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Relationships between indicators of acid-base chemistry and fish assemblages in streams of the Great Smoky Mountains National Park

The acidity of many streams in the Great Smoky Mountains National Park (GRSM) has increased significantly since pre-industrial (∼1850) times due to the effects of highly acidic atmospheric deposition in poorly buffered watersheds. Extensive stream-monitoring programs since 1993 have shown that fish and macroinvertebrate assemblages have been adversely affected in many streams across the GRSM. Matching chemistry and fishery information collected from 389 surveys performed at 52 stream sites over a 22-year period were assessed using logistic regression analysis to help inform the U.S. Environmental Protection Agency’s assessment of the environmental impacts of emissions of oxides of nitrogen (NO x ) and sulfur (SO x ). Numerous logistic equations and associated curves were derived that defined the relations between acid neutralizing capacity (ANC) or pH and different levels of community richness, density, and biomass; and density and biomass of brook trout, rainbow trout, and small prey (minnow) populations in streams of the GRSM. The equations and curves describe the status of fish assemblages in the GRSM under contemporary emission levels and deposition loads of nitrogen (N) and sulfur (S) and provide a means to estimate how newly proposed (and various alternative) target deposition loads, which strongly influence stream ANC, might affect key ecological indicators. Several examples using ANC, community richness, and brook trout density are presented to illustrate the steps needed to predict how future changes in stream chemistry (resulting from different target deposition loads of N and S) will affect the probabilities of observing specific levels of selected biological indicators in GRSM streams. The implications of this study to the regulation of NO x and SO x emissions, water quality, and fisheries management in streams of the GRSM are discussed, but also qualified by the fact that specific examples provided need to be further explored before recommendations concerning their use as ecological indicators could be proposed.

North Carolina, Tennessee

Standard atomic weights of the elements 2021 (IUPAC Technical Report)

Following the reviews of atomic-weight determinations and other cognate data in 2015, 2017, 2019 and 2021, the IUPAC (International Union of Pure and Applied Chemistry) Commission on Isotopic Abundances and Atomic Weights (CIAAW) reports changes of standard atomic weights. The symbol A r °(E) was selected for standard atomic weight of an element to distinguish it from the atomic weight of an element E in a specific substance P, designated A r (E, P). The CIAAW has changed the values of the standard atomic weights of five elements based on recent determinations of terrestrial isotopic abundances: Ar (argon): from 39.948 ± 0.001 to [39.792, 39.963] Hf (hafnium): from 178.49 ± 0.02 to 178.486 ± 0.006 Ir (iridium): from 192.217 ± 0.003 to 192.217 ± 0.002 Pb (lead): from 207.2 ± 0.1 to [206.14, 207.94] Yb (ytterbium): from 173.054 ± 0.005 to 173.045 ± 0.010 The standard atomic weight of argon and lead have changed to an interval to reflect that the natural variation in isotopic composition exceeds the measurement uncertainty of A r (Ar) and A r (Pb) in a specific substance. The standard atomic weights and/or the uncertainties of fourteen elements have been changed based on the Atomic Mass Evaluations 2016 and 2020 accomplished under the auspices of the International Union of Pure and Applied Physics (IUPAP). A r ° of Ho, Tb, Tm and Y were changed in 2017 and again updated in 2021: Al (aluminium), 2017: from 26.981 5385 ± 0.000 0007 to 26.981 5384 ± 0.000 0003 Au (gold), 2017: from 196.966 569 ± 0.000 005 to 196.966 570 ± 0.000 004 Co (cobalt), 2017: from 58.933 194 ± 0.000 004 to 58.933 194 ± 0.000 003 F (fluorine), 2021: from 18.998 403 163 ± 0.000 000 006 to 18.998 403 162 ± 0.000 000 005 (Ho (holmium), 2017: from 164.930 33 ± 0.000 02 to 164.930 328 ± 0.000 007) Ho (holmium), 2021: from 164.930 328 ± 0.000 007 to 164.930 329 ± 0.000 005 Mn (manganese), 2017: from 54.938 044 ± 0.000 003 to 54.938 043 ± 0.000 002 Nb (niobium), 2017: from 92.906 37 ± 0.000 02 to 92.906 37 ± 0.000 01 Pa (protactinium), 2017: from 231.035 88 ± 0.000 02 to 231.035 88 ± 0.000 01 Pr (praseodymium), 2017: from 140.907 66 ± 0.000 02 to 140.907 66 ± 0.000 01 Rh (rhodium), 2017: from 102.905 50 ± 0.000 02 to 102.905 49 ± 0.000 02 Sc (scandium), 2021: from 44.955 908 ± 0.000 005 to 44.955 907 ± 0.000 004 (Tb (terbium), 2017: from 158.925 35 ± 0.000 02 to 158.925 354 ± 0.000 008) Tb (terbium), 2021: from 158.925 354 ± 0.000 008 to 158.925 354 ± 0.000 007 (Tm (thulium), 2017: from 168.934 22 ± 0.000 02 to 168.934 218 ± 0.000 006) Tm (thulium), 2021: from 168.934 218 ± 0.000 006 to 168.934 219 ± 0.000 005 (Y (yttrium), 2017: from 88.905 84 ± 0.000 02 to 88.905 84 ± 0.000 01) Y (yttrium), 2021: from 88.905 84 ± 0.000 01 to 88.905 838 ± 0.000 002

Pure and Applied Chemistry

Mineralogical, chemical, and physical properties of the regolith overlying crystalline rocks, Fairfax County, Virginia: a preliminary report

Undisturbed cores of saprolite developed on crystalline rocks of the Piedmont Province in Fairfax County, Virginia have been obtained using a combination of Shelby tubes, Denison sampler, and modified diamond core-drilling. The principal purpose of the core study is to correlate variations in chemistry, mineralogy and texture with engineering properties throughout the weathering profile. Coring sites were chosen to obtain a maximum depth of weathering on diverse lithologies. The rocks investigated include pelitic schist, metagraywacke, granite, diabase and serpentinite. Four to twelve samples per core were selected, depending on thickness of 1) the weathering profile (from about 1 m in serpentinite to more than 30 m in pelitic schist) and on 2) megascopic changes in saprolite character for analysis of petrography, texture, clay mineralogy andd major element chemistry. Shear strength and compressibility were determined on corresponding segments of core. Standard penetration tests were performed adjacent to coring sites to evaluate engineering properties in situ. Geochemical changes of saprolite developed from each rock type follow predictable trends from fresh rock to soil profile, with relative Increases in Si, Ti, Al, Fe3+ and H20; variable K; and relative loss of Fe 2+, Mg, Ca, and Na. These variations are more pronounced in the weathering profiles over mafic and ultramafic rocks than metagraywacke. Clay minerals in granite, schist and metagraywacke saprolite are kaolinite, dioctahedral vermiculite, interlayered micavermiculite, and minor illite. Gibbsite is locally developed in near-surface samples of schist. Standard penetration test data for the upper 7 m of saprolite over schist and metagraywacke suggest alternations between stronger and weaker horizons than probably reflect variations in lithology including the presence of quartz lenses. Results for granite saprolite are most consistent but indicate lower strength. Shear strength increases fairly regularly downward in the weathering profile. The engineering behavior of diabase saprolite is controlled by a dense, plastic, near-surface clay layer (montmorillonite and kaolinite)overlying rock which is weathered to a granular state (grus), while engineering properties of serpentinite are determined by a very thin weathering profile.

Open-File Report

Widespread chemical dilution of streams continues as long-term effects of acidic deposition slowly reverse

Studies of recovery from acidic deposition have focused on reversal of acidification and its associated effects, but as recovery proceeds slowly, chemical dilution of surface waters is emerging as a key factor in the recovery process that has significant chemical and biological implications. This investigation uses long-term chemical records from 130 streams in the Adirondack region of New York, USA, to evaluate the role of ongoing decreases in conductance, an index of dilution, in the recovery of these streams. Stream chemistry data spanning up to 40 years (1980s–2022) showed that acid-neutralizing capacity has increased in 92% of randomly selected streams, but that harmful levels of acidification still occur in 37% of these streams. Conductance and Ca 2+ concentrations decreased in 79% of streams, and SO 4 2− concentrations in streams continued to show strong decreases but remained several times higher than concentrations in precipitation. These changes were ongoing through 2022 even though acidic deposition levels were approaching those estimated for pre-industrialization. Further dilution is continuing through ongoing decreases in stream SO 4 2− . Nevertheless, Ca 2+ continued to be leached from soils by SO 4 2− , organic acids and NO 3 − , limiting the replenishment of available soil Ca 2+ , a prerequisite to stem further dilution of stream water.

Environmental Pollution

Hydrogeology, chemical characteristics, and water sources and pathways in the zone of contribution of a public-supply well in San Antonio, Texas

In 2001, the National Water-Quality Assessment (NAWQA) Program of the U.S. Geological Survey initiated a series of studies on the transport of anthropogenic and natural contaminants (TANC) to public-supply wells (PSWs). The main goal of the TANC project was to better understand the source, transport, and receptor factors that control contaminant movement to PSWs in representative aquifers of the United States. Regional- and local-scale study areas were selected from within existing NAWQA study units, including the south-central Texas Edwards aquifer. The local-scale TANC study area, nested within the regional-scale NAWQA study area, is representative of the regional Edwards aquifer. The PSW selected for study is within a well field of six production wells. Although a single PSW was initially selected, because of constraints of well-field operation, samples were collected from different wells within the well field for different components of the study. Data collected from all of the well-field wells were considered comparable because of similar well construction, hydrogeology, and geochemistry. An additional 38 PSWs (mostly completed in the confined part of the aquifer) were sampled throughout the regional aquifer to characterize water quality. Two monitoring well clusters, with wells completed at different depths, were installed to the east and west of the well field (the Zarzamora and Timberhill monitoring well clusters, respectively). One of the monitoring wells was completed in the overburden to evaluate potential hydrologic connectivity with the Edwards aquifer. Geophysical and flowmeter logs were collected from one of the well-field PSWs to determine zones of contribution to the wellbore. These contributing zones, associated with different hydrogeologic units, were used to select monitoring well completion depths and groundwater sample collection depths for depth-dependent sampling. Depth-dependent samples were collected from the PSW from three different depths and under three different pumping conditions. Additionally, selected monitoring wells and one of the well-field PSWs were sampled several times in response to a rainfall and recharge event to assess short-term (event-scale) temporal variations in water quality. For comparison purposes, groundwater samples were categorized as being from regional aquifer PSWs, from the well field (wellhead samples), from the monitoring wells (excluding the overburden well), from the overburden well, from the PSW depth-dependent sampling, and from temporal sampling. Groundwater samples were analyzed for inorganic, organic, isotopic, and age-dating tracers to characterize geochemical conditions in the aquifer and provide understanding of the mechanisms of mobilization and movement of selected constituents from source areas to a PSW. Sources, tracers, and conditions used to assess water quality and processes affecting the PSW and the aquifer system included (1) carbonate host rock composition; (2) physicochemical constituents; (3) major and trace element concentrations; (4) saturation indices with respect to minerals in aquifer rocks; (5) elemental ratios, such as magnesium to calcium ratios, that are indicative of water-rock interaction processes; (6) oxidation-reduction conditions; (7) nutrient concentrations, in particular nitrate concentrations; (8) the isotopic composition of nitrate, which can point to specific nitrate sources; (9) strontium isotopes; (10) stable isotopes of hydrogen and oxygen; (11) organic contaminant concentrations, including pesticides and volatile organic compounds; (12) age tracers, apparent-age distribution, and dissolved gas data used in age interpretations; (13) depth-dependent water chemistry collected from the PSW under different pumping conditions to assess zones of contribution; and (14) temporal variability in groundwater composition from the PSW and selected monitoring wells in response to an aquifer recharge event. Geochemical results indicate that the well-field and monitoring well samples were largely representative of groundwater in the regional confined aquifer. Constituents of concern in the Edwards aquifer for the long-term sustainability of the groundwater resource include the nutrient nitrate and anthropogenic organic contaminants. Nitrate concentrations (as nitrogen) for regional aquifer PSWs had a median value of 1.9 milligrams per liter, which is similar to previously reported values for the regional aquifer. Nitrate-isotope compositions for groundwater samples collected from the well-field PSWs and monitoring wells had a narrow range, with values indicative of natural soil organic values. A comparison with historical nitrate-isotope values, however, suggests that a component of nitrate in groundwater from biogenic sources might have increased over the last 30 years. Several organic contaminants (the pesticide atrazine, its degradate deethylatrazine, trichloromethane (chloroform; a drinking-water disinfection byproduct), and the solvent tetrachloroethene (PCE)) were widely distributed throughout the regional aquifer and in the local-scale TANC study area at low concentrations (less than 1 microgram per liter). Higher concentrations of PCE were detected in samples from the well-field PSWs and Zarzamora monitoring wells relative to the regional aquifer PSWs. The urban environment is a likely source of contaminants to the aquifer, and these results indicate that one or more local urban sources might be supplying PCE to the Zarzamora monitoring wells and the well-field wells. Samples from the well field also had high concentrations of chloroform relative to the monitoring wells and regional aquifer PSWs. For samples from the regional aquifer PSWs, the most frequently detected organic contaminants generally decreased in concentration with increasing well depth. Deeper wells might intercept longer regional flow paths with higher fractions of older water or water recharged in rural recharge areas in the western part of the aquifer that have been less affected by anthropogenic contaminants. A scenario of hypothetical contaminant loading was evaluated by using results from groundwater-flow-model particle tracking to assess the response of the aquifer to potential contamination. Results indicate that the aquifer responds quickly (less than 1 year to several years) to contaminant loading; however, it takes a relatively long time (decades) for concentrations to reach peak values. The aquifer also responds quickly (less than 1 year to several years) to the removal of contaminant loading; however, it also takes a relatively long time (decades) to reach near background concentrations. Interpretation of geochemical age tracers in this well-mixed karst system was complicated by contamination of a majority of measured tracers and complexities of extensive mixing. Age-tracer results generally indicated that groundwater samples were composed of young, recently recharged water with piston-flow model ages ranging from less than 1 to 41 years, with a median of 17 years. Although a piston-flow model is typically not valid for karst aquifers, the model ages provide a basis for comparing relative ages of different samples and a reference point for more complex hydrogeologic models for apparent-age interpretations. Young groundwater ages are consistent with particle-tracking results from hydrogeologic modeling for the local-scale TANC study area. Age-tracer results compared poorly with other geochemical indicators of groundwater residence time and anthropogenic effects on water quality, indicating that hydrogeologic conceptual models used in groundwater age interpretations might not adequately account for mixing in this karst system. Groundwater samples collected from the well field under a variety of pumping conditions were relatively homogeneous and well mixed for numerous geochemical constituents (with the notable exception of age tracers). Groundwater contributions to the PSW were dominated by well-mixed, relatively homogeneous groundwater, typical of the regional confined aquifer. Zones of preferential flow were determined for the PSW, but groundwater samples from different stratigraphic units were not geochemically distinct. Variations in chemical constituents in response to a rainfall and aquifer recharge event occurred but were relatively minor in the PSW and monitoring wells. This observation is consistent with the hypothesis that the response to individual recharge events in the confined aquifer, unless intersecting conduit flow paths, might be attenuated by mixing processes along regional flow paths. Results of this study are consistent with the existing conceptual understanding of aquifer processes in this karst system and are useful for water-resource development and management practices.

Texas

Chemical Constituents in Groundwater from Multiple Zones in the Eastern Snake River Plain Aquifer at the Idaho National Laboratory, Idaho, 2005-08

From 2005 to 2008, the U.S. Geological Survey's Idaho National Laboratory (INL) Project office, in cooperation with the U.S. Department of Energy, collected water-quality samples from multiple water-bearing zones in the eastern Snake River Plain aquifer. Water samples were collected from six monitoring wells completed in about 350-700 feet of the upper part of the aquifer, and the samples were analyzed for major ions, selected trace elements, nutrients, selected radiochemical constituents, and selected stable isotopes. Each well was equipped with a multilevel monitoring system containing four to seven sampling ports that were each isolated by permanent packer systems. The sampling ports were installed in aquifer zones that were highly transmissive and that represented the water chemistry of the top four to five model layers of a steady-state and transient groundwater-flow model. The model's water chemistry and particle-tracking simulations are being used to better define movement of wastewater constituents in the aquifer. The results of the water chemistry analyses indicated that, in each of four separate wells, one zone of water differed markedly from the other zones in the well. In four wells, one zone to as many as five zones contained radiochemical constituents that originated from wastewater disposal at selected laboratory facilities. The multilevel sampling systems are defining the vertical distribution of wastewater constituents in the eastern Snake River Plain aquifer and the concentrations of wastewater constituents in deeper zones in wells Middle 2051, USGS 132, and USGS 103 support the concept of groundwater flow deepening in the southwestern part of the INL.

Scientific Investigations Report

Groundwater hydrology and chemistry of Jamestown Island, Virginia—Potential effects of tides, storm surges, and sea-level rise on archaeological, cultural, and ecological resources

As the site of the first permanent English settlement in North America in 1607, Jamestown Island, Colonial National Historical Park (COLO), Virginia, contains a rich archaeological record that extends from the Paleoindian period (15,000 to 8,000 years ago) through the 20th century. The island is located on the lower James River near the mouth of Chesapeake Bay. Jamestown Island vegetation is dominated by upland forests surrounded by tidal, freshwater-to-oligohaline marshes. Along the Virginia coast, relative sea-level rise was more than 2.5 times the global average during the 20th century. Consequently, the National Park Service (NPS) has identified COLO as one of the 25 national parks most threatened by climate change. Surface waters across the island are hydraulically connected to the laterally continuous Surficial aquifer. The land-surface altitude of the island is low, with two-thirds of the island less than 5 feet (ft) above the North American Vertical Datum of 1988 (NAVD 88). Consequently, sea-level rise, combined with tides and storm surges, threatens the island and its resources as surface-water and groundwater levels rise, saltwater enters the Surficial aquifer, and groundwater chemistry changes. The impact of sea-level rise on the island’s surface-water resources has been well studied, but groundwater effects have been largely ignored. Quantifying the effects of tides, storm surges, and sea-level rise on groundwater levels and chemistry is essential to developing an effective strategy for managing climate-induced changes. The first step in developing a response strategy includes a parkwide general risk assessment for archaeological sites on the island, so that sites can be prioritized for management actions. The U.S. Geological Survey and the NPS began a study in 2015 to develop a long-term groundwater-monitoring program to evaluate this risk and to develop an updated management strategy. The groundwater-monitoring program consists of 45 wells and piezometers in two individual clusters and three transects across the island in different hydrologic and chemical settings. Samples for water quality were collected from the wells and piezometers from October 2015 through September 2018 at variable time intervals. Results of the monitoring identified disparate hydrologic and chemical responses to saltwater intrusion across the island. Specific conductance (an indicator of salinity) of groundwater beneath several marshes responded differently to changes in James River salinity. Groundwater response to changes in James River specific conductance appeared to be controlled by land-surface altitude and slope, differences in lateral and vertical sediment characteristics, distance from surface waters, and the degree of surface water/groundwater connectivity between channels and the aquifer. Groundwater chemistry data from monitoring wells at Black Point, a low-altitude, upland setting, are in contrast with conditions observed in Island House observation wells, a high-altitude, upland setting. Specific conductance (less than 200 microsiemens per centimeter [μS/cm]) and pH (greater than 5.0) of groundwater beneath much of the uplands that characterize the Island House observation wells are typical of groundwater in noncarbonate sedimentary aquifers recharged by precipitation. At Black Point, specific conductance ranged from 2,490 to 15,200 μS/cm, and pH ranged from 3.1 to 6.6 standard units. At the Black Point observation wells, the most saline and dense water was at the water table rather than deeper in the aquifer, causing a density inversion that persisted throughout the study. The density inversion likely resulted from differences in permeability between the shallow clay and fine-grained sands and the deeper coarse-grained sand and gravel. Groundwater with the lowest pH was at the water table. As saline groundwater flows through organic sediment beneath the marshes, bacterial biodegradation of organic matter creates anoxic conditions. Continued biodegradation concomitantly reduces iron-oxide minerals in the sediment and sulfate in saline water. When oxygen is reintroduced into groundwater, iron and sulfur can reoxidize to form sulfuric acid, locally lowering the pH of the water. This report describes the groundwater monitoring network design, rationale for site selection, monitoring approach, and results of monitoring from October 2015 through September 2018. Maps of inundation at selected water-level altitudes are included to identify the risk to archaeological, cultural, and ecological resources. The monitoring results of the hydrology and chemistry data are interpreted, and the different hydrologic and chemical settings are described. The implications of the study results for management decisions are presented, and suggestions for improving the monitoring network are included.

Virginia

Questa baseline and pre-mining ground-water quality investigation. 5. Well installation, water-level data, and surface- and ground-water geochemistry in the Straight Creek drainage basin, Red River Valley, New Mexico, 2001-03

The U.S. Geological Survey, in cooperation with the New Mexico Environment Department, is investigating the pre-mining ground-water chemistry at the Molycorp molybdenum mine in the Red River Valley, northern New Mexico. The primary approach is to determine the processes controlling ground-water chemistry at an unmined, off-site, proximal analog. The Straight Creek drainage basin, chosen for this purpose, consists of the same quartz-sericite-pyrite altered andesitic and rhyolitic volcanic rock of Tertiary age as the mine site. The weathered and rugged volcanic bedrock surface is overlain by heterogeneous debris-flow deposits that interfinger with alluvial deposits near the confluence of Straight Creek and the Red River. Pyritized rock in the upper part of the drainage basin is the source of acid rock drainage (pH 2.8-3.3) that infiltrates debris-flow deposits containing acidic ground water (pH 3.0-4.0) and bedrock containing water of circumneutral pH values (5.6-7.7). Eleven observation wells were installed in the Straight Creek drainage basin. The wells were completed in debris-flow deposits, bedrock, and interfingering debris-flow and Red River alluvial deposits. Chemical analyses of ground water from these wells, combined with chemical analyses of surface water, water-level data, and lithologic and geophysical logs, provided information used to develop an understanding of the processes contributing to the chemistry of ground water in the Straight Creek drainage basin. Surface- and ground-water samples were routinely collected for determination of total major cations and selected trace metals; dissolved major cations, selected trace metals, and rare-earth elements; anions and alkalinity; and dissolved-iron species. Rare-earth elements were determined on selected samples only. Samples were collected for determination of dissolved organic carbon, mercury, sulfur isotopic composition (34S and 18O of sulfate), and water isotopic composition (2H and 18O) during selected samplings. One set of ground-water samples was collected for helium-3/tritium and chlorofluorocarbon (CFC) age dating. Several lines of evidence indicate that surface water is the primary input to the Straight Creek ground-water system. Straight Creek streamflow and water levels in wells closest to the apex of the Straight Creek debris fan and closest to Straight Creek itself appear to respond to the same seasonal inputs. Oxygen and hydrogen isotopic compositions in Straight Creek surface water and ground water are similar, and concentrations of most dissolved constituents in most Straight Creek surface-water and shallow (debris-flow and alluvial) aquifer ground-water samples correlate strongly with sulfate (concentrations decrease linearly with sulfate in a downgradient direction). After infiltration of surface water, dilution along the flow path is the dominant mechanism controlling ground-water chemistry. However, concentrations of some constituents can be higher in ground water than can be accounted for by concentrations in Straight Creek surface water, and additional sources of these constituents must therefore be inferred. Constituents for which concentrations in ground water can be high relative to surface water include calcium, magnesium, strontium, silica, sodium, and potassium in ground water from debris-flow and alluvial aquifers and manganese, calcium, magnesium, strontium, sodium, and potassium in ground water from the bedrock aquifer. All ground water is a calcium sulfate type, often at or near gypsum saturation because of abundant gypsum in the aquifer material developed from co-existing calcite and pyrite mineralization. Calcite dissolution, the major buffering mechanism for bedrock aquifer ground water, also contributes to relatively higher calcium concentrations in some ground water. The main source of the second most abundant cation, magnesium, is probably dissolution of magnesium-rich carbonates or silicates.

New Mexico

Episodic acidification and changes in fish diversity in Pennsylvania headwater streams

Current water chemistry and fish communities in 70 Pennsylvania streams were compared with historical records to determine whether fish species richness had declined and, if so, the possible role of acidification. First‐, second‐, and third‐order streams were selected, and stream sites sampled during the 1961–1971 survey were resampled during May and June 1994 in the Appalachian Plateaus province and during June 1995 in the Valley and Ridge province. Streamflow was measured and a habitat assessment was completed at each site. Dominant bedrock types influencing the stream sampling site were determined for the Appalachian Plateaus streams. Episodic water chemistry was collected for 39 of the 50 Appalachian Plateaus streams and 14 of the 20 Valley and Ridge streams during the winter and spring of 1996. Thirty‐eight (76%) streams of the Appalachian Plateaus province and 13 (65%) streams in the Valley and Ridge province had a loss of fish species since the 1961–1971 sampling period. Habitat scores were not related to losses of fish species. Of the 53 streams sampled during runoff episodes 22 (42%) increased in total dissolved aluminum by more than 50 μg/L, and 31 (58%) streams decreased in pH by 0.5 units or more. Minnows (Cyprinidae) and darters (Percidae) are sensitive to acidity and were the species most often lost. Streams draining watersheds of the Appalachian Plateaus province dominated by Pottsville bedrock had more acidic water quality during base flow and storm flow sampling periods than streams dominated by Pocono bedrock. The results of this study indicate that many Pennsylvania streams have undergone an alarming reduction in fish diversity during the past 25–34 years. In many of these streams the loss in fish diversity may be attributed to episodic acidification.

Pennsylvania

Discharge, sediment, and water chemistry in Clear Creek, western Nevada, water years 2013–16

Clear Creek is a small stream that drains the eastern Carson Range near Lake Tahoe, flows roughly parallel to the Highway 50 corridor, and discharges to the Carson River near Carson City, Nevada. Historical and ongoing development in the drainage basin is thought to be affecting Clear Creek and its sediment-transport characteristics. Previous studies from water years (WYs) 2004 to 2007 and from 2010 to 2012 evaluated discharge, selected water-quality parameters, and suspended-sediment concentrations, loads, and yields at three Clear Creek sampling sites. This report serves as a continuation of the data collection and analyses of the Clear Creek discharge regime and associated water-chemistry and sediment concentrations and loads during WYs 2013–16. Total annual sediment loads ranged from 870 to 5,300 tons during WYs 2004–07, from 320 to 1,770 tons during WYs 2010–12, and from 50 to 200 tons during WYs 2013–16. Ranges in annual loads during the three study periods were not significantly different; however, total loads were greater during 2004–07 than they were during 2013–16. Annual suspended-sediment loads in WYs 2013–16 showed no significant change since WYs 2010–12 at sites 1 (U.S. Geological Survey reference site 10310485; Clear Creek above Highway 50, near Spooner Summit, Nevada) or 2 (U.S. Geological Survey streamgage 10310500; Clear Creek above Highway 50, near Spooner Summit, Nevada), but significantly lower loads at site 3 (U.S. Geological Survey site 10310518; Clear Creek at Fuji Park, at Carson City, Nevada), supporting the theory of sediment deposition between sites 2 and 3 where the stream gradient becomes more gradual. Currently, a threshold discharge of about 3.3 cubic feet per second is required to mobilize streambed sediment (bedload) from site 2 in Clear Creek. Mean daily discharge was significantly lower in 2010–12 than in 2004–07 and also significantly lower in 2013–16 than in 2010–12. During this study, lower bedload, and therefore lower total sediment load in Clear Creek was primarily due to significantly lower discharge and cannot be directly attributed to sediment mitigation work in the basin. Water chemistry in Clear Creek shows that the general water type of the creek under base-flow conditions in autumn is a dilute calcium bicarbonate. During winter and spring, the chemistry shifts toward a slightly more sodium and chloride character. Though the chemical characteristics show seasonal change, the water chemistries examined as part of this investigation remain within ecological criteria as adopted by the Nevada Division of Environmental Protection. There was no evidence of aqueous polynuclear aromatic hydrocarbons (PAHs) present in Clear Creek water during this study. Concentrations of PAHs, as determined in one bed-sediment sample and multiple semi-permeable membrane device extracts, were either less than quantifiable limits of analysis or were found at similar concentrations as blank samples. In July 2014, a 250–300-acre fire burned in the Clear Creek drainage basin. One day after the fire was extinguished, a thunderstorm washed sediment into the creek. A water chemistry sample collected as part of the post-fire storm event showed that the stormwater entering the creek had increased the concentrations of ammonium and organic nitrogen, phosphorus, manganese, and potassium; a similar finding of many other studies evaluating the effects of fires in small drainage basins. Subsequent chemical analyses of Clear Creek water in August 2014 (one month later) showed that these constituents had returned to pre-fire concentrations.

Nevada

2D micromodel study of clogging behavior of fine-grained particles associated with gas hydrate production in NGHP-02 gas hydrate reservoir sediments

Fine-grained particles (fines) commonly coexist with coarse-grained sediments that host gas hydrate. These fines can be mobilized by liquid and gas flow during gas hydrate production. Once mobilized, fines can clog pore throats and reduce reservoir permeability. Even where particle sizes are smaller than pore-throat sizes, clogs can form due to clusters of fines. For certain types of fines, particularly swelling clays, cluster sizes depend on pore-fluid chemistry, which changes as pore-fluid freshens during gas hydrate dissociation. Fines can also be concentrated by a moving gas/liquid interface, increasing the chances of pore-throat clogging regardless of fines type. To test the relative significance of these clogging mechanisms, 2D micromodel experiments have been conducted with different pore-throat widths (20, 40, 60 and 100 m), single-phase pore-fluids (deionized water and 2M-sodium-chloride solution), and moving gas/liquid interfaces on specimens from Sites NGHP-02-09 and NGHP-02-16 (NGHP-02: National Gas Hydrate Program Expedition 02) as well as a selection of pure fines (silica silt, mica, calcium carbonate, diatoms, kaolin, and bentonite). Clogging depended on the ratio of particle-to-pore throat size, and also on pore-fluid chemistry because the pore-fluid chemistry changes effectively increased or decreased the fines cluster size relative to the pore-throat width. These interactions can be predicted based on the fines electrical sensitivity (defined by Jang and Santamarina, 2016). The fine-grained sediment component (grain size < 75 m) from the primary gas hydrate reservoir layers at Sites NGHP-02-09 and -16 show clogging via blocking or size exclusion (sieving) due to the large particles. Clogs also formed due to bridging or blocking by clusters of the smaller particles. Clogging generally occurred for pore-water sediment concentrations so low (0.2% by mass or less), that it was difficult to resolve the enhanced clogging in the presence of the gas/liquid meniscus.

Bay of Bengal

Selected data on characteristics of glacial-deposit and carbonate-rock aquifers, Midwestern Basin and Arches region

In 1988, the Geological Survey (USGS) began study to examine the hydrogeologic framework, ground-water-flow systems, water chemistry, and withdrawal response of aquifers in glacial deposits and carbonate rock in the Midwestern Basins and Arches Region in western Ohio and eastern Indiana. As part of this study, data from pumped-well tests and instantaneous-rechange tests (slug tests) of wells completed in the glacial-deposit and carbonate-rock aquifers were compiled from reports and information on file with State agencies, environmental consulting firms, drilling firms, municipalities, universities, and the USGS. The data, from 73 counties in Ohio and Indiana, were entered into a computerized data base in a spreadsheet format and subsequently into a geographic information system (GIS). Aquifer-characteristics data from this compilation include the results of 105 pumped-well tests and 39 slug tests in wells completed in glacial deposits, 174 pumped-well tests in wells completed in the carbonate-rock aquifer, and 4 slug tests in wells completed in limestones and shales of Ordovician age. Transmissivities from the pumped-well tests in wells completed in glacial till and glacial-deposit aquifers (sands and gravels) range from 1.54 to 69,700 feet squared per day. Storage coefficients or specific yields range from 0.00002 to 0.38 at these wells. Horizontal-hydraulic conductivities from the slug tests in wells completed in glacial-deposit aquifers range from 0.33 to 1,000 feet per day. Transmissivities from the pumped-well tests in wells completed in the carbonate-rock aquifer range from 70 to 52,000 feet squared per day. Storage coefficient or specific yields at these wells range from 0.00001 to 0.05. Horizontal hydraulic conductivities from the slug tests in wells completed in limestones and shales of Ordovician age range from 0.0016 to 12 feet per day. These data are summarized in tables and figures within this report. The collection and compilation of selected aquifer-characteristic data for the glacial-deposit and carbonate-rock aquifers within the Midwestern Basin and Arches Region of Shaver (1985) are an essential part of the Midwestern Basins and Arches Regional Aquifer-Systems Analysis (Midwestern Basins and Arches RASA) project of the U.S. Geological Survey (USGS). Specifically, the data are needed to help describe ground-water flow in the regional aquifer system, which isone of the objectives of the Midwestern Basins and Arches RASA project (Bugliosi, 1990). To meet this objective, the Midwestern Basins and Arches RASA began subprojects in the Ohio and Indiana offices of the USGS to collect and compile available aquifer-characteristics data from aquifer tests of the glacial-deposit and carbonate-rock aquifers. The data were not reanalyzed to verify accuracy because of time constraints and insufficient data in many cases.

Illinois, Indiana, Kentucky, Ohio, West Virginia

Modelling streamwater chemistry as a mixture of soilwater end-members - An application to the Panola Mountain catchment, Georgia, U.S.A.

Streamwater chemistry at Panola Mountain research catchment, Georgia, U.S.A., is explained as a mixture of representative soilwater solutions that are considered to be temporally invariant to a first approximation. The selection of three end-members from all sampled soil waters is evaluated by comparing the observed and predicted streamwater concentration of six solutes (alkalinity, sulfate, sodium, magnesium, calcium and dissolved silica), which are assumed to mix conservatively, and by assessing the consistency of the implied hydrograph separation with the hydrological mechanisms that are believed to be operating in this catchment. The percentage of variation in the streamwater solute concentrations explained by the end-member mixing analysis (EMMA) ranges from 82 to >97%, and the hydrograph separation is, intuitively, physically reasonable. If the correct end-members have been identified, the streamwater chemical response to different levels of acidic deposition can be predicted by examining the change in each end-member under different loads; no hydrological model is required. If a traditional hydrochemical model, which is driven by rainfall quantity and quality, is desired, this analysis provides an indication of the model structure that would be necessary to reproduce both streamwater and soilwater chemistry.

Georgia

Ground-water quality data in the Monterey Bay and Salinas Valley Basins, California, 2005— Results from the California GAMA program

Ground-water quality in the approximately 1,000-square-mile Monterey Bay and Salinas Valley study unit was investigated from July through October 2005 as part of the California Ground-Water Ambient Monitoring and Assessment (GAMA) program. The study was designed to provide a spatially unbiased assessment of raw ground-water quality, as well as a statistically consistent basis for comparing water quality throughout California. Samples were collected from 94 public-supply wells and 3 monitoring wells in Monterey, Santa Cruz, and San Luis Obispo Counties. Ninety-one of the public-supply wells sampled were selected to provide a spatially distributed, randomized monitoring network for statistical representation of the study area. Six wells were sampled to evaluate changes in water chemistry: three wells along a ground-water flow path were sampled to evaluate lateral changes, and three wells at discrete depths from land surface were sampled to evaluate changes in water chemistry with depth from land surface. The ground-water samples were analyzed for volatile organic compounds (VOCs), pesticides, pesticide degradates, nutrients, major and minor ions, trace elements, radioactivity, microbial indicators, and dissolved noble gases (the last in collaboration with Lawrence Livermore National Laboratory). Naturally occurring isotopes (tritium, carbon-14, helium-4, and the isotopic composition of oxygen and hydrogen) also were measured to help identify the source and age of the sampled ground water. In total, 270 constituents and water-quality indicators were investigated for this study. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, water typically is treated, disinfected, and (or) blended with other waters to maintain water quality. In addition, regulatory thresholds apply to treated water that is served to the consumer, not to raw ground water. In this study, only six constituents, alpha radioactivity, N-nitrosodimethylamine, 1,2,3-trichloropropane, nitrate, radon-222, and coliform bacteria were detected at concentrations higher than health-based regulatory thresholds. Six constituents, including total dissolved solids, hexavalent chromium, iron, manganese, molybdenum, and sulfate were detected at concentrations above levels set for aesthetic concerns. One-third of the randomized wells sampled for the Monterey Bay and Salinas Valley GAMA study had at least a single detection of a VOC or gasoline additive. Twenty-eight of the 88 VOCs and gasoline additives investigated were found in ground-water samples; however, detected concentrations were one-third to one-sixty-thousandth of their respective regulatory thresholds. Compounds detected in 10 percent or more of the wells sampled include chloroform, a compound resulting from the chlorination of water, and tetrachloroethylene (PCE), a common solvent. Pesticides and pesticide degradates also were detected in one-third of the ground-water samples collected; however, detected concentrations were one-thirtieth to one-fourteen-thousandth of their respective regulatory thresholds. Ten of the 122 pesticides and pesticide degradates investigated were found in ground-water samples. Compounds detected in 10 percent or more of the wells sampled include the herbicide simazine, and the pesticide degradate deethylatrazine. Ground-water samples had a median total dissolved solids (TDS) concentration of 467 milligrams per liter (mg/L), and 16 of the 34 samples had TDS concentrations above the recommended secondary maximum contaminant level (SMCL-a threshold established for aesthetic qualities: taste, odor, and color) of 500 mg/L, while four samples had concentrations above the upper SMCL of 1,000 mg/L. Concentrations of nitrate plus nitrite ranged from 0.04 to 37.8 mg/L (as nitrogen), and two samples had concentrations above the health-based threshold for nitrate of 10 mg/L (as nitrogen). The median sulfate concentration

California

Dissolved pesticide data for the San Joaquin River at Vernalis and the Sacramento River at Sacramento, California, 1991-94

Water samples were collected from sites on the San Joaquin and Sacramento Rivers, California and were analyzed for dissolved organic pesticides. This data collection and analysis are a part of an ongoing project by the U.S. Geological Survey Toxic Contaminants Hydrology program to determine the fate and transport of organic pesticides that enter the San Francisco Bay Estuary. Concentrations of selected pesticides were measured in filtered water samples using solid-phase extraction and gas chromatograph-mass spectrometry at the U.S. Geological Survey organic chemistry laboratory in Sacramento.

California

Ground-water quality data in the Southern Sacramento Valley, California, 2005 — Results from the California GAMA Program

Ground-water quality in the approximately 2,100 square-mile Southern Sacramento Valley study unit (SSACV) was investigated from March to June 2005 as part of the Statewide Basin Assessment Project of Ground-Water Ambient Monitoring and Assessment (GAMA) Program. This study was designed to provide a spatially unbiased assessment of raw ground-water quality within SSACV, as well as a statistically consistent basis for comparing water quality throughout California. Samples were collected from 83 wells in Placer, Sacramento, Solano, Sutter, and Yolo Counties. Sixty-seven of the wells were selected using a randomized grid-based method to provide statistical representation of the study area. Sixteen of the wells were sampled to evaluate changes in water chemistry along ground-water flow paths. Four additional samples were collected at one of the wells to evaluate water-quality changes with depth. The GAMA Statewide Basin Assessment project was developed in response to the Ground-Water Quality Monitoring Act of 2001 and is being conducted by the California State Water Resources Control Board (SWRCB) in collaboration with the U.S. Geological Survey (USGS) and the Lawrence Livermore National Laboratory (LLNL). The ground-water samples were analyzed for a large number of man-made organic constituents (volatile organic compounds [VOCs], pesticides and pesticide degradates, pharmaceutical compounds, and wastewater-indicator constituents), constituents of special interest (perchlorate, N -nitrosodimethylamine [NDMA], and 1,2,3-trichloropropane [1,2,3-TCP]), naturally occurring inorganic constituents (nutrients, major and minor ions, and trace elements), radioactive constituents, and microbial indicators. Naturally occurring isotopes (tritium, and carbon-14, and stable isotopes of hydrogen, oxygen, and carbon), and dissolved noble gases also were measured to help identify the source and age of the sampled ground water. Quality-control samples (blanks, replicates, matrix spikes) were collected at ten percent of the wells, and the results for these samples were used to evaluate the quality of the data for the ground-water samples. Assessment of the quality-control data resulted in censoring of less than 0.03 percent of the analyses of ground-water samples. This study did not evaluate the quality of water delivered to consumers; after withdrawal from the ground, water typically is treated, disinfected, and (or) blended with other waters to maintain acceptable water quality. Regulatory thresholds apply to treated water that is served to the consumer, not to raw ground water. However, to provide some context for the results, concentrations of constituents measured in the raw ground water were compared with health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and California Department of Health Services (CADHS) (Maximum Contaminant Levels [MCLs], notification levels [NLs], or lifetime health advisories [HA-Ls]) and thresholds established for aesthetic concerns (Secondary Maximum Contaminant Levels [SMCLs]). All wells were sampled for organic constituents and selected general water quality parameters; subsets of wells were sampled for inorganic constituents, nutrients, and radioactive constituents. Volatile organic compounds were detected in 49 out of 83 wells sampled and pesticides were detected in 34 out of 82 wells; all detections were below health-based thresholds, with the exception of 1 detection of 1,2,3-trichloropropane above a NL. Of the 43 wells sampled for trace elements, 27 had no detections of a trace element above a health-based threshold and 16 had at least one detection above. Of the 18 trace elements with health-based thresholds, 3 (arsenic, barium, and boron) were detected at concentrations higher an MCL. Of the 43 wells sampled for nitrate, only 1 well had a detection above the MCL. Twenty wells were sampled for radioactive constituents; only 1 (radon-222) was measured at activities higher than the proposed MCL. Radon-222 was detected below the threshold in 7 wells and above the threshold in 13 wells. SMCLs have been established for nine constituents or parameters analyzed in SSACV. Six were measured at levels higher than an SMCL: chloride, iron, manganese, pH, specific conductance, and total dissolved solids. Chloride, iron, manganese, pH, and total dissolved solids were measured in 43 wells: 27 wells had no measurements above a threshold and 16 wells had a measurement above a threshold. Specific conductance was measured in 83 wells. In 68 wells, specific conductance was measured lower than the threshold and in 15 wells it was measured above the threshold.

California

Hydrogeology and geochemistry of aquifers underlying the San Lorenzo and San Leandro areas of the East Bay Plain, Alameda County, California

The East Bay Plain, on the densely populated eastern shore of San Francisco Bay, contains an upper aquifer system to depths of 250 feet below land surface and an underlying lower aquifer system to depths of more than 650 feet. Injection and recovery of imported water has been proposed for deep aquifers at two sites within the lower aquifer system. Successful operation requires that the injected water be isolated from surface sources of poor-quality water during storage and recovery. Hydraulic, geochemical, and isotopic data were used to evaluate the isolation of deeper aquifers. Ground-water responses to tidal changes in the Bay suggest that thick clay layers present within these deposits effectively isolate the deeper aquifers in the northern part of the study area from overlying surficial deposits. These data also suggest that the areal extent of the shallow and deep aquifers beneath the Bay may be limited in the northern part of the study area. Despite its apparent hydraulic isolation, the lower aquifer system may be connected to the overlying upper aquifer system through the corroded and failed casings of abandoned wells. Water-level measurements in observation wells and downward flow measured in selected wells during nonpumped conditions suggest that water may flow through wells from the upper aquifer system into the lower aquifer system during nonpumped conditions. The chemistry of water from wells in the East Bay Plain ranges from fresh to saline; salinity is greater than seawater in shallow estuarine deposits near the Bay. Water from wells completed in the lower aquifer system has higher pH, higher sodium, chloride, and manganese concentrations, and lower calcium concentrations and alkalinity than does water from wells completed in the overlying upper aquifer system. Ground-water recharge temperatures derived from noble-gas data indicate that highly focused recharge processes from infiltration of winter streamflow and more diffuse recharge processes from infiltration of precipitation occur within the study area. However, recharge of imported water from leaking water-supply pipes, believed by previous investigators to be a large source of ground-water recharge, was not supported on the basis of oxygen-18 and deuterium data collected as part of this study. Based on tritium/helium-3 ages, most water in the upper aquifer system is relatively young and was recharged after 1952; however, water in the lower aquifer system is older and does not contain detectable tritium. Carbon-14 ages interpreted for water from wells in the lower aquifer system and underlying partly consolidated rocks range from 500 to more than 20,000 years before present. The greatest ages were in water from wells completed in the partly consolidated deposits that underlie the northern part of the study area. Ground water from wells in the lower aquifer system near the proposed Bayside injection/recovery site was recharged about 9,400 years before present and appears to be isolated from surface sources of recharge and ground-water contamination.

California