laboratory's LabMaster data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality-control samples analyzed from July 1999 through June 2001. Results for the quality-control samples for 18 analytical procedures were evaluated for bias and precision. Control charts indicate that data for eight of the analytical procedures were occasionally biased for either high-concentration or low-concentration samples but were within control limits; these procedures were: acid-neutralizing capacity, total monomeric aluminum, total aluminum, calcium, chloride and nitrate (ion chromatography and colormetric method) and sulfate. The total aluminum and dissolved organic carbon procedures were biased throughout the analysis period for the high-concentration sample, but were within control limits. The calcium and specific conductance procedures were biased throughout the analysis period for the low-concentration sample, but were within control limits. The magnesium procedure was biased for the high-concentration and low concentration samples, but was within control limits. Results from the filter-blank and analytical-blank analyses indicate that the procedures for 14 of 15 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. The data-quality objective was not met for dissolved organic carbon. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 17 of the 18 analytes. At least 90 percent of the samples met data-quality objectives for all analytes except ammonium (81 percent of samples met objectives), chloride (75 percent of samples met objectives), and sodium (86 percent of samples met objectives). Results of the USGS interlaboratory Standard Reference Sample (SRS) Project indicated good data quality over the time period, with most ratings for each sample in the good to excellent range. The P-sample (low-ionic-strength constituents) analysis had one satisfactory rating for the specific conductance procedure in one study. The T-sample (trace constituents) analysis had one satisfactory rating for the aluminum procedure in one study and one unsatisfactory rating for the sodium procedure in another. The remainder of the samples had good or excellent ratings for each study. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 89 percent of the samples met data-quality objectives for 10 of the 14 analytes; the exceptions were ammonium, total aluminum, dissolved organic carbon, and sodium. Results indicate a positive bias for the ammonium procedure in all studies. Data-quality objectives were not met in 50 percent of samples analyzed for total aluminum, 38 percent of samples analyzed for dissolved organic carbon, and 27 percent of samples analyzed for sodium. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 91 percent of the samples analyzed for calcium, chloride, fluoride, magnesium, pH, potassium, and sulfate. Data-quality objectives were met by 75 percent of the samples analyzed for sodium and 58 percent of the samples analyzed for specific conductance.

Open-File Report