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Groundwater quality and geochemistry of West Virginia’s southern coal fields

Coal mining has been the dominant industry and land use in West Virginia’s southern coal fields since the mid-1800s. Mortality rates for a variety of serious chronic conditions, such as diabetes, heart disease, and some forms of cancer in Appalachian coal mining regions, are higher than in areas lacking substantial coal mining activity within the Appalachian Region or elsewhere in the United States. Causes of the increased mortality and morbidity are not clear, but poor diet, high rates of smoking, socioeconomic factors, and the quality of groundwater used by area residents are all possible contributing factors. This study was conducted by the U.S. Geological Survey in cooperation with the West Virginia Department of Health and Human Resources and the West Virginia Department of Environmental Protection, with grant support from the Centers for Disease Control and Prevention (CDC) to assess the quality of groundwater in southern West Virginia. The data from this assessment of groundwater quality may be used by the CDC and other agencies to potentially investigate the role or lack thereof of groundwater quality with respect to mortality and morbidity rates in the region. The study was conducted in a region where a high density of current or past coal mining combined with a lack of advanced sewage treatment could affect concentrations of commonly occurring constituents plus contaminants, including nitrate, trace metals, major ions, indicator bacteria, radon, hydrogen sulfide, and dissolved hydrocarbons. Because rural residential wells and mine outfalls are considered private sources of water in the region, and are therefore unregulated and unmonitored, water-quality data are sparse. To fill the data gap and assess the groundwater quality in the region, water-quality samples were collected from 60 sites in a 10-county area. The 60 sites sampled included 46 rural residential homeowner wells and 14 mine outfall discharges used for residential supply. For this study, all samples were collected prior to any filtration or other treatments, typically at the pressure tank, and are indicative of total and dissolved constituents in the untreated water. Generally, data for the 60 sites indicate that most waters sampled do not exceed thresholds for most U.S. Environmental Protection Agency (EPA) drinking-water standards and U.S. Geological Survey (USGS) drinking-water screening criteria. However, there were several notable exceptions. Turbidity exceeded the 5-Nephelometric Turbidity Unit (NTU) EPA treatment technique (TT) drinking-water standard in 14 of 60 (23 percent) sites sampled and exceeded the 1-NTU TT standard in 51 of 60 (85 percent) sites sampled. Turbidity is common in many wells in southern West Virginia and may be attributed to iron oxyhydroxide precipitates, sediment carried into the aquifers from the shallow soil zone due to improperly constructed or cased wells or transported to the aquifer in shallow stress-relief fracture zones or through permeable bedding-plane partings. For the sites sampled, 31 of 60 (52 percent) had pH values at, above, or below the upper and lower range of the EPA Secondary Maximum Contaminant Level (SMCL, 6.5–8.5 standard units). Of those 31 sites, 28 (90 percent) were indicative of acidic corrosive water and 3 (10 percent) were indicative of alkaline water. The Langelier Saturation Index (LSI), which is a measure of the corrosivity of the water, was computed for all sites sampled for the study. Eighty-two percent of the sites sampled had waters that were classified as corrosive, based on a LSI less than −0.5. Corrosive water has the potential to leach lead, copper, and other metals from lead, copper, galvanized, or lead-tin soldered connections in water lines. The chloride to sulfate mass ratio also was assessed with the alkalinity to indicate the potential to promote galvanic corrosion (PPGC) of water lines and plumbing fixtures. Only one of the sites (1.7 percent) classified as a corrosive water site, had a PPGC considered high; the remaining sites were classified as having either a moderate (53.3 percent) or low (45 percent) PPGC. Therefore, the type of plumbing systems sampled for this study may be affected by corrosive water, but the potential for leaching trace metals and other constituents from residential plumbing systems containing older galvanized pipes or lead-tin soldered copper pipes is moderate to low. The indicator bacteria total coliform and Escherichia coli ( E. coli ) also were detected in groundwater samples to varying degrees. Total coliforms, which are a broad class of indicator bacteria, are common in groundwater in southern West Virginia and were detected in 39 of the 60 sites (65 percent) sampled. The presence of total coliform bacteria is a potential indicator of surface contamination, due to improperly constructed or cased wells, or infiltration of soil or other surface contaminants into the aquifer or well bore. E. coli bacteria, however, are much more indicative of fecal contamination of groundwater from either human or animal sources, and 14 of the 60 (23 percent) sites sampled had detections of E. coli . Although only a few strains of E. coli are known pathogens, their presence in groundwater may be an indicator of other related pathogens such as viruses and should be regarded as a serious potential issue. Water treatment such as chlorination, ozonation, or ultraviolet light may be appropriate to kill potential pathogenic bacteria or viruses in the source water. Manganese and iron were prevalent contaminants in the groundwater samples collected for this study, with 30 of 60 (50 percent) sites analyzed for manganese and 25 of 60 (42 percent) sites analyzed for iron exceeding the proposed 50- and 300-micrograms per liter (µg/L) SMCL drinking-water standards, respectively, for aesthetic criteria such as taste, odor, or staining of plumbing fixtures. Fourteen of the 60 sites sampled (23 percent) had concentrations of manganese that exceeded the 300-µg/L USGS health-based screening level, and 1 site exceeded the 1,600-µg/L EPA drinking-water equivalent level, which is based on a lifetime exposure level. Sodium is another common constituent in groundwater within the study area. Sodium has an EPA health-based value (HBV) of 20 milligrams per liter (mg/L) for individuals who are on a sodium-restricted diet for blood pressure or other health reasons. Sodium concentrations exceeded the 20-mg/L EPA HBV in 27 of 60 (45 percent) samples. Radon, a naturally occurring carcinogenic radioactive gas known to cause lung cancer, was detected at concentrations at or exceeding the proposed 300-picocuries per liter (pCi/L) EPA Maximum Contaminant Level (MCL) in 12 of the 60 (20 percent) sites sampled. Sites with radon gas concentrations exceeding the 300-pCi/L proposed MCL have the potential for airborne concentrations of radon to exceed the 4-pCi/L indoor air standard. Inhalation of radon can cause lung cancer, and the 4-pCi/L indoor air standard is based on an inhalation standard. Therefore, homeowners whose wells have radon gas concentrations exceeding 300 pCi/L may be advised to have their indoor air tested to determine if indoor air concentrations exceed the 4-pCi/L indoor air standard established by the EPA. Various factors were analyzed statistically and graphically to determine whether they have an influence on groundwater quality within the study area, including topographic setting, well depth, type of mining (surface or underground), type of site (well or mine outfall), and geologic formation. Only geologic formation and the type of site sampled had strong statistical correlations with one or more of the constituents of concern for this study. The overall chemistry of outfalls (mine outfalls) and wells was significantly different, with a much higher dissolved oxygen content in outfalls than in wells. The dissolved oxygen content is the primary component driving the oxidation and reduction of minerals, and the precipitation of minerals that are saturated or super saturated with respect to various cations and anions. Median dissolved oxygen concentrations for the outfalls sampled was 8.75 mg/L, and only 0.4 mg/L for the wells sampled. Median concentrations of sulfate and selenium were much higher in waters from the outfalls sampled, with median concentrations of 73.75 mg/L and 2.35 µg/L, respectively, compared to the wells sampled, which had median concentrations of 18.3 mg/L and less than (<) the 0.05-µg/L method detection limit, respectively. The maximum selenium concentration was for a well, with a concentration of 16.6 µg/L. The geochemical processes that control sulfate and selenium concentrations in groundwater are similar and are the result of the oxidation of sulfide minerals such as pyrite and ferroselite. Iron and manganese concentrations were elevated in most of the wells sampled, with median concentrations of 269.5 and 124.5 µg/L, respectively, but were rarely detected in the outfalls sampled, with median concentrations of < 4.0 and < 0.4 µg/L, respectively. The difference in iron and manganese between wells and outfalls is indicative of the role of dissolved oxygen on processes controlling groundwater chemistry in the region. Three principal geologic formations were assessed for the study, and the overall chemistry for the Pocahontas, New River, and Kanawha Formations varied substantially with respect to several constituents. Concentrations of calcium, magnesium, and total dissolved solids were highest for sites sampled in the Pocahontas Formation, with median concentrations of 41.9, 18.6, and 312 mg/L, respectively. For constituents that are commonly associated with mining activity, the highest concentrations were for sites sampled in the New River Formation, with median concentrations of iron and manganese of 2,450 µg/L and 482 µg/L, respectively, and a median pH of 6.35 standard units. Concentrations of barium also were elevated in samples collected from sites in the New River Formation, with a median barium concentration of 184 µg/L. The source of the barium is not fully known but may be associated with commingling of shallow groundwater with deeper brines or dissolution of the mineral barite. The highest median sulfate concentrations were from sites sampled in the Pocahontas Formation, with a median concentration of 64.0 mg/L. Of the 12 sites at or exceeding the 300-pCi/L proposed drinking-water standard for radon, 8 (67 percent of MCL exceedances) were for sites deriving water from the Kanawha Formation, 3 (25 percent of MCL exceedances) were for sites deriving water from the New River Formation, and only 1 site was for water from the Pocahontas Formation (8 percent of proposed MCL exceedances). Dissolved hydrocarbons, including methane, ethane, propane, propene, n - and i -butane, 1-butene, n - and i -pentane, pentane, 2- and 3-ethyl pentane, hexane, and benzene were analyzed in samples collected from 59 of the 60 sites to assess the potential occurrence and sources of these trace gases in groundwater within the study area. Results of the analysis indicate that most of the gas is of shallow biogenic origin, possibly associated with coal-bed methane, but a subset of samples has a gas signature and a chloride to bromide ratio indicative of potential mixing with deeper thermogenic gases. Only 2 of the 59 (3.3 percent) sites sampled had concentrations of methane gas, which is a highly combustible and explosive gas, exceeding the 10 milligrams per kilogram level of concern established by the U.S. Office of Surface Mining Reclamation and Enforcement. Principal components analysis was used to assess the primary geochemical processes occurring in the aquifers sampled. The first principal component had significant positive loadings for bromide, chloride, silica, ammonia, barium, iron, manganese, and arsenic, and significant negative loadings for dissolved oxygen, potassium, nitrate, and uranium, and reflects reduction and oxidation (redox) processes occurring in deeper anoxic groundwater or shallow oxic groundwater. The strong positive loadings for iron, manganese, barium, and arsenic are correlated with reducing conditions often found deeper in the aquifer. More oxic water is correlated with oxidation of nitrogen species to nitrate and environmental mobilization of uranium and sulfate in shallow wells and mine outfalls.

West Virginia↗

Relation of water chemistry of the Edwards aquifer to hydrogeology and land use, San Antonio Region, Texas

Water-chemistry data from the Edwards aquifer for 1976-85, consisting of nearly 1,500 chemical analyses from 280 wells and 3 springs, were used to statistically evaluate relations among ground-water chemistry, hydrogeology, and land use. Five land uses associated with sampled wells were classified on the basis of published information and field surveys. Four major subareas of the aquifer were defined to reflect the relative susceptibility of ground water to contamination originating from human activities using hydrogeologic and tritium data. Water from an agricultural area over the unconfined zone of the aquifer had the largest median concentration of nitrite plus nitrate. Large nitrite plus nitrate concentrations were spatially associated with large tritium concentrations and nitrogen isotopic ratios characteristic of streamflow recharge. Detections of fecal-coliform bacteria were associated mainly with water from wells completed in the unconfined zone. Most of the occurrences of tetrachloroethylene, l,2-(trans)-dichloroethylene, trichlorofluoromethane, 1,1,1-trichloroethane, and 2,4-D in ground water were associated with wells completed in the unconfined zone of the aquifer. Fatty acids detected in water from some wells may commonly be present naturally in ground water. The percentage of samples in which arsenic, barium, lead, and zinc were detected was similar among subareas; the samples were from the freshwater parts of the aquifer. Large lead and zinc concentrations were associated with volumes of pumpage less than 1,000 gallons. In general, the quality of ground water in the freshwater parts of the aquifer (north of the "bad-water" line) is suitable for all uses including human consumption. Two areas that are exceptions are: (1) Northeast of Garner Field in Uvalde, Texas, where PCE (tetrachloroethylene) has been detected in groundwater samples, and (2) north-central Bexar County near the former West Avenue landfill where PCE and benzene have been detected in ground-water samples. Concentrations of these organic compounds in water from many wells in the two areas exceed the maximum contaminant level for human consumption set by the U.S. Environmental Protection Agency.

Water-Resources Investigations Report↗

Temporal analysis of water chemistry and smallmouth bass (Micropterus dolomieu) health at two sites with divergent land use in the Susquehanna River watershed, Pennsylvania, USA

Monitoring wild fish health and exposure effects in impacted rivers and streams with differing land use has become a valuable research tool. Smallmouth bass ( Micropterus dolomieu ) are a sensitive, indicator species that exhibit signs of immunosuppression and endocrine disruption in response to water quality changes and contaminant exposure. To determine the impact of agriculture and development on smallmouth bass health, two sites (a developed/agriculture site and a forested site) in the Susquehanna River watershed, Pennsylvania were selected where bass and water chemistry were sampled from 2015 to 2019. Smallmouth bass were sampled for histopathology to assess parasite and macrophage aggregate density in the liver and spleen, condition factor (Ktl), hepatic gene transcript abundance, hepatosomatic index (HSI), and a health assessment index (HAI). Land use at the developed/agriculture site included greater pesticide application rates and phytoestrogen crop cover and more detections and higher concentrations of pesticides, wastewater-associated contaminants, hormones, phytoestrogens, and mycotoxins than at the forested site. Additionally, at the developed/agriculture site, indicators of molecular changes, including oxidative stress, immune/inflammation, and lipid metabolism-related hepatic gene transcripts, were associated with more contaminants and land use variables. At both sites, there were multiple associations of contaminants with liver and/or spleen macrophage aggregate density, indicating that changes at the molecular level seemed to be a better indicator of exposures unique to each site. The findings illustrate the importance of timing for land management practices, the complex mixtures aquatic animals are exposed to, and the temporal changes in contaminant concentration. Agricultural practices that affect hepatic gene transcripts associated with immune function and disease resistance were demonstrated which could negatively affect smallmouth bass populations.

Pennsylvania↗

Double-disk solid-phase extraction--Simultaneous cleanup and trace enrichment of herbicides and metabolites from environmental samples

Phenylurea and triazine herbicides, including some metabolites, were isolated from water and soil extracts by solid-phase extraction using a layered system of two extraction disks, a method called double-disk solid-phase extraction. The first disk consisted of strong anion exchange (SAX) of 10-μm styrene divinylbenzene (SDB) particles embedded in Teflon, and the second disk was a C 18 disk of 10-μm particles also embedded in Teflon. A volume of 500 mL of water or aqueous soil extract is passed through the layered system with the SAX disk first. The purpose of the SAX disk is to remove the humic and fulvic acids from the water or aqueous soil extract by ion exchange through their carboxyl groups. Even during methanol elution of herbicides, the humic substances remain bound to the SAX disk with >85% retention. Elution with methanol results in more than 90% recovery of the herbicides from the layered extraction disks. Removal of the humic and fulvic acids results in greater sensitivity for diode array detection quantitation (0.05 μg/L for herbicides) by substantially reducing the absorbance of the humic peak on the LC chromatogram. The herbicides adsorb to the SAX disk either through hydrogen bonding to the anion-exchange sites or by hydrophobic interaction with the SDB surface of the anion-exchange disk. The method was tested for the analysis of natural water samples from the Mississippi Embayment, a cotton-growing area of the southeastern United States.

Analytical Chemistry↗

The saturated zone at Yucca Mountain: An overview of the characterization and assessment of the saturated zone as a barrier to potential radionuclide migration

The US Department of Energy is pursuing Yucca Mountain, Nevada, for the development of a geologic repository for the disposal of spent nuclear fuel and high-level radioactive waste, if the repository is able to meet applicable radiation protection standards established by the US Nuclear Regulatory Commission and the US Environmental Protection Agency (EPA). Effective performance of such a repository would rely on a number of natural and engineered barriers to isolate radioactive waste from the accessible environment. Groundwater beneath Yucca Mountain is the primary medium through which most radionuclides might move away from the potential repository. The saturated zone (SZ) system is expected to act as a natural barrier to this possible movement of radionuclides both by delaying their transport and by reducing their concentration before they reach the accessible environment. Information obtained from Yucca Mountain Site Characterization Project activities is used to estimate groundwater flow rates through the site-scale SZ flow and transport model area and to constrain general conceptual models of groundwater flow in the site-scale area. The site-scale conceptual model is a synthesis of what is known about flow and transport processes at the scale required for total system performance assessment of the site. This knowledge builds on and is consistent with knowledge that has accumulated at the regional scale but is more detailed because more data are available at the site-scale level. The mathematical basis of the site-scale model and the associated numerical approaches are designed to assist in quantifying the uncertainty in the permeability of rocks in the geologic framework model and to represent accurately the flow and transport processes included in the site-scale conceptual model. Confidence in the results of the mathematical model was obtained by comparing calculated to observed hydraulic heads, estimated to measured permeabilities, and lateral flow rates calculated by the site-scale model to those calculated by the regional-scale flow model. In addition, it was confirmed that the flow paths leaving the region of the potential repository are consistent with those inferred from gradients of measured head and those independently inferred from water-chemistry data. The general approach of the site-scale SZ flow and transport model analysis is to calculate unit breakthrough curves for radionuclides at the interface between the SZ and the biosphere using the three-dimensional site-scale SZ flow and transport model. Uncertainties are explicitly incorporated into the site-scale SZ flow and transport abstractions through key parameters and conceptual models. ?? 2002 Elsevier Science B.V. All rights reserved.

Journal of Contaminant Hydrology↗

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↗

Trace element geochemistry and surface water chemistry of the Bon Air coal, Franklin County, Cumberland Plateau, southeast Tennessee

Mean contents of trace elements and ash in channel, bench-column, and dump samples of the abandoned Bon Air coal (Lower Pennsylvanian) in Franklin County, Tennessee are similar to Appalachian COALQUAL mean values, but are slightly lower for As, Fe, Hg, Mn, Na, Th, and U, and slightly higher for ash, Be, Cd, Co, Cr, REEs, Sr, and V, at the 95% confidence level. Compared to channel samples, dump sample means are slightly lower in chalcophile elements (As, Cu, Fe, Ni, Pb, S, Sb, and V) and slightly higher in clay or heavy-mineral elements (Al, K, Mn, REEs, Th, Ti, U, and Y), but at the 95% confidence level, only As and Fe are different. Consistent abundances of clay or heavy-mineral elements in low-Br, high-S, high-ash benches that are relatively enriched in quartz and mire-to-levee species like Paralycopodites suggest trace elements are largely fluvial in origin. Factor analysis loadings and correlation coefficients between elements suggest that clays host most Al, Cr, K, Ti, and Th, significant Mn and V, and some Sc, U, Ba, and Ni. Heavy accessory minerals likely house most REEs and Y, lesser Sc, U, and Th, and minor Cr, Ni, and Ti. Pyrite appears to host As, some V and Ni, and perhaps some Cu, but Cu probably exists largely as chalcopyrite. Data suggest that organic debris houses most Be and some Ni and U, and that Pb and Sb occur as Pb-Sb sulfosalt(s) within organic matrix. Most Hg, and some Mn and Y, appear to be hosted by calcite, suggesting potential Hg remobilization from original pyrite, and Hg sorption by calcite, which may be important processes in abandoned coals. Most Co, Zn, Mo, and Cd, significant V and Ni, and some Mn probably occur in non-pyritic sulfides; Ba, Sr, and P are largely in crandallite-group phosphates. Selenium does not show organic or "clausthalite" affinities, but Se occurrence is otherwise unclear. Barium, Mn, Ni, Sc, U, and V, with strongly divided statistical affinities, likely occur subequally in multiple modes. For study area surface waters, highest levels of most trace elements occur in mine-adit or mine-dump drainage. Effluent flow rates strongly affect both acidity and trace element levels. Adit drainages where flow is only a trickle have the most acidic waters (pH 3.78-4.80) and highest trace element levels (up to two orders of magnitude higher than in non-mine site waters). Nonetheless, nearly all surface waters have low absolute concentrations of trace elements of environmental concern, and all waters sampled meet U.S. EPA primary drinking water standards and aquatic life criteria for all elements analyzed. Secondary drinking water standards are also met for all parameters except Al, pH, Fe, and Mn, but even in extreme cases (mine waters with pH as low as 3.78 and up to 1243 ppb Al, 6280 ppb Fe, and 721 ppb Mn, and non-mine dam-outflow waters with up to 18,400 ppb Fe and 1540 ppb Mn) downslope attenuation is apparently rapid, as down-drainage plateau-base streams show background levels for all these parameters. ?? 2005 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

Quantifying form resistance is essential for estimating summer low and bankfull flow from stream survey channel morphology

Reliable estimates of low flow and flood discharge at ungaged locations are required for evaluating stream flow alteration, designing culverts and stream crossings, and interpreting regional surveys of habitat and biotic condition. Very few stream gaging stations are located on small, remote streams, which typically have complex channel morphology. Adequate gaging is also lacking on larger streams that are remote, smaller than those typically gaged, or have channel morphology not conducive to installation of gages. Complex channels typically contain large scale hydraulic roughness elements that dominate flow patterns (i.e., form roughness), making it difficult to measure channel cross-section area and water velocity, or to measure channel volume even where discharge is known. In channels with large channel form roughness, it is equally difficult to estimate discharge using commonly applied equations based on slope and channel dimensions or basin area. We employed a novel approach that explicitly accounts for hydraulic resistance from large wood and riffle-pool morphology (form roughness) in calculating low flow and bankfull discharge from stream and river physical habitat data collected from 4229 stream and river sites in the conterminous US (CONUS) sampled in 2008–9 and 2013–14 as part of the US Environmental Protection Agency's N ational R ivers and S treams A ssessment (NRSA). Hydraulic resistance derived from form roughness clearly dominated resistance derived from bed particles (particle resistance) during summer low flows in wadeable streams across the spectrum of channel slopes and substrate sizes smaller than boulders. Under bankfull conditions, the influence of form resistance relative to particle resistance was diminished, but form resistance still dominated except in large low gradient rivers lacking complex channels, and in streams or rivers with boulder-size bed particles. We validated our hydraulic resistance estimates by comparing measured discharges with calculated discharges that used those hydraulic resistance estimates along with measured NRSA channel morphology data. Morphology-based summer discharge (low flow) estimates and direct field measurements of discharge in 2333 wadeable CONUS streams showed reasonable agreement (median difference < 2.5×) for discharges ranging from 3.6 × 10 −5 to 123 m 3 /s and drainage areas of 0.12 to 171,000 km 2 . In a subset of 759 of NRSA's larger wadeable stream and non-wadeable river sites where nearby U.S. Geological Survey (USGS) gage data were available and adequate, our morphology-based summer discharge estimates agreed fairly well (median difference < 2.0×) with USGS 20-yr average August mean flows ranging from 0.003 to 16,000 m 3 /s. Similarly, morphology-based estimates of bankfull flow ranging from 0.3 to 100,000 m 3 /s agreed reasonably well with the 1.5-yr recurrence interval flood in these gaged sites (median deviation <2.2×). These findings demonstrate the importance of quantifying flow resistance from large-scale form roughness features in natural channels and provide a novel approach for estimating discharge from widely available survey data. This will allow examination of discharge and its ecological influence across the full range of stream and river sizes sampled by NRSA or other synoptic surveys where comprehensive measures of biota, physical habitat, and chemistry are also made. Although these morphology-based estimates exhibit some variability, they are adequate for examining regional patterns in discharge and flow alteration and their association with instream biota and anthropogenic disturbances, providing summer low and bankfull flow information where reliable estimates are lacking.

Geomorphology↗

Toxicity of alkalinity to Hyalella azteca

Toxicity testing and chemical analyses of sediment pore water have been suggested for use in sediment quality assessments and sediment toxicity identification evaluations. However, caution should be exercised in interpreting pore-water chemistry and toxicity due to inherent chemical characteristics and confounding relationships. High concentrations of alkalinity, which are typical of sediment pore waters from many regions, have been shown to be toxic to test animals. A series of tests were conducted to assess the significance of elevated alkalinity concentrations to Hyalella azteca, an amphipod commonly used for sediment and pore-water toxicity testing. Toxicity tests with 14-d old and 7-d old animals were conducted in serial dilutions of sodium bicarbonate (NaHCO3) solutions producing alkalinities ranging between 250 to 2000 mg/L as CaCO3. A sodium chloride (NaCl) toxicity test was also conducted to verify that toxicity was due to bicarbonate and not sodium. Alkalinity was toxic at concentrations frequently encountered in sediment pore water. There was also a significant difference in the toxicity of alkalinity between 14-d old and 7-d old animals. The average 96-h LC50 for alkalinity was 1212 mg/L (as CaCO3) for 14-d old animals and 662 mg/L for the younger animals. Sodium was not toxic at levels present in the NaHCO3 toxicity tests. Alkalinity should be routinely measured in pore-water toxicity tests, and interpretation of toxicity should consider alkalinity concentration and test-organism tolerance.

Bulletin of Environmental Contamination and Toxico↗

Variation of lead isotopic composition and atomic weight in terrestrial materials (IUPAC Technical Report)

The isotopic composition and atomic weight of lead are variable in terrestrial materials because its three heaviest stable isotopes are stable end-products of the radioactive decay of uranium ( 238 U to 206 Pb; 235 U to 207 Pb) and thorium ( 232 Th to 208 Pb). The lightest stable isotope, 204 Pb, is primordial. These variations in isotope ratios and atomic weights provide useful information in many areas of science, including geochronology, archaeology, environmental studies, and forensic science. While elemental lead can serve as an abundant and homogeneous isotopic reference, deviations from the isotope ratios in other lead occurrences limit the accuracy with which a standard atomic weight can be given for lead. In a comprehensive review of several hundred publications and analyses of more than 8000 samples, published isotope data indicate that the lowest reported lead atomic weight of a normal terrestrial materials is 206.1462 ± 0.0028 ( k = 2), determined for a growth of the phosphate mineral monazite around a garnet relic from an Archean high-grade metamorphic terrain in north-western Scotland, which contains mostly 206 Pb and almost no 204 Pb. The highest published lead atomic weight is 207.9351 ± 0.0005 ( k = 2) for monazite from a micro-inclusion in a garnet relic, also from a high-grade metamorphic terrain in north-western Scotland, which contains almost pure radiogenic 208 Pb. When expressed as an interval, the lead atomic weight is [206.14, 207.94]. It is proposed that a value of 207.2 be adopted for the single lead atomic-weight value for education, commerce, and industry, corresponding to previously published conventional atomic-weight values.

Pure and Applied Chemistry↗

Limited occurrence of denitrification in four shallow aquifers in agricultural areas of the United States

The ability of natural attenuation to mitigate agricultural nitrate contamination in recharging aquifers was investigated in four important agricultural settings in the United States. The study used laboratory analyses, field measurements, and flow and transport modeling for monitoring well transects (0.5 to 2.5 km in length) in the San Joaquin watershed, California, the Elkhorn watershed, Nebraska, the Yakima watershed, Washington, and the Chester watershed, Maryland. Ground water analyses included major ion chemistry, dissolved gases, nitrogen and oxygen stable isotopes, and estimates of recharge date. Sediment analyses included potential electron donors and stable nitrogen and carbon isotopes. Within each site and among aquifer-based medians, dissolved oxygen decreases with ground water age, and excess N 2 from denitrification increases with age. Stable isotopes and excess N 2 imply minimal denitrifying activity at the Maryland and Washington sites, partial denitrification at the California site, and total denitrification across portions of the Nebraska site. At all sites, recharging electron donor concentrations are not sufficient to account for the losses of dissolved oxygen and nitrate, implying that relict, solid phase electron donors drive redox reactions. Zero-order rates of denitrification range from 0 to 0.14 μmol N L −1 d −1 , comparable to observations of other studies using the same methods. Many values reported in the literature are, however, orders of magnitude higher, which is attributed to a combination of method limitations and bias for selection of sites with rapid denitrification. In the shallow aquifers below these agricultural fields, denitrification is limited in extent and will require residence times of decades or longer to mitigate modern nitrate contamination.

Journal of Environmental Quality↗

Factors related to occurrence and distribution of selected bacterial and protozoan pathogens in Pennsylvania streams

The occurrence and distribution of fecal indicator bacteria (FIB) and bacterial and protozoan pathogens are controlled by diverse factors. To investigate these factors in Pennsylvania streams, 217 samples were collected quarterly from a 27-station water-quality monitoring network from July 2007 through August 2009. Samples were analyzed for concentrations of Escherichia coli (EC) and enterococci (ENT) indicator bacteria, concentrations of Cryptosporidium oocysts and Giardia cysts, and the presence of four genes related to pathogenic types of EC ( eae A, stx 2, stx 1, rfb O157 ) plus three microbial source tracking (MST) gene markers that are also associated with pathogenic ENT and EC ( esp , LTIIa, STII). Water samples were concurrently analyzed for basic water chemistry, physical measures of water quality, nutrients, metals, and a suite of 79 organic compounds that included hormones, pharmaceuticals, and antibiotics. For each sample location, stream discharge was measured by using standardized methods at the time of sample collection, and ancillary sample site information, such as land use and geological characteristics, was compiled. Samples exceeding recreational water quality criteria were more likely to contain all measured pathogen genes but not Cryptosporidium or Giardia (oo)cysts. FIB and Giardia density and frequency of eae A gene occurrence were significantly related to season. When discharge at a sampling location was high (>75th percentile of daily mean discharge), there were greater densities of FIB and Giardia , and the stx2 , rfb O157 , STII, and esp genes were found more frequently than at other discharge conditions. Giardia occurrence was likely related to nonpoint sources, which are highly influential during seasonal overland transport resulting from snowmelt and elevated precipitation in late winter and spring in Pennsylvania. When MST markers of human, swine, or bovine origin were present, samples more frequently carried the eae A, stx 2, stx 1, and rfb O157 genes, but no genes were related exclusively to an individual MST marker. The human source pharmaceuticals (HSPs) acetaminophen and caffeine were correlated with Giardia , and the presence of HSPs proved to be more useful than MST markers in distinguishing the occurrence of Giardia . The HSPs caffeine and carbamazepine were correlated with the sum total of pathogen genes detected in a sample, demonstrating the value of using HSPs as an indicator of fecally derived pathogens. Sites influenced by urban land use with less forest were more likely to have greater FIB and Giardia densities and sum of the array of pathogen genes. Sites dominated by shallow carbonate bedrock in the upstream catchment were likely to have greater FIB densities and higher sum totals of pathogen genes but no correlation with Giardia detection. Our study provides a range of specific environmental, chemical, geologic, and land-use variables related to occurrence and distribution of FIB and selected bacterial and protozoan pathogens in Pennsylvania streams. The information presented could be useful for resource managers in understanding bacterial and protozoan pathogen occurrence and their relation to fecal indicator bacteria in similar settings.

Pennsylvania↗

Environmental assessment of metal exposure to corals living in Castle Harbour, Bermuda

Environmental contamination in Castle Harbour, Bermuda, has been linked to the dissolution and leaching of contaminants from the adjacent marine landfill. This study expands the evidence for environmental impact of leachate from the landfill by quantitatively demonstrating elevated metal uptake over the last 30 years in corals growing in Castle Harbour. Coral Pb/Ca, Zn/Ca and Mn/Ca ratios and total Hg concentrations are elevated relative to an adjacent control site in John Smith's Bay. The temporal variability in the Castle Harbour coral records suggests that while the landfill has increased in size over the last 35 years, the dominant input of metals is through periodic leaching of contaminants from the municipal landfill and surrounding sediment. Elevated contaminants in the surrounding sediment suggest that resuspension is an important transport medium for transferring heavy metals to corals. Increased winds, particularly during the 1990s, were accompanied by higher coral metal composition at Castle Harbour. Coupled with wind-induced resuspension, interannual changes in sea level within the Harbour can lead to increased bioavailability of sediment-bound metals and subsequent coral metal assimilation. At John Smith's Bay, large scale convective mixing may be driving interannual metal variability in the coral record rather than impacts from land-based activities. Results from this study provide important insights into the coupling of natural variability and anthropogenic input of contaminants to the nearshore environment.

Castle Harbour↗

Field evidence for a protistan role in an organically-contaminated aquifer

The association between protists, bacteria, and dissolved organic carbon (DOC) in an oxygen-depleted, 6 km-long wastewater contaminant plume within a sandy aquifer (Cape Cod, MA) was investigated by comparing abundance patterns along longitudinal and vertical transects and at a control site. Strong linear correlations were observed between unattached bacterial abundance and DOC for much of the upgradient-half of the plume (0.1−2.5 km downgradient from the source) that is characterized by quasi-steady state chemistry. However, a logarithmic decrease was observed between the number of protists supported per mg of DOC and the estimated age of the DOC within the plume. The relatively labile dissolved organic contaminants that characterize the groundwater sampled from the plume ≤0.1 km downgradient from the contaminant source appeared to indirectly support 3−4 times as many protists (per mg of DOC) as the older, more recalcitrant DOC in the alkylbenzene sulfonate (ABS)-contaminated zone at 3 km downgradient (∼30 years travel time). Substantive numbers of protists (>10 4 /cm 3 ) were recovered from suboxic zones of the plume. The higher than expected ratios of protists to unattached bacteria (10 to 100:1) observed in much of the plume suggest that protists may be grazing upon both surface-associated and unattached bacterial communities to meet their nutritional requirements. In closed bottle incubation experiments, the presence of protists caused an increase in bacterial growth rate, which became more apparent at higher amendments of labile DOC (3−20 mgC/L). The presence of protists resulted in an increase in the apparent substrate saturation level for the unattached bacterial community, suggesting an important role for protists in the fate of more-labile aquifer organic contaminants.

Massachusetts↗

Role of sediment resuspension in the remobilization of particulate-phase metals from coastal sediments

The release of particulate-phase trace metals due to sediment resuspension has been investigated by combining erosion chamber experiments that apply a range of shear stresses typically encountered in coastal environments with a shear stress record simulated by a hydrodynamic model. Two sites with contrasting sediment chemistry were investigated. Sediment particles enriched in silver, copper, and lead, 4−50 times greater than the bulk surface-sediment content, were the first particles to be eroded. As the shear-stress level was increased in the chamber, the total mass eroded increased, but the enrichment of these trace metals fell, approaching the bulk-sediment content. From the temporal distribution of shear stress generated by the hydrodynamic model for a site in Boston Harbor, resuspension fluxes were estimated. The erosion threshold of this site is exceeded during spring tides, releasing the particles enriched in trace metals into the water column. Due to the higher trace metal content and the regularity of resuspension, low-energy resuspension events (up to a shear stress of 0.2 N/m 2 ) contribute up to 60% of the resuspension metal flux in an average year. The estimated annual quantity of copper and lead resuspended into the water column is higher than estimates of the total riverine flux for these metals. These results indicate that sediment resuspension is a very important mechanism for releasing metals into the water column and provide new insight into the chemical and physical processes controlling the long-term fate of trace metals in contaminated sediments.

Massachusetts↗

Four decades of regional wet deposition, local bulk deposition, and stream-water chemistry show the influence of nearby land use on forested streams in Central Appalachia☆

Hydrologic monitoring began on two headwater streams (<1 km 2 ) on the University of Kentucky's Robinson Forest in 1971. We evaluated stream-water (1974–2013) and bulk-deposition (wet + dust) (1984–2013) chemistry in the context of regional wet-deposition patterns that showed decreases in both sulfate and nitrate concentrations as well as proximal surface-mine expansion. Decadal time steps (1974–83, 1984–93, 1994–2003, 2004–2013) were used to quantify change. Comparison of the first two decades showed similarly decreased sulfate (minimum flow-adjusted annual-mean concentration of ≈13.5 mg/L in 1982 to 8.8 mg/L in 1992) and increased pH (6.6–6.8) in both streams, reflecting contemporaneous changes in both bulk and wet deposition. In contrast, concentrations of nitrate (0.14 to >0.25 mg/L) and base cations increased between these two decades, coinciding with expansion of surface mining between 1985 and 1995. In 2004, stream-water pH (6.7 in 2004), sulfate (9.2 mg/L), and nitrate (>0.11 mg/L) were similar to 1982, despite wet-deposition concentrations being lower. Base-cation concentrations were higher in the stream adjacent to ongoing surface mining relative to the stream situated near the middle of the experimental forest. However, pH decreased to approximately 5.7 by 2013 for both streams, which, combined with a shift in dominant cations from calcium to magnesium and potassium, indicates that the soil-buffering capacity of this landscape has been exceeded. Ratios of bulk deposition and stream-water concentrations indicate enrichment of sulfate (1.7–25.2) and cations (0.5–64.8), but not nitrogen (0.1–5.6), indicating that the Forest is not nitrogen saturated and that ongoing changes in water-quality are sulfate driven. When concentrations were adjusted to account for changes in streamflow (climate) over the 4 decades, external influences (land management/regulation) explained most change. The amount and direction of change differed among constituents, both between consecutive decades and between the first and last decades, reflecting the influence of localized surface mining even as regional wet deposition continued to improve due to the Clean Air Act. The implication is that localized stressors have the potential to out-pace the benefits of national environmental policies for communities that depend on local water-resources in similar environments.

Kentucky↗

Transcriptomic effects-based monitoring for endocrine active chemicals: Assessing relative contribution of treated wastewater to downstream pollution

The present study investigated whether a combination of targeted analytical chemistry information with unsupervised, data-rich biological methodology (i.e., transcriptomics) could be utilized to evaluate relative contributions of wastewater treatment plant (WWTP) effluents to biological effects. The effects of WWTP effluents on fish exposed to ambient, receiving waters were studied at three locations with distinct WWTP and watershed characteristics. At each location, 4 d exposures of male fathead minnows to the WWTP effluent and upstream and downstream ambient waters were conducted. Transcriptomic analyses were performed on livers using 15 000 feature microarrays, followed by a canonical pathway and gene set enrichment analyses. Enrichment of gene sets indicative of teleost brain–pituitary–gonadal–hepatic (BPGH) axis function indicated that WWTPs serve as an important source of endocrine active chemicals (EACs) that affect the BPGH axis (e.g., cholesterol and steroid metabolism were altered). The results indicated that transcriptomics may even pinpoint pertinent adverse outcomes (i.e., liver vacuolization) and groups of chemicals that preselected chemical analytes may miss. Transcriptomic Effects-Based monitoring was capable of distinguishing sites, and it reflected chemical pollution gradients, thus holding promise for assessment of relative contributions of point sources to pollution and the efficacy of pollution remediation.

Environmental Science & Technology↗

Evaluation of numerical sediment quality targets for the St. Louis River Area of Concern

Numerical sediment quality targets (SQTs) for the protection of sediment-dwelling organisms have been established for the St. Louis River Area of Concern (AOC), 1 of 42 current AOCs in the Great Lakes basin. The two types of SQTs were established primarily from consensus-based sediment quality guidelines. Level I SQTs are intended to identify contaminant concentrations below which harmful effects on sediment-dwelling organisms are unlikely to be observed. Level II SQTs are intended to identify contaminant concentrations above which harmful effects on sediment-dwelling organisms are likely to be observed. The predictive ability of the numerical SQTs was evaluated using the matching sediment chemistry and toxicity data set for the St. Louis River AOC. This evaluation involved determination of the incidence of toxicity to amphipods (Hyalella azteca) and midges (Chironomus tentans) within five ranges of Level II SQT quotients (i.e., mean probable effect concentration quotients [PEC-Qs]). The incidence of toxicity was determined based on the results of 10-day toxicity tests with amphipods (endpoints: survival and growth) and 10-day toxicity tests with midges (endpoints: survival and growth). For both toxicity tests, the incidence of toxicity increased as the mean PEC-Q ranges increased. The incidence of toxicity observed in these tests was also compared to that for other geographic areas in the Great Lakes region and in North America for 10- to 14-day amphipod (H. azteca) and 10- to 14-day midge (C. tentans or C. riparius) toxicity tests. In general, the predictive ability of the mean PEC-Qs was similar across geographic areas. The results of these predictive ability evaluations indicate that collectively the mean PEC-Qs provide a reliable basis for classifying sediments as toxic or not toxic in the St. Louis River AOC, in the larger geographic areas of the Great Lakes, and elsewhere in North America.

Archives of Environmental Contamination and Toxico↗