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Prediction and visualization of redox conditions in the groundwater of Central Valley, California

Regional-scale, three-dimensional continuous probability models, were constructed for aspects of redox conditions in the groundwater system of the Central Valley, California. These models yield grids depicting the probability that groundwater in a particular location will have dissolved oxygen (DO) concentrations less than selected threshold values representing anoxic groundwater conditions, or will have dissolved manganese (Mn) concentrations greater than selected threshold values representing secondary drinking water-quality contaminant levels (SMCL) and health-based screening levels (HBSL). The probability models were constrained by the alluvial boundary of the Central Valley to a depth of approximately 300 m. Probability distribution grids can be extracted from the 3-D models at any desired depth, and are of interest to water-resource managers, water-quality researchers, and groundwater modelers concerned with the occurrence of natural and anthropogenic contaminants related to anoxic conditions. Models were constructed using a Boosted Regression Trees (BRT) machine learning technique that produces many trees as part of an additive model and has the ability to handle many variables, automatically incorporate interactions, and is resistant to collinearity. Machine learning methods for statistical prediction are becoming increasing popular in that they do not require assumptions associated with traditional hypothesis testing. Models were constructed using measured dissolved oxygen and manganese concentrations sampled from 2767 wells within the alluvial boundary of the Central Valley, and over 60 explanatory variables representing regional-scale soil properties, soil chemistry, land use, aquifer textures, and aquifer hydrologic properties. Models were trained on a USGS dataset of 932 wells, and evaluated on an independent hold-out dataset of 1835 wells from the California Division of Drinking Water. We used cross-validation to assess the predictive performance of models of varying complexity, as a basis for selecting final models. Trained models were applied to cross-validation testing data and a separate hold-out dataset to evaluate model predictive performance by emphasizing three model metrics of fit: Kappa; accuracy; and the area under the receiver operator characteristic curve (ROC). The final trained models were used for mapping predictions at discrete depths to a depth of 304.8 m. Trained DO and Mn models had accuracies of 86–100%, Kappa values of 0.69–0.99, and ROC values of 0.92–1.0. Model accuracies for cross-validation testing datasets were 82–95% and ROC values were 0.87–0.91, indicating good predictive performance. Kappas for the cross-validation testing dataset were 0.30–0.69, indicating fair to substantial agreement between testing observations and model predictions. Hold-out data were available for the manganese model only and indicated accuracies of 89–97%, ROC values of 0.73–0.75, and Kappa values of 0.06–0.30. The predictive performance of both the DO and Mn models was reasonable, considering all three of these fit metrics and the low percentages of low-DO and high-Mn events in the data.

California

Research plan and preliminary results: A field research site for emerging contaminants in Iowa

Research has recently documented the prevalence of a wide variety of pharmaceuticals and other emerging contaminants (ECs) in streams across the United States. Wastewater treatment plants (WWTPs) have been found to be an important source and collection point of ECs to streams as many ECs are incompletely removed during treatment. To investigate the complex in-stream processes (e.g., dilution, sorption, degradation, dispersion, etc.) that can affect ECs following their input from a WWTP and determining if such input is having an effect on the aquatic ecosystem requires the integration of multi-disciplinary efforts at a carefully selected field site. Preliminary work has identified an 8-km reach of Fourmile Creek in central Iowa as an ideal research site to investigate such important research questions pertaining to ECs. Unique aspects of Fourmile Creek included: (1) it single source effluent-dominated stream, (2) background data document the input of a wide variety of ECs from WWTP discharge, (3) small basin size, (4) relatively simple flow system, (5) background data suggest that undefined processes are taking place decreasing the level of select ECs during stream transport, (6) the WWTP uses a treatment technology (activated sludge) typical of many towns in Iowa and the United States (7) a hydrogeologic setting of a low-gradient, small stream (average discharge less than 1.41 m³/s) in glacial drift is typical of many areas in Iowa and across the Midwest, and (8) the existence of a low-head clam approximately 2 km upstream of the WWTP outfall allowing more accurate "above WWTP" and "below WWTP" comparisons in aquatic ecosystems. Furthermore, the WWTP is scheduled to close by 2011 providing a unique opportunity to determine how stream hydrology, water chemistry and aquatic biota react to the removal of the primary source of flow and ECs in this system. This will allow a novel "before" and "after" assessment not previously available in EC research. Research to date at the site has included installation of a streamflow gauging station, dye-tracing tests (to determine water travel times), Lagrangian water-quality sampling at two flow/water temperature regimes, and sampling for ECs in bed sediment. Selected fish have been collected for analysis and identification. In addition, basic fish community and fish health assessment for different seasons and spawning conditions are being analyzed. The research "framework" is unique at Fourmile Creek for investigating the important question of how ECs are transported through the environment and if the presence of such compounds is having a deleterious effect on aquatic ecosystems.

Iowa

Selected water-resources activities of the U.S. Geological Survey in New England in 2017

The New England Water Science Center of the U.S. Geological Survey (USGS) is headquartered in Pembroke, New Hampshire, with offices in East Hartford, Connecticut; Augusta, Maine; Northborough, Massachusetts; and Montpelier, Vermont. The areas of expertise covered by the water science center’s staff of 130 include aquatic biology, chemistry, geographic information systems, geology, hydrologic sciences and engineering, and water use.

Connecticut, Maine, Massachusetts, New Hampshire,

A compilation of whole-rock and glass major-element geochemistry of Kilauea Volcano, Hawai'i, near-vent eruptive products: January 1983 through September 2001

This report presents major-element geochemical data from 652 glasses (~6,520 analyses) and 795 whole-rock aliquots from 1,002 fresh samples of olivine-tholeiitic lava collected throughout the near-continuous eruption of Kïlauea Volcano, Hawai'i, from January 1983 through September 2001. The data presented herein provide a unique temporal compilation of lava geochemistry that best reflects variations of pre-eruptive magma compositions during prolonged rift-zone eruption. This document serves as a repository for geochemical data referred to in U.S. Geological Survey Professional Paper 1676 (Heliker, Swanson, and Takahashi, eds., 2003) which includes multidisciplinary research papers pertaining to the first twenty years of Puu Oo-Kupaianaha eruption activity. Details of eruption characteristics and nomenclature are provided in the introductory chapter of that volume (Heliker and Mattox, 2003). Geochemical relations among all or portions of this data set are depicted and interpreted by Thornber (2003), Thornber and others (2003) and Thornber (2001). Trace element compositions and Nd, Sr and Pb isotopic analyses of representative samples of this select eruption suite will be provided in a separate and complimentary open file report. From 1983 to October 2001, approximately 2,500 eruption samples were collected and archived by the U.S. Geological Survey’s Hawaiian Volcano Observatory (HVO). Geochemical data for 1,002 of these samples are included here. Previous reports present bulk-lava major- element chemistry for eruption samples collected from 1983 to 1986 and from 1990 to 1994 (Neal and others, 1988 and Mangan and others, 1995, respectively). Major element glass chemistry and thermometry data for samples collected from 1983 to 1994 is reported by Helz and Hearn (1998) and whole-rock and glass chemistry for samples collected from September 1994 to October 2001 is provided by Thornber and others (2002). This report is a compilation of previously published data along with unpublished whole-rock data for the 1986–1990 eruptive interval (episode 48, see Heliker and Mattox, 2003). The geochemical data in this report is mostly limited to well-quenched samples collected at or near their respective vents. The samples include tephra and spatter, in addition to lava dipped from lava lakes, lava tubes, and surface lava flows. The details of sample collection techniques as described by Thornber and others (2002) are generally applicable for this entire sampling interval. Specifically excluded from this database are samples of distal surface flows, many of which were collected for topical studies of emplacement dynamics (for example, Cashman and others, 1999). Samples of sluggish or crystal-laden tube flows collected during eruptive pauses were also excluded, because they bear visual, petrographic and geochemical evidence for crystal accumulation during surface-flow stagnation. In addition, the pre-1992 whole-rock major element data reported here has been corrected to compensate for minor analytical discrepancies between pre- and post-1991 XRF analyses. These discrepancies resulted from a change in instrumentation at the USGS Denver analytical laboratories. This select suite of time-constrained geochemical data is suitable for constructing petrologic models of pre-eruptive magmatic processes associated with prolong rift zone eruption of Hawaiian shield volcanoes.

Hawai'i

Shape-selective adsorption of aromatic molecules from water by tetramethylammonium-smectite

The adsorption of aromatic compounds by smectite exchanged with tetramethylammonium (TMA) has been studied. Aromatic compounds adsorbed by TMA-smectite are assumed to adopt a tilted orientation in a face-to-face arrangment with the TMA tetrahedra. The sorptive characteristics of TMA-smectite were influenced strongly by the presence of water. The dry TMA-smectite showed little selectivity in the uptake of benzen, toluene and xylene. In the presence of water, TMA-smectite showed a high degree of selectivity based on molecular size/shape, resulting in high uptake of benzene and progressively lower uptake of larger aromatic molecules. This selectivity appeared to result from the shrinkage of interlamellar cavities by water.

Journal of the Chemical Society, Faraday Transacti

Modeling, mapping, and measuring the risk of freshwater invasive species across Alaska

Freshwater ecosystems of the Alaskan Arctic and Subarctic provide resources that are culturally, ecologically, and economically invaluable. Presently, these regions are relatively free of the impacts from invasive species compared to southern latitudes. To date, there have been relatively few verified introductions of aquatic invasive species (AIS) to freshwater ecosystems in Alaska. The expanding list and distribution of AIS has led to significant negative ecological and economic impacts (e.g., waterweed Elodea nuttalli ; E. canadensis and northern pike Esox Lucius introduced outside its native range in Alaska). Escalating human activity across Alaskan lands and waters, coupled with rapidly shifting environmental conditions, increases the potential for new species introductions and subsequent establishment. Creating a proactive framework for well-informed decision-making and action can improve the effectiveness of prevention efforts and bolster decision support tools that help resource managers direct limited resources. Prioritizing AIS that may be introduced and become established, as well as the locations at highest risk of invasion, is foundational to building a proactive invasive species management framework in Alaska. This project sought to identify and prioritize AIS known to be invasive in the contiguous United States, evaluate current and future habitat suitability for AIS in Alaska, and assess potential for AIS to be transported to habitats across Alaska, utilizing similar assessment methods as implemented for Bering Sea marine invasive species and non-native plants in Alaska. To accomplish this goal, the objectives of the project were to: 1) develop a formal ranked list of potential AIS to freshwater systems of Alaska; 2) assess the level of establishment risk for potential AIS by developing habitat suitability models for waterbodies across Alaska; and 3), identify potential pathways and specific vectors for high-risk AIS to invade Alaska and develop a framework for how vector analysis will be completed to understand transport risk. Overall, our goal is horizon scanning which is defined by Roy et al. (2019) as “a systematic examination of potential threats and opportunities, within a given context, and likely future developments, which are at the margin of current thinking and planning.” The scans include pathway analyses and risk screening of species present at pathway origin points, with a focus on identifying species at high risk of being introduced, becoming established, spreading, and causing harm. We refined a list of 28 AIS from a list of hundreds based on characterizations of species’ invasiveness and species’ proximity to Alaska (USGS 2020; GBIF 2022). Next, we evaluated the relative invasiveness of individual species to create an initial AIS ranking. We sought to characterize habitat suitability of AIS by selecting variables that were continental in scale, covering North America to include Alaska as well as the lower 48 states comparing natural discharge, sub-basin average terrain slope (degrees), average silt fraction, average organic carbon, lithological class, and human footprint in sub-basin in 2009. We estimated AIS habitat suitability across the entire state of Alaska using the physiological tolerances of the AIS (Appendix 2). We also evaluated pathways and vectors for the introduction of AIS (Appendix 2). Many pathways and vectors considered did not meet the criteria for Alaska or freshwater systems. Of the 28 ranked species that we categorized as very high, high, and moderate levels of invasiveness; all three risk groups included fish and mollusks (Appendix 2). One commonality of the very high-invasiveness-ranked species was the availability of Ecological Risk Screening Summary documents (USFWS, 2022) produced by U.S. Fish and Wildlife Service (USFWS), except for the goldfish ( Carassius auratus ) and the New Zealand mudsnail ( Potamopyrgus antipodarum ). The Ecological Risk Screening Summary is now available for New Zealand mudsnails. In general, fish species often ranked very high or high in invasiveness and included sportfish and aquarium fish, suggesting the importance of pathways such as aquarium trade, fishing industry, intentional (but illegal) introductions of sportfishes and aquarium fishes for establishment. The technique we used for habitat suitability models necessitated aquatic environmental datasets that were continental in scale, which was often interpolated from very coarse resolution source data layers, particularly in Alaska. Better spatial data representing aquatic environments would likely improve this approach. While the lack of introductions in Alaska and nearby provinces and states is encouraging, the lack of occurrence data for the focal species also created complications for habitat suitability modeling. Despite the challenges, the habitat suitability models indicated limited suitability for warmwater species while some species, such as Brook trout (S alvelinus fontinalis ), have high habitat suitability across Alaska no matter what threshold approach is taken. Some environmental predictors were more important than others. Specifically, the most important predictor variable, ‘frost free days,’ was critical for 15 out of 28 species as expected due to harsh winter conditions in Arctic and Subarctic regions. The second most important predictor was ‘subbasin land surface runoff’, a variable that indicates the amount of discharge and runoff, while the third most important predictor was ‘snow cover’ another indication of winter conditions. Overall, the ability to understand the effect of future climate scenarios on the establishment of AIS was challenging. A detailed dataset of freshwater temperatures and water chemistry (e.g., pH, calcium) would greatly improve the ability to predict invasiveness of freshwater species to Alaska’s ecosystems on a regional basis. Future studies may benefit from a more focused geographic scope examining a group of subbasins or a regional basin rather than the entire state. These drainages could be selected based upon the mostly likely locations of introduction pathways. The two most prevalent pathway risks for AIS are in-state transfer and stowaways/contaminants. Although there are examples of introductions from other pathways, the risk is somewhat mitigated by Alaska’s climate and regulations. However, variable application of protocols for inspection and cleaning of fishing gear, watercraft, and other similar items while traveling into Alaska as well as transferring from waterbody to waterbody within the state creates a substantial risk in introducing invasive species. We plot cumulative invasive vulnerability for all subbasins and for the top 10% of subbasins (Appendix 3).

Alaska

Evaluation of Water-Chemistry and Water-Level Data at the Henderson Road Superfund Site, Upper Merion Township, Montgomery County, Pennsylvania, 1991-2008

Several shutdown-rebound tests have been conducted at the Henderson Road Superfund Site, which has been on the U.S. Environmental Protection Agency's National Priorities List since 1984. For a given test, the extraction wells are turned off, and water samples are collected from selected monitor wells at regular intervals before and during cessation of pumping to monitor for changes in chemical concentrations. A long-term shutdown-rebound test began on July 17, 2006. In support of this test, the U.S. Geological Survey conducted this study to determine the effects of shutting down on-site extraction wells on concentrations of selected contaminants and water levels. Concentrations were compared to ARARs (applicable relevant and appropriate requirements), which were set as remediation goals in the Henderson Road Site Record of Decision. Water from 10 wells in and near the source area and to the north, northeast, and northwest of the source area sampled in 2008 exceeded the 5.52 ug/L (micrograms per liter) ARAR for benzene. The greatest changes in benzene concentration between pre-shutdown samples collected in July 2006 and samples collected in February and March 2008 (19 months after the shutdown) were for wells in and north of the source area; increases in benzene concentration ranged from 1.5 to 164 ug/L. Water from five wells in the source area and to the north and northwest of the source area sampled in 2008 exceeded the 60 ug/L ARAR for chlorobenzene. The greatest changes in chlorobenzene concentration between pre-shutdown samples collected in July 2006 and samples collected in February and March 2008 were for wells north of the source area; increases in chlorobenzene concentration ranged from 6.9 to 99 ug/L. The highest concentrations of chlorobenzene were near or outside the northern site boundary, indicating chlorobenzene may have moved north away from the source area; however, no monitor well clusters are on the northern side of the Pennsylvania Turnpike, which is about 190 feet north of the source area. A much larger area was affected by chlorobenzene than benzene. Chlorobenzene concentrations decreased in the source area and increased at and beyond the site boundary. Water from four wells in and northeast of the source area sampled in 2008 exceeded the 5.06 ug/L ARAR for 1,1-dichloroethane (1,1-DCA). Increases in 1,1-DCA concentration between pre-shutdown samples collected in July 2006 and samples collected in February 2008 ranged from 0.4 to 20 ug/L. Water from two wells in the source area sampled in 2008 exceeded the 175 ug/L ARAR for total xylene. The 1,1-DCA and xylene plumes appear to extend in an east-northeast direction from the source area. Large drawdowns in the Upper Merion Reservoir during droughts in 1998 and 2001 affected water levels in the Chester Valley and at the Henderson Road Site, except for well HR-17-170. After the drought of 2001, water levels in the Chester Valley showed a protracted recovery lasting from September 2001 until June 2005 (46 months). Water-level data were evaluated temporally for 1997-2008 and spatially for (1) June 16, 2003, when the extraction wells were pumping at the full rate prior to the start of the June 2003 shutdown test; (2) July 10, 2006, during the period of reduced pumping after the June 2003 shutdown test; and (3) February 25-29, 2008, when the extraction wells were not pumping. Except for well HR-5-195, wells were categorized as shallow, intermediate-depth, and deep wells. The potentiometric surface for shallow wells did not appear to be affected by pumping of the extraction wells. The general direction of ground-water flow was to the north. The potentiometric surface for intermediate-depth wells showed a cone of depression when the extraction wells were pumping at the full rate but did not show a cone of depression when the extraction wells were pumping at the reduced rate. The ground-water-flow direction was toward the north and northeast, similar to

Scientific Investigations Report

Comparison of two estrogen chemically activated luciferase expression cell bioassays to liquid chromatography–mass spectrometry for quantifying estrone in water samples

Chemically activated luciferase expression (CALUX) cell bioassays are popular tools for assessing endocrine activity of chemicals such as certain environmental contaminants. Although activity equivalents can be obtained from CALUX analysis, directly comparing these equivalents to those obtained from analytical chemistry methods can be problematic because of the complexity of endocrine active pathways. We explored the suitability of two estrogen CALUX bioassays (the Organisation for Economic Co-operation and Development–approved VM7Luc4E2 cell bioassay and the VM7LucERβc9 cell bioassay) for quantitation of estrogen. Quadrupole-time of flight ultraperformance liquid chromatography–mass spectrometry (LC/MS) was selected as a comparative method. Regression analysis of measured estrone (E1) calibration samples showed all three methods to be highly predictive of nominal concentrations ( p ≤ 7.5 × 10 –51 ). Extracts of water sampled from laboratory dilutor tanks containing E1 at 0, 20, and 200 ng/L alone and in combination with atrazine were selected to test the quantitative capabilities of the CALUX assays. Process controls (0 and 100 ng E1/L) and a separate E1 standard (10 ng/ml, used to prepare the E1 process control) were also tested. Levels of E1 determined by LC/MS analysis and bioanalytical equivalents (ng E1/L) determined by CALUX analyses were comparable except in certain instances where the samples required dilution prior to CALUX analyses (e.g., the E1 process control and E1 standard). In those instances, measurements by CALUX were slightly but significantly decreased relative to LC/MS. Atrazine had no effect on the ability of either LC/MS or the CALUX bioassays to quantify E1. The present study illustrates the CALUX bioassays as successful in quantifying an estrogen in simple water samples and further characterizes their utility for screening. Environ Toxicol Chem 2023;42:333–339. Published 2022. This article is a U.S. Government work and is in the public domain in the USA.

Environmental Toxicology and Chemistry

Episodic acidification of small streams in the northeastern United States: Fish mortality in field bioassays

In situ bioassays were performed as part of the Episodic Response Project, to evaluate the effects of episodic stream acidification on mortality of brook trout (Salvelinus fontinalis) and forage fish species. We report the results of 122 bioassays in 13 streams of the three study regions: the Adirondack mountains of New York, the Catskill mountains of New York, and the Northern Appalachian Plateau of Pennsylvania. Bioassays during acidic episodes had significantly higher mortality than did bioassays conducted under nonacidic conditions, but there was little difference in mortality rates in bioassays experiencing acidic episodes and those experiencing acidic conditions throughout the test period. Multiple logistic regression models were used to relate bioassay mortality rates to summary statistics of time-varying stream chemistry (inorganic monomeric aluminum, calcium, pH, and dissolved organic carbon) estimated for the 20-d bioassay periods. The large suite of candidate regressors also included biological, regional, and seasonal factors, as well as several statistics summarizing various features of aluminum exposure duration and magnitude. Regressor variable selection and model assessment were complicated by multicolinearity and overdispersion. For the target fish species, brook trout, bioassay mortality was most closely related to time-weighted median inorganic aluminum. Median Ca and minimum pH offered additional explanatory power, as did stream-specific aluminum responses. Due to high multicollinearity, the relative importance of different aluminum exposure duration and magnitude variables was difficult to assess, but these variables taken together added no significant explanatory power to models already containing median aluminum. Between 59 and 79% of the variation in brook trout mortality was explained by models employing between one and five regressors. Simpler models were developed for smaller sets of bioassays that tested slimy and mottled sculpin (Cottus cognatus and C. bairdi) as well as blacknose dace (Rhinichthys atratulus). For these forage species a single inorganic aluminum exposure variable successfully accounted for 86-98% of the observed mortality. Even though field bioassays showed evidence of multiple toxicity factors, models results suggest that adequate mortality predictions can be obtained from a single index of inorganic Al concentrations during exposure periods.

Ecological Applications

Passive sampling of groundwater wells for determination of water chemistry

Introduction Passive groundwater sampling is defined as the collection of a water sample from a well without the use of purging by a pump or retrieval by a bailer (Interstate Technology and Regulatory Council [ITRC], 2006; American Society for Testing and Materials [ASTM], 2014). No purging means that advection of water is not involved in collecting the water sample from the well. Passive samplers rely on diffusion as the primary process that drives their collection of chemical constituents. Diffusion is the transport of chemicals caused by the presence of a chemical gradient. Chemicals tend to move or diffuse from areas of higher concentration to areas of lower concentration to reach an average or equilibrium concentration. Passive sampling of groundwater relies on the ambient exchange of groundwater in the formation with water in the screened or open interval of a well. In this report, the term formation is used to describe all saturated hydrogeologic units that yield water to a well. If the well opening is unclogged and free of a film of deposits from physical turbidity or chemical precipitation, then the exchange of groundwater is likely adequate, and the water in the open interval will be representative of water in the formation. In some cases, the passive sample from the well opening can be more representative of groundwater from the formation than a sample collected by pumping if pumping induces mixing of water in the open interval with stagnant casing water that has undergone chemical alteration (Harte and others, 2018). In most cases, passive sampling will better represent the ambient groundwater chemistry flowing through the open interval of a well because pumping may capture water of different chemistry from downgradient or lateral areas that would not normally pass through the well. Three basic types of passive samplers are discussed in this report. The first type of passive sampler is the equilibrium-membrane type, which includes a semi-permeable membrane through which chemicals diffuse or permeate. Permeation is simply the process of water or chemicals moving through openings in the membrane. The authors contend that permeation is dominated by diffusion for many of the passive samplers discussed in this report. Some passive equilibrium-membrane-type samplers allow most types of chemical constituents through, whereas others allow the diffusion of only selected groups of chemicals. Once the chemical constituents are inside the membrane, they are retained by the equilibration of concentrations inside the sampler with those outside the sampler. The second type of passive sampler is an equilibrium-thief type, which has no semi-permeable membrane. Chemical constituents simply move through the openings in the body of the sampler either initially through advection and dispersion or over time primarily by diffusion. Chemical constituents reach equilibrium between the water in the sampler and the water in the well and are captured in the sampler when the sampler is closed. The third type of passive sampler is an accumulation-type sampler that contains sorptive media. Selected chemical constituents are sorbed onto the media that the sampler contains for later extraction and analysis. Although passive samplers have been available for more than 15 years (from present [2020]), their use by U.S. Geological Survey (USGS) hydrologists and hydrologic technicians to monitor groundwater quality largely has been limited to selected research studies. The authors believe that this may be the result of (1) a lack of exposure of most USGS personnel to passive samplers and the uses of these samplers and (2) the lack of a USGS-approved protocol for the proper use of these samplers by USGS personnel. This report is an effort to fill those two needs. The focus of this report is on hydraulic, hydrologic, and chemical considerations in the application of passive samplers and interpretation of groundwater chemistry results obtained using passive samplers in wells. This report describes the differences between purging and passive sampling methods in groundwater and explains how and why passive samplers work. The report points out the advantages and limitations of passive samplers in general and for each particular type of passive sampler. Important considerations to be taken into account prior to the use of passive samplers are discussed, such as defining the data-quality objectives, the water-quality constituents to be sampled, sample volumes required for analysis, well construction of the sampling network, and the geologic formations that will be sampled. Potential applications of passive samplers also are discussed, such as chemical-vertical profiling of wells. A general field protocol for the deployment, recovery, and sample collection using these devices is described, and some overall guidance for the practitioner with application examples is given. Comparison methods used to evaluate results from passive sampling versus purge sampling also are discussed.

Techniques and Methods

Physical, chemical, and biological characteristics of selected headwater streams along the Allegheny Front, Blair County, Pennsylvania, July 2011–September 2013

The Altoona Water Authority (AWA) obtains all of its water supply from headwater streams that drain western Blair County, an area underlain in part by black shale of the Marcellus Formation. Development of the shale-gas reservoirs will require new access roads, stream crossing, drill-pad construction, and pipeline installation, activities that have the potential to alter existing stream channel morphology, increase runoff and sediment supply, alter streamwater chemistry, and affect aquatic habitat. The U.S. Geological Survey, in cooperation with Altoona Water Authority and Blair County Conservation District, investigated the water quality of 12 headwater streams and biotic health of 10 headwater streams. Channel morphology was characterized at 10 of 12 stream sites using 500-foot (minimum) longitudinal profiles, four cross-sections each, and pebble counts. Channel slopes ranged from 0.008 in Poplar Run near Newry to 0.045 in Mill Run. In general, streams draining watersheds of 5 square miles or less and at higher elevation had the steepest slopes. On the basis of the median particle size, determined during pebble counts, the streambed substrate can be characterized as cobble (Mill Run, Bells Gap Run, Tipton Run, and Sink Run), a mix of gravel and cobble (South Poplar Run, Dry Gap Run, Glenwhite Run, Sugar Run, Blair Gap Run), and gravel (Poplar Run, Newry). Daily mean values of gage height were determined, and continuous (30-minute interval) data consisting of specific conductance and water temperature were collected, at four sites; each site showed typical seasonal fluctuations and the effects of precipitation. Streamflow affected discrete water-quality. Dissolved oxygen always increased with increased streamflow. Most cations (including barium and strontium), along with pH, specific conductance, and total dissolved solids, decreased with greater streamflow, reflecting the dilution effect of moderately acidic surface runoff and precipitation on groundwater discharge (base flow) into the stream channels. Concentrations of trace elements varied by constituent and streamflow. On the basis of the results of water-quality analyses for the selected constituents, the water quality in 9 of the 12 streams can be considered fair or attaining with no measured constituent exceeding a U.S. Environmental Protection Agency maximum or secondary contaminant level. Abandoned mine drainage (AMD) affects Glenwhite Run, Blair Gap Run, and Sugar Run. For Sugar Run, the AMD is reflected in the elevated iron concentration (greater than 300 micrograms per liter). Manganese concentrations greater than 50 micrograms per liter were measured in Glenwhite Run, Sugar Run, and Blair Gap Run. A mixing curve based upon chloride/bromide ratios for two end points—precipitation and deicing salts—indicate that deicing salt is migrating to the streams. A similar curve representative of late-emerging flowback water from Marcellus gas wells indicated that the surface-water samples had not been influenced by such brines. On the basis of the concentration of major ions, the streams in the study area generally had mixed cation and anion compositions. Calcium is the dominant cation in one stream. Carbonate and bicarbonate are the dominant anions for two streams, and sulfate is dominant in three streams. The remaining six streams do not have a dominant ion. Biotic health was characterized at 10 of 12 stream sites; the two sites excluded were established late in the study period (May 2013) for refinement of water quality in the headwaters of Poplar Run and the location of Marcellus Formation gas wells. On the basis of the Maryland Index of Biotic Integrity (MdIBI) for fish assemblages, 8 of 10 streams can be considered in fair health. Tipton Run had the highest MdIBI score (3.75) and the greatest number of native species. South Poplar Run had the lowest MdIBI score (1.75); pollution tolerant blacknose dace was dominant. On the basis of the Pennsylvania Department of Environmental Protection macroinvertebrate index of biotic integrity, 9 of 10 streams were characterized as attaining, with scores as high as 88.9 at Tipton Run. Only Sugar Run was characterized as impaired, with a score of 40.4.

Pennsylvania

Selected natural attenuation monitoring data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, June 2002

Previous investigations indicated that natural attenuation and biodegradation of chlorinated volatile organic compounds (CVOCs) are substantial in shallow ground water beneath the 9-acre former landfill at Operable Unit 1 (OU 1), Naval Undersea Warfare Center (NUWC), Division Keyport, Washington. The U.S. Geological Survey (USGS) has continued to monitor ground-water geochemistry to assure that conditions remain favorable for contaminant biodegradation. This report presents the geochemical and selected CVOC data for ground water at OU 1, collected by the USGS during June 10-14, 2002, in support of long-term monitoring for natural attenuation. Overall, the geochemical data for June 2002 indicate that redox conditions in the upper-aquifer water remain favorable for reductive dechlorination of chlorinated VOCs because strongly reducing conditions persisted beneath much of the former landfill. Redox conditions in the intermediate aquifer downgradient of the landfill also remained favorable for reductive dechlorination, although the 2002 dissolved hydrogen (H2) concentration from well MW1-28 is questionable. Changes in redox conditions were observed at certain wells during 2002, but a longer monitoring period and more thorough interpretation are needed to ascertain if phytoremediation activities are affecting redox conditions and if biodegradation processes are changing over time. The Navy intends to complete a more thorough interpretation in preparation for the 5-year review of OU 1 scheduled for 2004. There were a few substantial differences between the 2002 concentrations and previously observed concentrations of volatile organic compounds. Total CVOC concentrations in 2002 samples decreased substantially in all piezometers sampled in the northern plantation, and the largest percentages of decrease were for the compounds trichloroethene (TCE) and cis-1,2-dichloroethene (cis-DCE). Changes in total CVOC concentrations in the southern plantation were less consistent. Historically high concentrations were observed in samples from three piezometers, with particularly substantial increases in TCE and cis-DCE concentrations, and historically low concentrations were observed in two piezometers, with particularly substantial decreases in TCE and cis-DCE concentrations. Similarly to the redox chemistry, a longer monitoring period and more thorough interpretation are needed to ascertain if phytoremediation activities are affecting CVOC concentrations and if biodegradation processes are changing over time. No changes in monitoring plans are proposed for June 2003, although the practice of deploying a data sonde downhole while purging the wells will be discontinued. Downhole monitoring added uncertainty to selected measured dissolved H2 concentrations because of the possibility that the sonde and cable created a bridge that resulted in non-equilibrium dissolved H2 concentrations at the wells.

Open-File Report

Geochemical conditions and the occurrence of selected trace elements in groundwater basins used for public drinking-water supply, Desert and Basin and Range hydrogeologic provinces, 2006-11: California GAMA Priority Basin Project

The geochemical conditions, occurrence of selected trace elements, and processes controlling the occurrence of selected trace elements in groundwater were investigated in groundwater basins of the Desert and Basin and Range (DBR) hydrogeologic provinces in southeastern California as part of the Priority Basin Project (PBP) of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA PBP is designed to provide an assessment of the quality of untreated (raw) groundwater in the aquifer systems that are used for public drinking-water supply. The GAMA PBP is being conducted by the California State Water Resources Control Board in collaboration with the U.S. Geological Survey and the Lawrence Livermore National Laboratory. The DBR hydrogeologic provinces consist of 141 defined groundwater basins separated by mountain ranges, faults, and other features. This report presents analyses of data collected from nine study areas within the DBR hydrogeologic provinces: Antelope Valley, Borrego Valley, the Central Desert area, Coachella Valley, Colorado River, Indian Wells Valley, Low-Use Basins of the Mojave and Sonoran Deserts, the Mojave, and Owens Valley. Collectively, these nine study areas are referred to as the DBR study unit. The study unit covers approximately 7,000 square miles and includes the 63 groundwater basins in the DBR hydrogeologic provinces in which groundwater is used for public drinking-water supply. The vast majority of the 223 wells sampled for this study were long-screened production wells used primarily for public supply. Uncorrected carbon-14 ( 14 C) groundwater ages for samples collected in the DBR study unit ranged from less than (<) 100 to 33,700 years before present (BP). Sixty-six percent of sample ages were greater than (>) 100 years BP, and 40 percent were >3,800 years BP. Samples collected from wells located adjacent to mountain-front recharge areas or major surface-water features generally had younger groundwater ages than did samples collected from wells located away from mountain fronts or towards the distal ends of basin groundwater flow paths. Most groundwater sampled in the DBR study unit had alkaline pH: 89 percent of sample pH values ranged from 7.1 to 9.8, with 37 percent greater than or equal to (&ge;) 7.9. Groundwater age was significantly correlated (positively) with pH, likely because silicate weathering is a primary control on groundwater pH and is a slow process. The oxidation-reduction (redox) condition of the groundwater sampled in the DBR study unit was predominantly oxic (71 percent), except in the Colorado River study area where organic-rich fluvial aquifers provide the electron donors necessary to support iron-reducing (anoxic-Fe) redox processes. The cation type of 78 percent of the samples was either sodium- or mixed-type, and the anion type of 83 percent of the samples was either bicarbonate- or mixed-type. Sodium-type groundwaters generally were older and more alkaline than calcium-type groundwaters, consistent with the change in water chemistry expected from cation exchange between groundwater and aquifer sediments over long periods of time. Because of the correlation with young groundwater, calcium-type groundwater was predominantly from wells located adjacent to mountain-front recharge areas. Arsenic (As), boron (B), fluoride (F), molybdenum (Mo), strontium (Sr), uranium (U), and vanadium (V) were selected for assessment in this study because they occurred at concentrations greater than California Department of Public Health or U.S. Environmental Protection Agency regulatory or non-regulatory drinking-water-quality benchmarks in more than 2 percent of the 223 samples collected in the DBR study unit. As and F were detected most commonly (18 and 13 percent, respectively) at concentrations above associated water-quality benchmarks and Sr and V least frequently (both at 3 percent). Given that 14 C groundwater ages are predominantly >100 years BP, land use in the study unit is primarily undeveloped, and chemicals derived from anthropogenic sources, such as volatile organic compounds, were infrequently detected, high concentrations of these trace elements in groundwater were most likely the result of natural factors and not anthropogenic factors. As, F, Mo, and V concentrations showed significant positive correlations to groundwater age and to pH. This relation is partly due to the sources of trace elements likely being the weathering of primary minerals, such as silicate minerals, which is a slow process that takes place over hundreds to thousands of years. This relation also reflects the positive correlation between groundwater age and pH. Geochemical modeling predicted that the dominant species of As, Mo, and V in solution were oxyanions (HAsO 4 2&ndash; , MoO 4 2&ndash; , and H 2 VO 4&ndash; ), which are likely to be mobile in alkaline groundwater because mineral surfaces composing aquifer matrices have a predominantly negative surface charge under alkaline conditions. F also exists predominantly as a negatively charged ion (F &ndash; ). At pH values >7.5, saturation indices generated by the geochemical modeling program PHREEQC indicated that F solubility may be somewhat limited by the precipitation of the mineral fluorapatite [Ca 5 (PO 4 ) 3 F]. Speciation modeling of As in anoxic-Fe groundwater (iron-reducing conditions) showed that samples were supersaturated with orpiment (As 2 S 3 ), indicating that mineral precipitation may be responsible for low As concentrations observed in reducing groundwater. In contrast, U concentrations showed significant negative correlations to groundwater age and to pH. Higher U concentrations generally occurred in samples for which geochemical modeling indicated that the uncharged ternary complex Ca 2 UO 2 (CO 3 ) 3 was the dominant aqueous U species. This uncharged complex is not attracted to the charged surfaces of minerals and thus increases U solubility. Formation of Ca 2 UO 2 (CO 3 ) 3 was greater in younger groundwaters because calcium and uranium concentrations generally were lower in older groundwaters, likely due to cation-exchange processes and precipitation of the mineral calcite as groundwater pH increased. Co-precipitation of U with the calcite (CaCO 3 ) may remove U from the aqueous phase. Saturation indices indicated that the anoxic-Fe groundwaters from the Colorado River study area were supersaturated with the mineral uraninite (UO 2 ), suggesting that UO 2 precipitation may be responsible for the low concentrations of U observed in these samples. Concentrations of strontium, which exists primarily in a cationic form (Sr 2+ ), were not significantly correlated with either groundwater age or pH. Strontium concentrations showed a strong positive correlation with total dissolved solids (TDS). Dissolved constituents, such as Sr, that interact with mineral surfaces through outer-sphere complexation become increasingly soluble with increasing TDS concentrations of groundwater. Boron concentrations also showed a significant positive correlation with TDS, indicating the B may interact to a large degree with mineral surfaces through outer-sphere complexation.

California

Effect of grain-coating mineralogy on nitrate and sulfate storage in the unsaturated zone

Unsaturated-zone sediments and the chemistry of shallow groundwater underlying a small (∼8-km 2 ) watershed were studied to identify the mechanisms responsible for anion storage within the Miocene Bridgeton Formation and weathered Coastal Plain deposits in southern New Jersey. Lower unsaturated-zone sediments and shallow groundwater samples were collected and concentrations of selected ions (including NO 3 − and SO 4 2− ) from 11 locations were determined. Grain size, sorting, and color of the lower unsaturated-zone sediments were determined and the mineralogy of these grains and the composition of coatings were analyzed by petrographic examination, scanning electron microscopy and energy dispersive analysis of x-rays, and quantitative whole-rock x-ray diffraction. The sediment grains, largely quartz and chert (80–94% w/w), are coated with a very fine-grained (<20 μm), complex mixture of kaolinite, halloysite, goethite, and possibly gibbsite and lepidocrocite. The mineral coatings are present as an open fabric, resulting in a large surface area in contact with pore water. Significant correlations between the amount of goethite in the grain coatings and the concentration of sediment-bound SO 4 2− were observed, indicative of anion sorption. Other mineral–chemical relations indicate that negatively charged surfaces and competition with SO 4 2− results in exclusion of NO 3 − from inner sphere exchange sites. The observed NO 3 − storage may be a result of matrix forces within the grain coatings and outer sphere complexation. The results of this study indicate that the mineralogy of grain coatings can have demonstrable effects on the storage of NO 3 − and SO 4 2− in the unsaturated zone.

Vadose Zone Journal

Restoration handbook for sagebrush steppe ecosystems with emphasis on greater sage-grouse habitat—Part 3. Site level restoration decisions

Sagebrush steppe ecosystems in the United States currently (2016) occur on only about one-half of their historical land area because of changes in land use, urban growth, and degradation of land, including invasions of non-native plants. The existence of many animal species depends on the existence of sagebrush steppe habitat. The greater sage-grouse ( Centrocercus urophasianus ) depends on large landscapes of intact habitat of sagebrush and perennial grasses for their existence. In addition, other sagebrush-obligate animals have similar requirements and restoration of landscapes for greater sage-grouse also will benefit these animals. Once sagebrush lands are degraded, they may require restoration actions to make those lands viable habitat for supporting sagebrush-obligate animals, livestock, and wild horses, and to provide ecosystem services for humans now and for future generations. When a decision is made on where restoration treatments should be applied, there are a number of site-specific decisions managers face before selecting the appropriate type of restoration. This site-level decision tool for restoration of sagebrush steppe ecosystems is organized in nine steps. Step 1 describes the process of defining site-level restoration objectives. Step 2 describes the ecological site characteristics of the restoration site. This covers soil chemistry and texture, soil moisture and temperature regimes, and the vegetation communities the site is capable of supporting. Step 3 compares the current vegetation to the plant communities associated with the site State and Transition models. Step 4 takes the manager through the process of current land uses and past disturbances that may influence restoration success. Step 5 is a brief discussion of how weather before and after treatments may impact restoration success. Step 6 addresses restoration treatment types and their potential positive and negative impacts on the ecosystem and on habitats, especially for greater sage-grouse. We discuss when passive restoration options may be sufficient and when active restoration may be necessary to achieve restoration objectives. Step 7 addresses decisions regarding post-restoration livestock grazing management. Step 8 addresses monitoring of the restoration; we discuss important aspects associated with implementation monitoring as well as effectiveness monitoring. Step 9 takes the information learned from monitoring to determine how restoration actions in the future might be adapted to improve restoration success.

Circular

Estimates of ground-water recharge rates for two small basins in central Nevada

Estimates of ground-water recharge rates developed from hydrologic modeling studies are presented for 3-Springs and East Stewart basins. two small basins (analog sites) located in central Nevada. The analog-site studies were conducted to aid in the estimation of recharge to the paleohydrologic regime associated with ground water in the vicinity of Yucca Mountain under wetter climatic conditions. The two analog sites are located to the north and at higher elevations than Yucca Mountain, and the prevailing (current) climatic conditions at these sites is thought to be representative of the possible range of paleoclimatic conditions in the general area of Yucca Mountain during the Quaternary. Two independent modeling approaches were conducted at each of the analog sites using observed hydrologic data on precipitation, temperature, solar radiation stream discharge, and chloride-ion water chemistry for a 6-year study period (October 1986 through September 1992). Both models quantify the hydrologic water-balance equation and yield estimates of ground-water recharge, given appropriate input data. The first model uses a traditional approach to quantify watershed hydrology through a precipitation-runoff modeling system that accounts for the spatial variability of hydrologic inputs, processes, and responses (outputs) using a dailycomputational time step. The second model is based on the conservative nature of the dissolved chloride ion in selected hydrologic environments, and its use as a natural tracer allows the computation of acoupled, water and chloride-ion, mass-balance system of equations to estimate available water (sum ofsurface runoff and groundwater recharge). Results of the modeling approaches support the conclusion that reasonable estimates of average-annual recharge to ground water range from about 1 to 3 centimeters per year for 3-Springs basin (the drier site), and from about 30 to 32 centimeters per year for East Stewart basin (the wetter site). The most reliable results are those derived from a reduced form of the chloride-ion model because they reflect integrated, basinwide processes in terms of only three measured variables: precipitation amount, precipitation chemistry, and streamflow chemistry.

Nevada

Choosing between atmospheric pressure chemical ionization and electrospray ionization interfaces for the HPLC/MS analysis of pesticides

An evaluation of over 75 pesticides by high-performance liquid chromatography/mass spectrometry (HPLC/MS) clearly shows that different classes of pesticides are more sensitive using either atmospheric pressure chemical ionization (APCI) or electrospray ionization (ESI). For example, neutral and basic pesticides (phenylureas, triazines) are more sensitive using APCI (especially positive ion). While cationic and anionic herbicides (bipyridylium ions, sulfonic acids) are more sensitive using ESI (especially negative ion). These data are expressed graphically in a figure called an ionization-continuum diagram, which shows that protonation in the gas phase (proton affinity) and polarity in solution, expressed as proton addition or subtraction (pKa), is useful in selecting APCI or ESI. Furthermore, sodium adduct formation commonly occurs using positive ion ESI but not using positive ion APCI, which reflects the different mechanisms of ionization and strengthens the usefulness of the ionization-continuum diagram. The data also show that the concept of "wrong-way around" ESI (the sensitivity of acidic pesticides in an acidic mobile phase) is a useful modification of simple pKa theory for mobile-phase selection. Finally, this finding is used to enhance the chromatographic separation of oxanilic and sulfonic acid herbicides while maintaining good sensitivity in LC/MS using ESI negative.

Analytical Chemistry

The deethylatrazine/atrazine ratio as an indicator of the onset of the spring flush of herbicides into surface water of the Midwestern United States

The ratio of deethylatrazine to atrazine (DAR) may be used to record the first major runoff of herbicides from non-point-source corn fields to surface water in the Midwestern United States. The DAR dramatically decreases from ∼0.5 to < 0.1 upon application of herbicide and the first major runoff event of a basin. The DAR then gradually increases to values of approximately 0.4–0.6 during the harvest season. Furthermore, the DAR may be used in studies of surface water movement to give a temporal indicator of water moving into reservoirs for possible storage of herbicides. It is hypothesized that deethylatrazine, which accounts for only 6% of the degradation of atrazine, becomes a significant metabolite in surface water (∼ 50% of parent compound) because of its selective removal from soil. This removal process may be an important concept for consideration in studies of herbicide contamination of rivers and reservoirs.

International Journal of Environmental Analytical