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Inorganic and organic mercury chloride toxicity to Coturnix: sensitivity related to age and quantal assessment of physiologic responses

The toxicities of mercuric chloride (HgCl(,2)) and methylmercuric chloride (CH(,3)HgCl) were compared for coturnix (Coturnix coturnix japonica) from hatching to adulthood. Comparisons were based on: (1) Median lethal dosages (LD50) derived by administering single peroral and single intramuscular dosages of mercury, (2) median lethal concentrations (LC50) derived by feeding mercury for 5 days, (3) median toxic concentrations (TC50) derived by feeding mercury 9 weeks and measuring plasma enzyme activity, plasma electrolytes, and other blood constituents, and (4) transient changes of various blood chemistries following a single peroral dose of mercury. Acute peroral and intramuscular LD50s for HgCl(,2) and CH(,3)HgCl increased by two- to threefold for coturnix chicks from hatching to 4 weeks of age. Concomitantly, the LC50s also increased, but the important difference between test procedures was that with both single dose routes of exposure the toxicity ratios, i.e., HgCl(,2)/CH(,3)HgCl, at each age were about 2 to 2.5 compared to about 100 for the LC50s. For example, at 2 weeks of age the peroral LD50s for HgCl(,2) and CH(,3)HgCl were 42 and 18 mg/kg; the dietary LC50s were 5086 and 47 ppm for HgCl(,2) and CH(,3)HgCl. The 9 week feeding trial was not associated with gross effects from either HgCl(,2) at 0.5 to 32 ppm or CH(,3)HgCl at 0.125 to 8 ppm. However, subtle responses were detected for the plasma enzymes aspartate aminotransferase, lactate dehydrogenase, and ornithine carbamoyl transferase and could be quantified by probit analysis. This quantal procedure was based on establishment of a normal value for each enzyme and classing outliers as respondents. A 'hazard index' based on the TC50 for an enzyme divided by the LD50 or LC50 was introduced. The single oral dosages of HgCl(,2) and CH(,3)HgCl showed that ratios of alanine aminotransferase, lactate dehydrogenase, and orinthine carbamoyl transferase for the liver and kidneys of adult coturnix were opposite from that accepted for mammals. It was concluded that a chronic study of sublethal responses of young birds should be required in addition to the current toxicity screens used for regulatory purposes.

Book

Inorganic and organic mercury chloride toxicity to Coturnix: Sensitivity related to age and quantal assessment of physiologic responses

The toxicities of mercuric chloride (HgCl(,2)) and methylmercuric chloride (CH(,3)HgCl) were compared for coturnix (Coturnix coturnix japonica) from hatching to adulthood. Comparisons were based on: (1) Median lethal dosages (LD50) derived by administering single peroral and single intramuscular dosages of mercury, (2) median lethal concentrations (LC50) derived by feeding mercury for 5 days, (3) median toxic concentrations (TC50) derived by feeding mercury 9 weeks and measuring plasma enzyme activity, plasma electrolytes, and other blood constituents, and (4) transient changes of various blood chemistries following a single peroral dose of mercury. Acute peroral and intramuscular LD50s for HgCl(,2) and CH(,3)HgCl increased by two- to threefold for coturnix chicks from hatching to 4 weeks of age. Concomitantly, the LC50s also increased, but the important difference between test procedures was that with both single dose routes of exposure the toxicity ratios, i.e., HgCl(,2)/CH(,3)HgCl, at each age were about 2 to 2.5 compared to about 100 for the LC50s. For example, at 2 weeks of age the peroral LD50s for HgCl(,2) and CH(,3)HgCl were 42 and 18 mg/kg; the dietary LC50s were 5086 and 47 ppm for HgCl(,2) and CH(,3)HgCl. The 9 week feeding trial was not associated with gross effects from either HgCl(,2) at 0.5 to 32 ppm or CH(,3)HgCl at 0.125 to 8 ppm. However, subtle responses were detected for the plasma enzymes aspartate aminotransferase, lactate dehydrogenase, and ornithine carbamoyl transferase and could be quantified by probit analysis. This quantal procedure was based on establishment of a normal value for each enzyme and classing outliers as respondents. A 'hazard index' based on the TC50 for an enzyme divided by the LD50 or LC50 was introduced. The single oral dosages of HgCl(,2) and CH(,3)HgCl showed that ratios of alanine aminotransferase, lactate dehydrogenase, and orinthine carbamoyl transferase for the liver and kidneys of adult coturnix were opposite from that accepted for mammals. It was concluded that a chronic study of sublethal responses of young birds should be required in addition to the current toxicity screens used for regulatory purposes.

Dissertation Abstracts International

Concentrations and spatial patterns of organic contaminants in tree swallow ( Tachycineta bicolor ) eggs at United States and binational Great Lakes Areas of Concern, 2010–2015

Tree swallows, Tachycineta bicolor , were sampled across the Great Lakes basin in 2010 through 2015 to provide a system-wide assessment of current exposure to organic contaminants. The results provide information identified as critical by regulators to assess the “bird or animal deformity or reproductive problems” beneficial use impairment. Eggs were collected from 69 sites across all 5 Great Lakes, including 27 Areas of Concern (AOCs), some with multiple sites, and 10 sites not listed as an AOC. Concentrations of organic contaminants in eggs were quantified and compared with background and reproductive effect thresholds. Approximately 30% of AOCs had geometric mean concentrations of total polychlorinated biphenyls (PCBs) at or below average background exposure (0.34 μg/g wet wt). Exposure to polybrominated diphenyl ethers (PBDEs) was minimal, and only 3 of 27 AOCs and 1 non-AOC had geometric mean concentrations that exceeded background for tree swallows (96 ng/g wet wt). Concentrations of both PCBs and PBDEs were 10 to 20 times below the lower limit associated with impaired hatching success. In contrast, geometric mean concentrations of polychlorinated dibenzo- p -dioxin and furan (PCDD-F) toxic equivalents (TEQs) at the Saginaw River and Bay AOC and Midland, Michigan, USA (a non-AOC site), exceeded the lower limit for hatching effects (181 pg/g PCDD-F TEQs). The rest of the sites had geometric mean concentrations of PCDD-F TEQs below background levels (87 pg/g PCDD-F TEQs). Other organic contaminants, including p,p ′-dichlorodiphenyldichloroethylene, mirex, heptachlor, and chlordane, were at or below background or adverse effect concentrations.

Great Lakes

Fate of Airborne Contaminants in Okefenokee National Wildlife Refuge

Designation of Okefenokee National Wildlife Refuge as a Class I Air Quality Area (given the highest level of protection possible from air pollutants under the Clean Air Act Amendments of 1977) affords mandatory protection of the Refuge's airshed through the permit-review process for planned developments. Rainfall is the major source of water to the swamp, and potential impacts from developments to the airshed are high. To meet management needs for baseline information, chemical contributions from atmospheric deposition and partitioning of anions and cations, with emphasis on mercury and lead, in the various matrices of the Swamp were determined between July 1993 and April 1995. Chemistry of rainfall was determined on an event basis from one site located at Refuge Headquarters. Field samples of surface water, pore water, floc and sediment were collected from four locations on the Refuge: Chesser Prairie, Chase Prairie, Durden Prairie, and the Narrows. A sediment core sample was collected from the Refuge interior at Bluff Lake for aging of mercury deposition. Rainfall was acidic (pH 4.8) with sulfate concentrations averaging 1.2 mg/L and nitrate averaging 0.8 mg/L. Lead in rainfall averaged 1 ?g/L and total and methylmercury concentrations were 11.7 ng/L and 0.025 ng/L, respectively. The drought of 1993 followed by heavy rains during the fall and winter caused a temporary alteration in the cycling and availability of trace-elements within the different matrices of the Swamp. Surface water was acidic (pH 3.8 to 4.1), dilute (specific conductance 35-60 ?S/cm), and highly organic (DOC 35-50 mg/L). Sediment and floc were also highly organic (>90%). Total mercury averaged 3.6 ng/L in surface water, 9.0 ng/L in pore water and about 170 ng/g in floc and sediments. Mercury bioaccumulated in the biota of the Refuge: fish fillets (Centrarchus macropterus, Esox niger, Lepomus gulosus and Amia calva) had >2 ?g/g dry weight, alligators (Alligator mississippiensis) >4 ?g/g dry weight in liver and kidney, and raccoons (Procyon lotor) >16 ?g/g dry weight in the liver and kidney. Lead averaged 1 ?g/L in rainfall, 6.6 ?g/L in surface water, 9.8 ?g/L in pore water, 12.3 ?g/g in floc and 12.5 ?g/g in sediments. Lead in fish muscle was ~0.1 ?g/g and >1.2 ?g/g in bone, alligator kidney had 1.5 ?g/g lead and liver had 3.8 ?g/g; raccoon kidney and liver averaged about 1 ?g/g. Historical patterns of mercury deposition based on 210Pb aging of the core sample showed mercury increased from pre-1800 concentrations of <250 ng/g to >500 ng/g in the 1950s, with a subsequent decline to current levels. Lead concentrations in the core sample followed a similar pattern as that of mercury. Okefenokee Swamp serves as a sump for the cations and anions deposited through rainfall. Although mercury and lead levels in the biota are not currently acutely hazardous, concentrations are high enough to cause adverse chronic effects on behavioral, physiological or reproductive functions of resident biota, especially piscivorous species. To protect trust resources associated with the Refuge, activities and developments in the airshed that have the potential to increase atmospheric contamination, especially for lead and mercury, should be curtailed.

Book

Assessment of methods for soil monitoring in the Adirondack region of New York

Repeated sampling to detect changes in forest soils was rarely used before 1990, but the value of soil monitoring in understanding environmental change is becoming well established. The growing number of resampling studies has shown that sampling designs and procedures must be adapted to the objectives of the monitoring program and the soils being monitored. In the Adirondack region, current priorities include the response of soils to large increases, and more recently, large decreases in acidic deposition, and changes driven by trending climate such as altered pools of soil organic carbon, as well as other unforeseen factors that will occur in the future. To improve methods and assess the feasibility of long-term soil monitoring in the Adirondack region, the United States Geological Survey (USGS) conducted a pilot project to evaluate a new sampling method for characterizing soils on a watershed basis. Results obtained with this new approach, referred to as the ADK sampling method, was compared to methods used in previous sampling conducted in 2004 as part of the Western Adirondack Stream Survey (WASS), and also to previous high-replication pit sampling in the North and South Tributary watersheds of Buck Creek (North Buck and South Buck). The number of sampling locations and spatial distribution of sampling points within watersheds differed among the methods, although pit excavation was used to obtain samples in all cases. In addition, this investigation evaluated the use of small diameter corers as a means to measure forest floor mass with greater accuracy and precision than commonly used methods such as pit excavation. Sufficient statistical power to detect ecologically relevant changes in upper profile horizons (Oe, Oa and upper 10 cm of the B) were achieved with the ADK sampling method that utilized 18 pit excavations per watershed. The sampling locations were organized within each watershed into three study areas (six sampling locations per study area) that represented the primary types of landscape within the watershed. Sampling at 18 locations per watershed was found to be nearly as effective at detecting changes as sampling at 28 locations per watershed. Numerous significant changes (P < 0.10) were detected with both 18 and 28 sampling locations at sampling intervals of 12 to 16 years. The relationship between soil data obtained with the ADK method and stream chemistry at the base of the watershed suggested that this approach adequately characterized soil variability within the watershed for the purpose of studying soil-stream linkages. Significant changes in upper B horizon calcium (P < 0.10) and Oa horizon aluminum (P < 0.01) were detected when the data from the four WASS watersheds were combined with the two Buck Creek watersheds, which suggested that there would be value in resampling other WASS watersheds previously sampled in 2004 to support a regional assessment. Study results support small diameter cores as a useful method to monitor changes in the organic matter mass of the forest floor. This method showed high reproducibility in repeated sampling tests and lower spatial variability in sample data than traditional approaches when compared on a watershed basis. Soil coring is also faster and requires less equipment than pit excavation methods, which makes it more conducive to sampling over large areas. However, organic matter mass of the forest floor determined by coring was consistently less than the values obtained by the ADK sampling method that used pit sampling and vertical horizon measurements, and also literature values of a previous Adirondack study that utilized pit sampling in which the entire horizon was collected over a measured area. However, a high correlation (R2 = 0.87) occurred between organic matter content (expressed as Mg ha-1) determined by coring and the ADK sampling method. Differing methods with regard to where sample could be collected, and how organic matter was collected for chemical analysis were the likely reasons for differences in quantification of forest floor organic mass. Collection of forest floor cores in conjunction with the ADK method is recommended to provide improved sensitivity in detecting changes in the forest floor in proximity of where full analyses of the soil profile are being done. This duel sampling approach represents an optimized method for measuring and understanding how Adirondack soils will change in the future.

New York

Workshop 3.5: Closing the gap between exposure and effects in monitoring studies

A major challenge to contaminant monitoring programs is the selection of an appropriate suite of measurements for assessing exposure and effects. Early monitoring programs relied solely on residue analysis to detect the organochlorine compounds that were in use at that time. A shift to the use of more transient, less persistent chemicals required that a new set of tools be developed to determine if an organism had been exposed. This led to the development of cellular and biochemical assays that could indicate the presence of these types of chemicals in biota and the environment. However, it was recognized that measures of contaminant presence alone were insufficient to assess the health of biota. As a result, considerable research began to be directed toward development of diagnostic tools for measuring chemical effects in fish and wildlife. Today, contaminant monitoring programs follow a paradigm for study design that emphasizes not only the use of measures of exposure, but also measures of effect. Using data from our monitoring and research studies for hormonally active substances, we discuss a variety of metrics of exposure and effects and their application to specific chemicals, and the current information gaps. We conclude that although several bioindicators of exposure and effect have been promoted and used, to date there continues to be a poor association between cause and effect for endocrine active substances. In part, this is due to the limited number of diagnostic tools that are available and to a lack of basic toxicological information concerning toxicokinetics and mechanisms of action of hormonally active chemicals in fish and wildlife species. In the foreseeable future, both tissue and environmental residue data, despite the many limitations, will continue to be an important component of monitoring programs for hormonally active chemicals as we continue to develop and validate more specific bioindicators of exposure and effects.

Pure and Applied Chemistry

Effects of Abandoned Coal-Mine Drainage on Streamflow and Water Quality in the Mahanoy Creek Basin, Schuylkill, Columbia, and Northumberland Counties, Pennsylvania, 2001

This report assesses the contaminant loading, effects to receiving streams, and possible remedial alternatives for abandoned mine drainage (AMD) within the Mahanoy Creek Basin in east-central Pennsylvania. The Mahanoy Creek Basin encompasses an area of 157 square miles (407 square kilometers) including approximately 42 square miles (109 square kilometers) underlain by the Western Middle Anthracite Field. As a result of more than 150 years of anthracite mining in the basin, ground water, surface water, and streambed sediments have been adversely affected. Leakage from streams to underground mines and elevated concentrations (above background levels) of acidity, metals, and sulfate in the AMD from flooded underground mines and (or) unreclaimed culm (waste rock) degrade the aquatic ecosystem and impair uses of the main stem of Mahanoy Creek from its headwaters to its mouth on the Susquehanna River. Various tributaries also are affected, including North Mahanoy Creek, Waste House Run, Shenandoah Creek, Zerbe Run, and two unnamed tributaries locally called Big Mine Run and Big Run. The Little Mahanoy Creek and Schwaben Creek are the only major tributaries not affected by mining. To assess the current hydrological and chemical characteristics of the AMD and its effect on receiving streams, and to identify possible remedial alternatives, the U.S. Geological Survey (USGS) began a study in 2001, in cooperation with the Pennsylvania Department of Environmental Protection and the Schuylkill Conservation District. Aquatic ecological surveys were conducted by the USGS at five stream sites during low base-flow conditions in October 2001. Twenty species of fish were identified in Schwaben Creek near Red Cross, which drains an unmined area of 22.7 square miles (58.8 square kilometers) in the lower part of the Mahanoy Creek Basin. In contrast, 14 species of fish were identified in Mahanoy Creek near its mouth at Kneass, below Schwaben Creek. The diversity and abundance of fish species in Mahanoy Creek decreased progressively upstream from 13 species at Gowen City to only 2 species each at Ashland and Girardville. White sucker (Catostomus commersoni), a pollution-tolerant species, was present at each of the surveyed reaches. The presence of fish at Girardville was unexpected because of the poor water quality and iron-encrusted streambed at this location. Generally, macroinvertebrate diversity and abundance at these sites were diminished compared to Schwaben Creek and other tributaries draining unmined basins, consistent with the observed quality of streamwater and streambed sediment. Data on the flow rate and chemistry for 35 AMD sources and 31 stream sites throughout the Mahanoy Creek Basin were collected by the USGS during high base-flow conditions in March 2001 and low base-flow conditions in August 2001. A majority of the base-flow streamwater samples met water-quality standards for pH (6.0 to 9.0); however, few samples downstream from AMD sources met criteria for acidity less than alkalinity (net alkalinity = 20 milligrams per liter as CaCO3) and concentrations of dissolved iron (0.3 milligram per liter) and total manganese (1.0 milligram per liter). Iron, aluminum, and various trace elements including cobalt, copper, lead, nickel, and zinc, were present in many streamwater samples at concentrations at which continuous exposure can not be tolerated by aquatic organisms without an unacceptable effect. Furthermore, concentrations of sulfate, iron, manganese, aluminum, and (or) beryllium in some samples exceeded drinking-water standards. Other trace elements, including antimony, arsenic, barium, cadmium, chromium, selenium, silver, and thallium, did not exceed water-quality criteria for protection of aquatic organisms or human health. Nevertheless, when considered together, concentrations of iron, manganese, arsenic, cadmium, chromium, copper, lead, nickel, and zinc in a majority of the streambed sediment samples from Mahanoy Creek and

Scientific Investigations Report

Geophysics- and geochemistry-based assessment of the geochemical characteristics and groundwater-flow system of the U.S. part of the Mesilla Basin/Conejos-Médanos aquifer system in Doña Ana County, New Mexico, and El Paso County, Texas, 2010–12

One of the largest rechargeable groundwater systems by total available volume in the Rio Grande/Río Bravo Basin (hereinafter referred to as the “Rio Grande”) region of the United States and Mexico, the Mesilla Basin/Conejos-Médanos aquifer system, supplies water for irrigation as well as for cities of El Paso, Texas; Las Cruces, New Mexico; and Ciudad Juárez, Chihuahua, Mexico. The U.S. Geological Survey in cooperation with the Bureau of Reclamation assessed the groundwater resources in the Mesilla Basin and surrounding areas in Doña Ana County, N. Mex., and El Paso County, Tex., by using a combination of geophysical and geochemical methods. The study area consists of approximately 1,400 square miles in Doña Ana County, N. Mex., and 100 square miles in El Paso County, Tex. The Mesilla Basin composes most of the study area and can be divided into three parts: the Mesilla Valley, the West Mesa, and the East Bench. The Mesilla Valley is the part of the Mesilla Basin that was incised by the Rio Grande between Selden Canyon to the north and by a narrow valley (about 4 miles wide) to the southeast near El Paso, Tex., named the Paso del Norte, which is sometimes referred to in the literature as the “El Paso Narrows.” Previously published geophysical data for the study area were compiled and these data were augmented by collecting additional geophysical and geochemical data. Geophysical resistivity measurements from previously published helicopter frequency domain electromagnetic data, previously published direct-current resistivity soundings, and newly collected (2012) time-domain electromagnetic soundings were used in the study to detect spatial changes in the electrical properties of the subsurface, which reflect changes that occur within the hydrogeology. The geochemistry of the groundwater system was evaluated by analyzing groundwater samples collected in November 2010 for physicochemical properties, major ions, trace elements, nutrients, pesticides (reported but not used in the assessment), and environmental tracers. The data obtained from these samples (with the exception of the pesticide data) were used to gain insights into processes controlling the groundwater movement through the groundwater system in the study area. Results from the geophysical and geochemical assessments facilitated the interpretation of the geochemical characteristics of the groundwater sources and geochemical groups within the groundwater system. The groundwater-flow system in the study area consists primarily of the Mesilla Basin aquifer system, which can be divided into four hydrogeologic units by using an informal classification scheme based on basin-fill stratigraphy and sedimentology with an emphasis on aquifer characteristics. The four hydrogeologic units are (1) the Rio Grande alluvium, which is the shallow aquifer of the Mesilla Basin within the confines of the Mesilla Valley, and the three hydrogeologic units that compose the Santa Fe Group: (2) the lower part of the Santa Fe Group, which is the least productive zone, (3) the middle part of the Santa Fe Group, which is the primary water-bearing hydrogeologic unit in the basin and is generally saturated, and (4) the upper part of the Santa Fe Group, which is the most productive water-bearing unit within the Santa Fe Group but is only partially saturated in the north and largely unsaturated in the south and western parts of the Mesilla Basin. The helicopter frequency domain electromagnetic survey results indicated that approximately half of the resistivity values were less than 10 ohm-meters at depths of 50 and 100 feet with a transition where the resistivity values changed from relatively high values (greater than 20 ohm-meters) to relatively low resistivity values (less than 10 ohm-meters) near Vado, New Mexico. Slightly more than 25 percent of the gridded resistivity values from the three-dimensional grid of the combined inverse modeling results of the direct-current resistivity and time-domain electromagnetic soundings were equal to or less than 10 ohm-meters with large regions of low resistivity becoming apparent in the southernmost part of the study area near the Paso Del Norte where these low resistivity features are spatially the widest at or below the top of the bedrock. These low resistivity values might represent clayey deposits, sediments composed largely of sand and gravel saturated with saline water, or both. Historical dissolved-solids-concentration data within the surface geophysical subset area of the study area were compiled and compared to the inverse modeling results of the combined direct-current resistivity and time-domain soundings; this comparison was done to strengthen the interpretation made from the combined inverse modeling results that the low resistivity features were representative of sand and gravel deposits saturated with saline water and not clayey deposits. Water-level altitudes within the Rio Grande alluvium generally decreased from north to south, with a west to east decrease in water-level altitudes near Las Cruces, New Mexico, as a result of groundwater pumping. Groundwater flow within the Santa Fe Group is more complex than the groundwater flow within the Rio Grande alluvium because of the larger lateral and vertical extent of the Santa Fe Group compared to the Rio Grande alluvium. Groundwater from the Organ Mountains flows directly south towards the Paso del Norte. Groundwater from the Robledo Mountains, the Rough and Ready Hills, and the Sleeping Lady Hills generally flows to the southeast. Groundwater flowing near the north end of the midbasin uplift generally continues east towards the Rio Grande and then flows south on the east side of the midbasin uplift. Groundwater flowing near the west side of the midbasin uplift generally continues south parallel to the faults that make up the midbasin uplift and then flows east towards the Paso del Norte when it reaches the south end of the midbasin uplift. Groundwater from the Aden Hills and the East and West Potrillo Mountains flows to the south end of the midbasin uplift and then continues east towards the Paso del Norte. Throughout most of the Mesilla Valley, the vertical hydraulic gradient was downward because the water-level altitude in the Rio Grande alluvium was higher than it was in the Santa Fe Group, but in some areas (typically in the middle and southern parts of the Mesilla Valley), the vertical hydraulic gradient was substantially reduced or even reversed to an upward hydraulic gradient. The geochemistry data indicate that there was a complex system of multiple geochemical endmembers and mixing between these endmembers with recharge to the Rio Grande alluvium and Santa Fe Group composed mostly of seepage from the Rio Grande, inflows from deeper or neighboring water systems, and mountain-front recharge. Five distinct geochemical groups were identified in the Mesilla Basin study area: (1) ancestral Rio Grande (pre-Pleistocene) geochemical group, (2) modern Rio Grande (Pleistocene to present) geochemical group, (3) mountain-front geochemical group, (4) deep groundwater upwelling geochemical group, and (5) unknown freshwater geochemical group. The ancestral Rio Grande groundwater was water that recharged into the system as seepage losses from the ancestral Rio Grande; this groundwater generally flows from north to south-southeast towards the Paso del Norte. Groundwater on the west side of the midbasin uplift generally flows south until it reaches the southern part of the study area; from the southern part of the study area, the groundwater flows east towards the Paso del Norte. Groundwater on the east side of the midbasin uplift flows south-southeast towards the Paso del Norte where it mixes with groundwater from the modern Rio Grande, uplifted areas in the west, and the deep saline source. The water type of the modern Rio Grande geochemical group ranged from calcium-sulfate water type in the northern part of the study area to sodium-chloride-sulfate water type in the southern part of the study area; from north to south there was a substantial increase in specific conductance, strontium-87/strontium-86 ratio, potassium, and the trace metals of iron and lithium, changing the water chemistry such that it became similar to the water chemistry of the deep groundwater upwelling geochemical group. From age-dating results, water in the modern Rio Grande geochemical group was recharged to the Rio Grande alluvium within the past 10 years. The mountain-front geochemical group was generally old water (apparent age was greater than 10,000 carbon-14 years before present) that was somewhat mineralized and has relatively high concentrations of fluoride and silica, which might indicate longer exposure to volcanic and siliciclastic rocks or aluminosilicate minerals. There were five different locations of recharge determined from the groundwater geochemistry within the mountain-front geochemical group, all having a slightly different geochemical signature: (1) the Rough and Ready Hills, Robledo Mountains, and the Sleeping Lady Hills, (2) the Doña Ana Mountains, (3) the Aden Hills and West Potrillo Mountains, (4) the East Potrillo Mountains, and (5) the Sierra Juárez in Mexico. The groundwater from the Rough and Ready Hills, Robledo Mountains, the Sleeping Lady Hills, and the Doña Ana Mountains generally flows toward the Rio Grande and eventually mixes together and with the modern Rio Grande groundwater. The groundwater originating from the Aden Hills and East and West Potrillo Mountains generally flows east to southeast at a slow rate and eventually mixes and continues east, where it mixes with groundwater from the ancestral Rio Grande geochemical group and with the groundwater from the Sierra Juárez. The groundwater from the Sierra Juárez flows north and then east towards the Paso del Norte where it mixes with groundwater from the uplifted areas in the west, ancestral and modern Rio Grande groundwater, and the upwelling groundwater from a deep saline source. The deep groundwater upwelling geochemical group had the highest concentrations of bicarbonate, potassium, silica, aluminum, iron, and lithium within the study area, indicating that it had been in contact with carbonate and siliciclastic rocks for a much longer period of time and at higher temperatures compared to the other geochemical groups, and was most likely ancient marine groundwater originating from the Paleozoic and Cretaceous carbonate rocks which was upwelling into the Mesilla Basin aquifer system in the southeastern part of the study area through the extensive fault systems. Direct-current resistivity and time-domain electromagnetic soundings support the interpretation of ancient marine groundwater upwelling into the Mesilla Basin aquifer system, as do the analytical results from wells, and the helicopter frequency domain electromagnetic data collected along the Rio Grande. The hydrogen-2/hydrogen-1 ratio and oxygen-18/oxygen-16 ratio isotopic results for samples in the unknown freshwater geochemical group did not plot on the Rio Grande evaporation line, indicating this group did not have a Rio Grande signature (that is, there was no isotopic evidence of a component of Rio Grande water) and it also had the lowest mineralized content of any geochemical group in the study area.

New Mexico, Texas

Riparian spiders: Sentinels of polychlorinated dibenzo-p-dioxin and dibenzofuran-contaminated sediment

Polychlorinated dibenzo- p -dioxin and polychlorinated dibenzofuran (PCDD/F) are persistent, toxic, and bioaccumulative. Currently, PCDD/F monitoring programs primarily use fish and birds with potentially large home ranges to monitor temporal trends over broad spatial scales; sentinel organisms that provide targeted sediment contaminant information across small geographic areas have yet to be developed. Riparian orb-weaving spiders, which typically have small home ranges and consume primarily adult aquatic insects, are potential PCDD/F sentinels. Recent studies have demonstrated that spider tissue concentrations indicate the source and magnitude of dioxin-like chlorinated compounds in contaminated sediments, including polychlorinated biphenyls (PCBs). Our aim in the present study was to assess the utility of riparian spiders as sentinels for PCDD/F-contaminated sediments. We measured PCDD/F (total [Σ] and homologs) in surface sediments and spiders collected from three sites within the St. Louis River basin (Minnesota and Wisconsin, USA). We then compared (1) patterns in ΣPCDD/F concentrations between sediment and spiders, (2) the distribution of homologs within sediments and spiders when pooled across sites, and (3) the relationship between sediment and spider concentrations of PCDD/F homologs across 13 stations sampled across the three sites. The ΣPCDD/F concentrations in sediment (mean ± standard error 286 591 ± 97 614 pg/g) were significantly higher than those in riparian spiders (2463 ± 977 pg/g, p < 0.001), but the relative abundance of homologs in sediment and spiders were not significantly different. Spider homolog concentrations were significantly and positively correlated with sediment concentrations across a gradient of sediment PCDD/F contamination ( R 2 = 0.47, p < 0.001). Our results indicate that, as has been shown for other legacy organic chemicals like PCBs, riparian spiders are suitable sentinels of PCDD/F in contaminated sediment.

Minnesota, Wisconsin

National water summary 1990-91: Hydrologic events and stream water quality

National Water Summary 1990-91 Hydrologic Events and Stream Water Quality was planned to complement existing Federal-State water-quality reporting to the U.S. Congress that is required by the Clean Water Act of 1972. This act, formally known as the Federal Water Pollution Control Act Amendments of 1972 (Public Law 92-500), and its amendments in 1977,1979,1980,1981,1983, and 1987, is the principal basis for Federal-State cooperation on maintaining and reporting on water quality in the United States. Under section 305(b) of the Clean Water Act, the States must designate uses for waterbodies, biennially assess whether the waterbodies meet designated uses, and report to the U.S. Environmental Protection Agency (EPA), which in turn summarizes the findings of the State assessments in a biennial National Water Quality Inventory report to the Congress. This volume of the National Water Summary uses a nationally consistent data base and methods of statistical analysis to document stream water quality in the United States, Puerto Rico, and the Western Pacific Islands. As a basis for preparation of this report, the U.S. Geological Survey (uses) created a data base of waterquality data from about 2,900 stream water-quality monitoring stations in the United States (Lanfear, 1993). These data, which were extracted primarily from the uses National Water Information System (NWIS) and supplemented with data from the EPA national data base known as STORET, consisted mostly of water-chemistry and physical-sediment data. About 1,400 of these stations met a criterion, used in this volume for trends analysis of data, of having a period of record that began before water year 1980. (A water year is the period from October 1 through September 30 and is identified by the calendar year at the end of the period.) Inasmuch as the determination of trends requires about 10 years of data, few biological data were suitable for trends analysis because biological indicators of water quality were not being collected extensively by water year 1980. Also, because of the lack of long-term data, an assessment of the water quality of lakes and reservoirs is not included in this National Water Summary . Constituent and waterproperty data were selected from this data base and analyzed with statistical techniques that have been used extensively by the uses to summarize conditions and trends in water quality. (Throughout the remainder of this article, the term "constituent" is used also to represent water properties, such as pH and alkalinity.) Selected results from this analysis are presented graphically, both by State and nationally, in this volume. The data base created for preparation of this volume and the resulting nationally consistent statistical analysis of these data provide a unique opportunity to compare and contrast stream water-quality conditions and trends nationally and State by State. Because of the complexity of water quality and the natural seasonal and diurnal variations in the concentrations of waterquality constituents, the determination of trends in water quality requires a relatively long period of record. Trends in constituent concentrations in the State summaries in this volume were calculated for one or more of four periods water years 1970-89,1975-89,1980- 89, and 1982-89. Unfortunately, few water-quality monitoring stations have periods of record of more than 10 or 15 years, and therefore most analyses in the State summaries were done for 8- or 10-year periods. Although interest in water quality has continued to heighten since passage of the Clean Water Act, funds for support of data-collection programs are limited and data records of many of the constituents now of current concern, especially organic constituents, do not exist or are less than 10-years long; consequently only a modest number of organic constituents are presented in this volume. Discussion of conditions and trends in water quality in this National Water Summary also draw upon information about land use, population, water use, application of agricultural chemicals in rural areas, the siting of industrial facilities, and other ancillary information. Because the results of analysis of a restricted number of constituents are presented in this volume, State 305(b) reports also are cited in the discussion of water quality in each State. The following discussion is an overview of the three parts of this 1990-91 National Water Summary - "Hydrologic Conditions and Water-Related Events, Water Years 1990-91," "Hydrologic Perspectives on Water Issues," and "State Summaries of Stream Water Quality."

Water Supply Paper

Natural attenuation of chlorinated volatile organic compounds in ground water at Area 6, Naval Air Station Whidbey Island, Washington

Natural attenuation is a viable alternative to pump and treat for meeting remediation objectives in the vicinity of the southern contaminant plume. The combination of historically low contaminant concentrations in ground water, a landfill cap that limits source area contributions, favorable conditions for degradation of VC, and a relatively long downgradient distance to potential receptors are all favorable for natural attenuation as a remediation alternative. Natural attenuation could effectively meet all but one remediation goal that extraction wells PW- 2, PW-4, PW-6, PW-7, PW-8 and PW-9 are currently being employed to meet. The goal of preventing migration of all VC across the site boundary could not be met by natural attenuation. Some VC would migrate south of the Navy boundary, but the potential for subsequent VC mineralization downgradient of the base and the existing institutional controls would result in minimal additional risk from using natural attenuation. In the western contaminant plume natural attenuation is not currently a viable alternative to pump and treat for meeting remediation objectives. There is a possibility that rates for reductive dechlorination of TCE and TCA could increase substantially if the plume was allowed to migrate beneath the Oak Harbor landfill, but there are not enough data to be certain of such an increase. TCA and TCE concentrations at the leading edge of the western plume need to be reduced to at least 25 and 40 µg/L, respectively, to be protective of potential downgradient receptors. Source area TCA and TCE concentrations have decreased substantially over the past ten years, and the extraction wells PW-3 and PW-5 in particular are removing a significant mass of contaminants from ground water, so natural attenuation may be a viable alternative for the western plume in the future. There would be some possible side benefits of using natural attenuation as an alternative to pump and treat in the southern contaminant plume. The first would be that the resulting decrease in the amount of treated water that would need to be recharged in the swale north of the landfill would result in less off-base migration of contamination across the western site boundary. The second benefit would be a substantial reduction in the amount of dissolved iron and manganese being extracted from the shallow aquifer and run through the treatment system. Removing that source of operation and maintenance problems would result in more effective containment and removal of contamination in the western contaminant plume. The most critical data gap identified in this evaluation is the paucity of contaminant chemistry information downgradient of the Navy boundary in the vicinity of the southern contaminant plume. Without such data, the behavior of the plume and the protectiveness of natural attenuation to downgradient receptors cannot be verified, and field attenuation rates for VC cannot be determined directly. The existing long-term monitoring plan would need to be reviewed and revised if natural attenuation is selected as a remedy for the contamination in the southern plume. In particular, additional performance monitoring wells may be required downgradient of the property.

Washington

Hydrogeology, Water Chemistry, and Factors Affecting the Transport of Contaminants in the Zone of Contribution of a Public-Supply Well in Modesto, Eastern San Joaquin Valley, California

Ground-water chemistry in the zone of contribution of a public-supply well in Modesto, California, was studied by the U.S. Geological Survey National Water Quality Assessment (NAWQA) Program's topical team for Transport of Anthropogenic and Natural Contaminants (TANC) to supply wells. Twenty-three monitoring wells were installed in Modesto to record baseline hydraulic information and to collect water-quality samples. The monitoring wells were divided into four categories that represent the chemistry of different depths and volumes of the aquifer: (1) water-table wells were screened between 8.5 and 11.7 m (meter) (28 and 38.5 ft [foot]) below land surface (bls) and were within 5 m (16 ft) of the water table; (2) shallow wells were screened between 29 and 35 m (95 and 115 ft) bls; (3) intermediate wells were screened between 50.6 and 65.5 m (166 and 215 ft) bls; and (4) deep wells are screened between 100 to 106 m (328 and 348 ft) bls. Inorganic, organic, isotope, and age-dating tracers were used to characterize the geochemical conditions in the aquifer and understand the mechanisms of mobilization and movement of selected constituents from source areas to a public-supply well. The ground-water system within the study area has been significantly altered by human activities. Water levels in monitoring wells indicated that horizontal movement of ground water was generally from the agricultural areas in the northeast towards a regional water-level depression within the city in the southwest. However, intensive pumping and irrigation recharge in the study area has caused large quantities of ground water to move vertically downward within the regional and local flow systems. Analysis of age tracers indicated that ground-water age varied from recent recharge at the water table to more than 1,000 years in the deep part of the aquifer. The mean age of shallow ground water was determined to be between 30 and 40 years. Intermediate ground water was determined to be a mixture of modern (Post-1950) and old (Pre-1950) ground water. As a result, concentrations of age tracers were detectable but diluted by older ground water. Deep ground water generally represented water that was recharged under natural conditions and therefore had much older ages. Ground water reaching the public-supply well was a mixture of older intermediate and deep ground water and young shallow ground water that has been anthropogenically-influenced to a greater extent than intermediate ground water. Uranium and nitrate pose the most significant threat to the quality of water discharged from the public-supply well. Although pesticides and VOCs were present in ground water from the public-supply well and monitoring wells, currently concentrations of these contaminants are generally less than one-hundredth the concentration of drinking water standards. In contrast, both uranium and nitrate were above half the concentration of drinking water standards for public-supply well samples, and were above drinking water standards for several water-table and shallow monitoring wells. Shallow ground water contributes roughly 20 percent of the total flow to the public-supply well and was the entry point of most contaminants reaching the public-supply well. Naturally-occurring uranium, which is commonly adsorbed to aquifer sediments, was mobilized by oxygen-rich, high-alkalinity water, causing concentrations in some monitoring wells to be above the drinking-water standard of 30 ug/L (microgram per liter). Adsorption experiments, sediment extractions, and uranium isotopes indicated uranium in water-table and shallow ground water was leached from aquifer sediments. Uranium is strongly correlated to bicarbonate concentrations (as measured by alkalinity) in ground water. Bicarbonate can effectively limit uranium adsorption to sediments. As a result, continued downward movement of high-alkalinity, oxygen-rich ground water will likely lead to larger portions of the aquifer having

Scientific Investigations Report

Spatial and temporal variation of stream chemistry associated with contrasting geology and land-use patterns in the Chesapeake Bay watershed—Summary of results from Smith Creek, Virginia; Upper Chester River, Maryland; Conewago Creek, Pennsylvania; and Difficult Run, Virginia, 2010–2013

Despite widespread and ongoing implementation of conservation practices throughout the Chesapeake Bay watershed, water quality continues to be degraded by excess sediment and nutrient inputs. While the Chesapeake Bay Program has developed and maintains a large-scale and long-term monitoring network to detect improvements in water quality throughout the watershed, fewer resources have been allocated for monitoring smaller watersheds, even though water-quality improvements that may result from the implementation of conservation practices are likely to be first detected at smaller watershed scales. In 2010, the U.S. Geological Survey partnered with the U.S. Environmental Protection Agency and the U.S. Department of Agriculture to initiate water-quality monitoring in four selected small watersheds that were targeted for increased implementation of conservation practices. Smith Creek watershed is an agricultural watershed in the Shenandoah Valley of Virginia that is dominated by cattle and poultry production, and the Upper Chester River watershed is an agricultural watershed on the Eastern Shore of Maryland that is dominated by row-cropping activities. The Conewago Creek watershed is an agricultural watershed in southeastern Pennsylvania that is characterized by mixed agricultural activities. The fourth watershed, Difficult Run, is a suburban watershed in northern Virginia that is dominated by medium density residential development. The objective of this study was to investigate spatial and temporal variations in water chemistry and suspended sediment in these four relatively small watersheds that represent a range of land-use patterns and underlying geology to (1) characterize current water-quality conditions in these watersheds, and (2) identify the dominant sources, sinks, and transport processes in each watershed. The general study design involved two components. The first included intensive routine water-quality monitoring at an existing streamgage within each study area (including continuous water-quality monitoring as well as discrete water-quality sampling) to develop a detailed understanding of the temporal and hydrologic variability in stream chemistry and sediment transport in each watershed. The second component involved extensive water-quality monitoring at various sites throughout each watershed to develop a detailed understanding of spatial patterns. Both components were used to improve understanding of sources and transport processes affecting stream chemistry, including nutrients and suspended sediments, and their implications for detecting long-term trends related to best management practices. This report summarizes the results of monitoring that was performed from April 2010 through September 2013. Individual Small Watershed Summaries Summaries for each of the four small watersheds are presented below. Each watershed has a more descriptive and detailed section in the report, but these summaries may be particularly useful for some watershed managers and stakeholders desiring slightly less technical detail. Smith Creek Smith Creek is a 105.39-mi 2 watershed within the Shenandoah Valley that drains to the North Fork Shenandoah River. The long-term Smith Creek base-flow index is 72.3 percent, indicating that on average, approximately 72 percent of Smith Creek flow was base flow, which suggests that Smith Creek streamflow is dominated by groundwater discharge rather than stormwater runoff. A series of cluster and principal components analyses demonstrated that the majority of the variability in Smith Creek water quality could be attributed to hydrologic and seasonal variability. Statistically significant positive correlations with flow were observed for turbidity, suspended sediments, total nitrogen, ammonium, orthophosphate, iron, total phosphorus, and the ratio of calcium to magnesium. Statistically significant inverse correlations with flow were observed for specific conductance, magnesium, δ 15 N of nitrate, pH, bicarbonate, calcium, and δ 18 O of nitrate. Of particular note, flow and nitrate were not statistically significantly correlated, likely because of the relatively complex concentration-discharge relationship observed in continuous and discrete datasets. Statistically significant seasonal patterns were observed for numerous water-quality constituents: water temperature, turbidity, orthophosphate, total phosphorus, suspended-sediment concentration, and silica were higher during the warm season, but pH, dissolved oxygen, and sulfate were higher during the cool season. Surrogate regression models were developed to compute sediment and nutrient loads in Smith Creek using the continuous water-quality monitors. The mean Smith Creek in-stream sediment load was approximately 6,900 tons per year, with nearly 90 percent of the sediment load over the 3-year study period contributed during the eight largest storm events during that period. The Smith Creek total phosphorus load was approximately 21,000 pounds of phosphorus per year, with the majority of the load contributed during stormflow periods, although a substantial phosphorus load still occurs during base-flow conditions. The Smith Creek total nitrogen load was approximately 400,000 pounds per year, with total nitrogen accumulation less dominated by stormflow contributions (as was the case for sediment and total phosphorus) and strongly affected by base-flow export of nitrogen from the basin. Extensive water-quality monitoring throughout the Smith Creek watershed revealed how the complex geology and hydrology interacted to result in variable water chemistry. During relatively dry and low base-flow periods, much of the discharge in Smith Creek was contributed by a single dominant spring—Lacey Spring. During wetter base-flow periods, the flows in Smith Creek were largely generated by a mixture of headwater springs and forested mountain tributaries with very different geochemical composition. The headwater springs generally issued from limestone bedrock and were characterized as having relatively high nitrate, specific conductance, calcium, and magnesium, as well as relatively low concentrations of phosphorus, ammonium, iron, and manganese. The undeveloped, high-gradient, forested mountain sites were generally characterized by low ionic strength waters with low nutrient concentrations. Nitrate isotope data from the limestone springs generally were consistent with manure-derived nitrogen sources (such as cattle and poultry), although the possibility of other mixed sources cannot be excluded. Nitrate isotope data from the undeveloped, high-gradient forested mountain sites were more consistent with nitrogen from undisturbed soils, atmospheric deposition, or nitrogen fixation. Regardless of the nitrogen source, oxygen isotope data indicate that the nitrate was largely a result of nitrification. Land-use data indicate that manure sources of nitrogen dominated watershed nitrogen inputs. Phosphorus sources were less well studied. The presence of a single point-source discharge near the town of New Market contributed the majority of the phosphorus to Smith Creek under base-flow conditions, but nonpoint sources of phosphorus dominated the loading to Smith Creek during stormflow periods. Implementation of conservation practices increased in the Smith Creek watershed during the study period, and even though a broad range of practice types was implemented, the most common practices included stream fencing (for cattle exclusion), the development of nutrient management plans, conservation crop rotation, and the planting of cover crops. While the implementation of these conservation practices is encouraging, results indicate small increases in nitrate concentrations at the streamgage over the last 29 years, concurrent with small decreases in nitrate fluxes. It will likely be years before the cumulative effect of these practices can be detected in the Smith Creek water quality, and the magnitude of the effect of these conservation practices detected in Smith Creek will depend largely on whether nutrient loading (of manure and commercial fertilizer) is reduced over time. Upper Chester River The Upper Chester River watershed includes the 36-square-mile (mi 2 ) watershed area around several nontidal tributaries that drain into the tidal Chester River. The streamgage is on Chesterville Branch, the largest nontidal tributary (approximately 6.12 mi 2 ) and is the site for continuous water-quality monitoring for this project. The base-flow index at Chesterville Branch is about 72 percent and indicates that, as in most of the Coastal Plain, groundwater is the greatest contributor to streamflow. As such, more than 90 percent of the nitrogen in the stream is in the form of nitrate from groundwater. Continuous and discrete data collected at Chesterville Branch show the effects of streamflow and season on water quality. Significantly positive correlations with flow were observed for ammonium, dissolved and total phosphorus, sediment, and turbidity as runoff carried these constituents from the land surface into Chesterville Branch. Other constituents that increased significantly with flow include potassium, sulfate, iron, and manganese, which are likely contributed from near-stream areas and ponds with high organic-matter content. Total nitrogen, pH, and specific conductance, along with chemical constituents associated with groundwater inputs including nitrate, calcium, ratio of calcium to magnesium, silica, bicarbonate, and sodium, were negatively correlated with flow because concentrations of these constituents were diluted by runoff. Seasonal differences in water chemistry, which are most likely related to increased biologic effects on the uptake and release of chemicals in the stream and near-stream areas, also were observed. Water temperature, orthophosphate, δ 15 N of nitrate, bicarbonate, sodium, and the ratio of sodium to chloride were higher during the warm season, and dissolved oxygen, total nitrogen, nitrate, magnesium, sulfate, and manganese were higher during the cool season. Surrogate-regression models developed by using continuous water-quality data showed that the annual sediment load for the 2013 water year was about 2,600 tons, with more than 90 percent of this sediment contributed during two storms. The total phosphorus load in 2013 was about 13,000 pounds with more than 90 percent contributed during the same two storms as sediment. The load of total nitrogen, 140,000 pounds, accumulated steadily throughout the 2013 water year as nitrate in groundwater continuously discharged into the stream. The same two large storms that contributed 90 percent of the suspended-sediment and total phosphorus load only contributed about 20 percent of the annual total nitrogen load. Extensive water-quality monitoring of stream base flow throughout the Upper Chester River watershed identified how differences in land use and hydrogeology affected water chemistry. In parts of the watershed with well-drained soil and thick sandy aquifer sediments, concentrations of nitrate and other chemicals associated with fertilizer and lime application increased in streams as agricultural land use increased. More than 90 percent of the nitrogen in streams from these areas was in the form of nitrate, and concentrations ranged from about 5 milligrams per liter (mg/L) to 8 mg/L as nitrogen in the two largest tributaries. Stream nitrate concentrations were about 1 mg/L as nitrogen where soils were more poorly drained, the surficial aquifer sediments were thinner, and forests and wetlands were more widespread than agriculture. Nitrate isotope data were consistent with inorganic fertilizers ± atmospheric deposition and N 2 fixation as sources of nitrogen, and with nitrification as the dominant nitrate-forming process. Nitrate reduction was indicated by elevated δ 15 N and δ 18 O values in some samples from streams draining watersheds with poorly drained soils. An analysis of land-use data and SPARROW modeling input data attributed almost 90 percent of the nitrogen sources in the Upper Chester River watershed to inorganic fertilizer and fixation of atmospheric nitrogen by legumes, which is in agreement with the isotopic characteristics of nitrate in this watershed. Local sources of manure are limited in this area. Total phosphorus concentrations during base flow ranged from below detection to about 0.2 mg/L. Stream phosphorus concentrations during base flow were generally lower than those measured during storms because most phosphorus transport likely occurs as phosphorus attached to sediment particles during runoff. Because manure is not widely used in this area, the major source of phosphorus is likely fertilizer. The implementation of conservation practices in the Upper Chester River watershed increased substantially during the study period, with a total implementation of 1,194 U.S. Department of Agriculture-compliant practices. The most frequently used practices were oriented towards nutrient and sediment control, including cover crops, nutrient management planning, conservation crop rotation, conservation tillage, and irrigation management. The current Chesapeake Bay model for this area predicts that implementation of best management practices should result in a 13-percent decrease in overall delivery of nitrogen to the Upper Chester River. Because most nitrogen travels through the groundwater system for years to decades before being discharged to streams, the time period of monitoring was not sufficient to see the effects of these practices on water quality. The magnitude of the effect that may eventually be detected will depend on the degree to which nitrate leaching into the groundwater system is reduced over time. Loadings of phosphorus and sediment are primarily transported during large runoff events and are difficult to control and analyze for trends because of their timing and episodic nature. Conewago Creek Conewago Creek has two primary monitoring locations—one near the middle of the 47-mi 2 watershed and the other near the outlet just upstream of the Susquehanna River. The base-flow index was 47.3 percent for 2012–2013, indicating that on average, approximately 53 percent of the streamflow in Conewago Creek exited the watershed as surface flow, which suggests that the stormwater runoff was somewhat greater than groundwater discharge (base flow). A series of cluster and principal components analyses demonstrated that the majority of the variability in the Conewago Creek water quality could be attributed to hydrologic and seasonal variability. Statistically significant positive correlations with flow were observed at both monitoring sites for ammonium, total phosphorus, orthophosphate, iron, and manganese; additionally, at the upstream monitoring station, total nitrogen demonstrated a statistically significant positive correlation with flow. Statistically significant inverse correlations with flow were observed at both sites for water temperature, specific conductance (at the downstream site only), sulfate, chloride, calcium, and magnesium. Statistically significant seasonal patterns were observed for several water-quality constituents. Water temperature, phosphorus (upstream site only), and orthophosphate were higher during the warm season, and nitrate and total nitrogen (upstream site only) were higher during the cool season. Surrogate regression models were developed to compute sediment and nutrient load in Conewago Creek by using the continuous water-quality monitors and water-quality samples. Conewago Creek sediment load was approximately 9,900 tons in 2012 and approximately 18,900 tons in 2013, with nearly 80 percent of the sediment load in 2013 contributed by the three largest storm events. Annual total nitrogen loads could not be estimated due to poor model performance. The addition of continued monitoring or a continuously recording nitrate sensor could improve estimates of total nitrogen loads. During 2012 and 2013, phosphorus loads in Conewago Creek were approximately 50,000 pounds in each year. Combining data from one high-flow synoptic sampling with the data from routine sampling revealed how the geology and hydrology interact to result in variable water chemistry throughout the Conewago Creek watershed. The areas above the upstream gage in the headwaters are generally underlain by forested non-carbonate bedrock and are characterized by relatively low nitrate, specific conductance, calcium, and magnesium, as well as relatively low concentrations of phosphorus, ammonium, iron, and manganese. The more developed, agricultural areas below the upstream site were generally characterized by higher ionic strength waters with higher nutrient and metal concentrations. An analysis of land-use data and SPAtially Referenced Regressions On Watershed (SPARROW) modeling data indicates that manure sources of nitrogen dominate the input of nitrogen to the watershed. Implementation of conservation practices increased in the Conewago Creek watershed during the study period, and while a broad range of practice types were implemented, the most common practices included residue and tillage management, cover crops, nutrient management, terracing, and stream fencing (for animal exclusion or bank restoration). While the implementation of these conservation practices is encouraging, the cumulative effects of these practices probably will not be detected in Conewago Creek water quality for several years. The magnitude of the effects of these conservation practices on water quality in Conewago Creek will depend largely on the extent to which nutrient loading (septic, manure, and commercial fertilizer) and sediment-producing activities are reduced over time. Difficult Run The Difficult Run watershed is a 57.82-mi 2 watershed that drains to the Potomac River. The long-term Difficult Run base-flow index (from 1936 to 2010) was 57.9, indicating that approximately 58 percent of streamflow exited the watershed as base flow and 42 percent as stormflow; however, with continued development and urbanization of the watershed, the base-flow index has decreased to 50 percent during the last 20 years. This base-flow index was less than those of the other watersheds evaluated in this study, likely because the Difficult Run watershed largely is underlain by crystalline piedmont metamorphic rocks and has a greater proportion of impervious urban land cover. A series of cluster and principal components analyses indicated that most of the variability in Difficult Run water quality could be attributed to hydrologic variability and seasonality. Statistically significant positive correlations with flow were observed for turbidity, dissolved oxygen, suspended sediments, ammonium, orthophosphate, iron, and total phosphorus. Statistically significant inverse correlations with flow were observed for water temperature, pH, specific conductance, bicarbonate, calcium, magnesium, nitrate, δ 15 N of nitrate, and silica. Statistically significant seasonal patterns were observed for numerous water-quality constituents: water temperature, ammonium, orthophosphate, and δ 15 N of nitrate were higher during the warm season, and dissolved oxygen, nitrate, and manganese were higher during the cool season. Surrogate regression models were developed to compute sediment and nutrient loading rates. The Difficult Run sediment load was approximately 8,000 tons per year, with greater than 95 percent of the sediment load in the 2013 water year contributed by the seven largest storm events. The total phosphorus load in Difficult Run was approximately 14,000 pounds of phosphorus per year, with the majority of the load contributed during stormflow periods. The total nitrogen load in Difficult Run is estimated to have been approximately 140,000 pounds per year, with total nitrogen accumulation less dominated by stormflow contributions than that of phosphorus and strongly affected by base-flow export of nitrogen from the basin. Extensive water-quality monitoring throughout the Difficult Run watershed revealed relatively uniform generation of flow per unit of watershed area, as well as spatial variation in water quality that is strongly related to land-use activities. Elevated nitrate concentrations were observed in a subset of monitoring sites that are inversely correlated with population density and positively correlated to the septic system density within each subwatershed. The majority of the elevated nitrate concentrations for these sites are hypothesized to be caused by nitrate leaching from septic systems, more so than homeowner fertilizer usage among these subwatersheds that have lower population densities than other parts of the watershed. Nitrate isotope data, temporal patterns in the water-quality data, mass-balance computations, and a separate land-use analysis all generally indicate that leachate from septic systems was the likely source of the elevated nitrate. Another group of water-quality sites have relatively low nitrogen concentrations, are located in areas that are served by city sewer lines, and have experienced stream restoration activities. A final group of sites drained the areas with the highest imperviousness and had strongly elevated specific conductance, chloride, and sodium, which were likely caused by a combination of road salting and other anthropogenic sources draining these urbanized areas in the watershed. A fourth group of sites represents a mixture of water sources and had water quality similar to that at the Difficult Run streamgage. Analysis of the nitrate isotope data generally indicates a broad range of composition indicative of mixed natural and anthropogenic nitrogen sources. Implementation of conservation practices increased in the Difficult Run watershed during the study period, and while a broad range of practice types was implemented, the most common practices included stream restoration. While the implementation of these conservation practices is encouraging, the cumulative effect of these practices probably will not be detected in Difficult Run water quality for several years.

Maryland, Pennsylvania, Virginia

Groundwater quality and simulation of sources of water to wells in the Marsh Creek valley at the U.S. Geological Survey Northern Appalachian Research Laboratory, Tioga County, Pennsylvania

This report provides a November 2010 snapshot of groundwater quality and an analysis of the sources of water to wells at the U.S. Geological Survey (USGS) Northern Appalachian Research Laboratory (NARL) near Wellsboro, Pennsylvania. The laboratory, which conducts fisheries research, currently (2011) withdraws 1,000 gallons per minute of high-quality groundwater from three wells completed in the glacial sand and gravel aquifer beneath the Marsh Creek valley; a fourth well that taps the same aquifer provides the potable supply for the facility. The study was conducted to document the source areas and quality of the water supply for this Department of Interior facility, which is surrounded by the ongoing development of natural gas from the Marcellus Shale. Groundwater samples were collected from the four wells used by the NARL and from two nearby domestic-supply wells. The domestic-supply wells withdraw groundwater from bedrock of the Catskill Formation. Samples were analyzed for major ions, nutrients, trace metals, radiochemicals, dissolved gases, and stable isotopes of oxygen and hydrogen in water and carbon in dissolved carbonate to document groundwater quality. Organic constituents (other than hydrocarbon gases) associated with hydraulic fracturing and other human activities were not analyzed as part of this assessment. Results show low concentrations of all constituents. Only radon, which ranged from 980 to 1,310 picocuries per liter, was somewhat elevated. These findings are consistent with the pristine nature of the aquifer in the Marsh Creek valley, which is the reason the laboratory was sited at this location. The sources of water and areas contributing recharge to wells were identified by the use of a previously documented MODFLOW groundwater-flow model for the following conditions: (1) withdrawals of 1,000 to 3,000 gallons per minute from the NARL wells, (2) average or dry hydrologic conditions, and (3) withdrawals of 1,000 gallons per minute from a new well 3,500 feet to the southwest that was drilled to provide water for Marcellus gas-well operations. Results of simulations indicate that during average hydrologic conditions, infiltration from Straight Run, a tributary to Marsh Creek, provides nearly all the water to the NARL wells. During dry conditions, the areas contributing recharge expand such that Asaph Run contributes about half of the water to the NARL wells when withdrawals are 1,000 or 2,000 gallons per minute. The addition of a simulated withdrawal of 1,000 gallons per minute from the nearby new well does not substantially affect the sources of water captured by the NARL wells. These results are subject to some limitations. The water-quality samples represent a snapshot of groundwater chemistry for only one hydrologic condition; the concentrations of some constituents may change temporally. In addition, samples were collected and analyzed for hydrocarbon gases, but not organic constituents associated with hydraulic fracturing; additional sampling for these constituents would provide a more complete water-quality baseline. The sources contributing water to the NARL wells and the new well were simulated by use of a simplified one-layer model of the glacial sand and gravel aquifer for steady-state conditions that in reality are never achieved. Steady-state simulations of dry hydrologic conditions show that it is possible for the NARL wells to capture water from Asaph Run; however, maps of simulated groundwater time-of-travel indicate that a dry period of unusually long duration would be required. A better analysis could be done by recalibrating the groundwater-flow model with a finite-difference grid having multiple layers, cells smaller than the 200-foot by 200-foot cells used in this study, and transient stress periods.

Pennsylvania

Relation between organic-wastewater compounds, groundwater geochemistry, and well characteristics for selected wells in Lansing, Michigan

In 2010, groundwater from 20 Lansing Board of Water and Light (BWL) production wells was tested for 69 organic-wastewater compounds (OWCs). The OWCs detected in one-half of the sampled wells are widely used in industrial and environmental applications and commonly occur in many wastes and stormwater. To identify factors that contribute to the occurrence of these constituents in BWL wells, the U.S. Geological Survey (USGS) interpreted the results of these analyses and related detections of OWCs to local characteristics and groundwater geochemistry. Analysis of groundwater-chemistry data collected by the BWL during routine monitoring from 1969 to 2011 indicates that the geochemistry of the BWL wells has changed over time, with the major difference being an increase in sodium and chloride. The concentrations of sodium and chloride were positively correlated to frequency of OWC detections. The BWL wells studied are all completed in the Saginaw aquifer, which consists of water-bearing sandstones of Pennsylvanian age. The Saginaw aquifer is underlain by the Parma-Bayport aquifer, and overlain by the Glacial aquifer. Two possible sources of sodium and chloride were evaluated: basin brines by way of the Parma-Bayport aquifer, and surficial sources by way of the Glacial aquifer. To determine if water from the underlying aquifer had influenced well-water geochemistry over time, the total dissolved solids concentration and changes in major ion concentrations were examined with respect to well depth, age, and pumping rate. To address a possible surficial source of sodium and chloride, 25 well, aquifer, or hydrologic characteristics, and 2 groundwater geochemistry variables that might influence whether, or the rate at which, water from the land surface could reach each well were compared to OWC detections and well chemistry. The statistical tests performed during this study, using available variables, indicated that reduced time of travel of water from the land surface to the well opening was significantly correlated with detections of OWCs. No specific well or aquifer characteristic was correlated with OWC detections; however, wells with detections tended to have less modeled confining material thickness (as simulated in the regional groundwater flow model), which is an estimate of the amount of clay or shale between the Glacial and Saginaw aquifers. Additional analyses and collection of other data would be required to more conclusively identify the source and to determine the potential vulnerability of other wells because each BWL well may have a somewhat unique set of characteristics that governs its response to pumping. Therefore, it is possible that a relevant explanatory variable was not included in this analysis. The current patterns of geochemistry, and the relation between these patterns and volume of pumpage for the BWL wells, indicates other wells may be susceptible to OWCs in the future.

Michigan

Effects of urbanization on stream ecosystems in the South Platte River basin, Colorado and Wyoming

This report describes the effects of urbanization on physical, chemical, and biological characteristics of stream ecosystems in 28 basins along an urban land-use gradient in the South Platte River Basin, Colorado and Wyoming, from 2002 through 2003. Study basins were chosen to minimize natural variability among basins due to factors such as geology, elevation, and climate and to maximize coverage of different stages of urban development among basins. Because land use or population density alone often are not a complete measure of urbanization, land use, land cover, infrastructure, and socioeconomic variables were integrated in a multimetric urban intensity index to represent the degree of urban development in each study basin. Physical characteristics studied included stream hydrology, stream temperature, and habitat; chemical characteristics studied included nutrients, pesticides, suspended sediment, sulfate, chloride, and fecal bacteria concentrations; and biological characteristics studied included algae, fish, and invertebrate communities. Semipermeable membrane devices (SPMDs), passive samplers that concentrate trace levels of hydrophobic organic contaminants like polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs), also were used. The objectives of the study were to (1) examine physical, chemical, and biological responses along the gradient of urbanization; (2) determine the major physical, chemical, and landscape variables affecting the structure of aquatic communities; and (3) evaluate the relevance of the results to the management of water resources in the South Platte River Basin. Commonly observed effects of urbanization on instream physical, chemical, and biological characteristics, such as increased flashiness, higher magnitude and more frequent peak flows, increased concentrations of chemicals, and changes in aquatic community structure, generally were not observed in this study. None of the hydrologic, temperature, habitat, or chemical variables were correlated strongly (Spearman's rho greater than or equal to 0.7) with urban intensity, with the exception of some of the SPMD-based toxicity and chemical variables. SPMD-based measures of potential toxicity and PAH concentrations were positively correlated with urban intensity. The PAH concentrations also were positively correlated with measures of road density and negatively correlated with distance to the nearest road, indicating that automobile exhaust is a major source of these compounds in the study area. This source may be localized enough that the transport of PAHs would be minimally affected by water-management practices such as diversion or storage upstream. In contrast, the predominant sources of nutrients, bacteria, suspended sediment, sulfate, chloride, and pesticides may be more dispersed throughout the drainage area and, therefore, their transport to downstream sites may be subject to greater disruption by water regulation. Although no direct link was found between most water-chemistry characteristics and urbanization, invertebrate, algae, and fish-community characteristics were strongly associated with nutrients, pesticides, sulfate, chloride, and suspended sediment. None of the biological community variables were strongly correlated with the urban intensity index. Algal biomass predominantly was associated with total nitrogen concentrations, nitrite-plus-nitrate concentrations, and the duration of high flows. Fish communities predominantly were associated with housing age, the percentage of suspended sediment finer than 0.063 millimeters and chloride concentrations. Invertebrate communities predominantly were associated with the frequency of rising and falling flow events, the duration of high flows, total nitrogen concentrations, nitrite-plus-nitrate concentrations, and total herbicide concentrations. Historical records indicate that aquatic communities in the region may have been altered prior to any substantial urban development by early agricultural and water-management practices. Present-day aquatic communities are composed primarily of tolerant species even in areas of minimal urban development; when development does occur, the communities already may be resistant to disturbance. In addition to the effects of historical stressors on aquatic community structure, it is possible that current water-management practices in the study basins are having an effect. In the absence of natural, unaltered hydrologic conditions, more sensitive taxa may be unable to recolonize urban streams. The movement and storage of water also may lead to a disconnect between the land surface and streams, resulting in instream physical, chemical, and biological characteristics that, to some degree, are independent of land-cover characteristics.

Colorado, Wyoming

Hydrogeologic characterization, groundwater chemistry, and vulnerability assessment, Ute Mountain Ute Reservation, Colorado and Utah

The U.S. Geological Survey, in cooperation with the Ute Mountain Ute Tribe (UMUT), initiated a study in 2016 to increase understanding of the hydrogeology and chemistry of groundwater within select areas of the Ute Mountain Ute Reservation (UMUR) in Colorado and Utah, identify vulnerabilities to the system and other natural resources, and outline information needs to aid in the understanding and protection of groundwater resources. The results presented for this study can be used to support the UMUT’s goal of protecting their vital groundwater resources on the UMUR. Hydrogeologic conditions were characterized for the surficial aquifer contained in Quaternary-age unconsolidated surficial deposits and the Dakota aquifer contained in the Cretaceous-age Dakota Sandstone. In the surficial aquifer, median depth to water ranges from about 5.4 to 17.2 feet below land surface in the Farm and Ranch Enterprise area and 11 to 34 feet below land surface in the Towaoc area, and the water table slopes generally southwest or south. A map of depth to the top of the Dakota Sandstone was constructed from existing well data. Depths range from zero in outcrop areas to more than 3,000 feet below land surface on mesas in the southeastern part of the UMUR. Groundwater-chemistry data were collected by the UMUT from 13 springs and 31 wells from 1996 through 2017. Specific conductance was much lower for samples from springs than from wells; median values were 512 and 6,024 microsiemens per centimeter at 25 degrees Celsius, respectively. Spring samples were well oxygenated. A few well samples were anoxic (dissolved oxygen concentrations less than 0.5 milligrams per liter [mg/L]), indicating reducing conditions in the aquifer. About 75 percent of spring samples had fresh water (total dissolved solids concentrations less than 1,000 mg/L), and about 85 percent of well samples had brackish or highly saline water (total dissolved solids concentrations greater than 1,000 mg/L). Water type for springs on the Ute Mountains was calcium bicarbonate. Lower-altitude springs had a calcium-sulfate water type. Most well samples had sodium as the dominant cation, and sulfate, bicarbonate, and chloride as the dominant anions. Fluoride concentrations in about 45 percent of well samples were greater than an agricultural-use standard of 2 mg/L. Nitrate plus nitrite concentrations in most spring and well samples were less than about 1.6 mg/L per liter. Concentrations in samples from wells in the irrigated agricultural area were elevated; the maximum concentration was 78.5 mg/L. About one-half of the trace-element samples had concentrations that were less than laboratory reporting limits. Only aluminum, arsenic, and selenium in spring samples, and boron and selenium in well samples, were detected at concentrations greater than surface-water standards or water-quality standards for agricultural use of groundwater. Only three organic compounds, the pesticides alachlor and atrazine and the volatile organic compound di(2-ethylhexyl) phthalate, were detected in well samples. The Escherichia coli bacteria was detected in 47 and 23 percent of samples from wells and springs, respectively. The E. coli detections included samples from three culturally significant springs, which did not meet the UMUT cultural-use standard of total absence of E. coli. Tritium and carbon-14 were the primary environmental tracers used for interpreting groundwater ages for Lopez 2 Spring and five wells (AP–1, 5000 Block, Cottonwood Spring, Goodknight, and SE Toe). Water from the AP–1 well contained a mixture of pre- and post-1950s recharge. Tritium and carbon-14 recharge ages for Lopez 2 Spring (post-1950s in age), Goodknight and SE Toe wells (pre-1950s in age), and Cottonwood Spring well (primarily pre-1950s in age) are supported by helium-4 data. The helium-4 data for the 5000 Block well are inconsistent with the tritium and carbon-14 age of pre-1950s recharge because of interference caused by high methane concentrations in the water. Springs and surficial deposits are more vulnerable to contamination from anthropogenic chemicals than deeper bedrock wells. Bedrock aquifers are vulnerable in areas where the geologic formations containing the aquifers are exposed at the land surface. Groundwater in deep bedrock aquifers is likely thousands of years old and is not currently affected by present-day land uses. Both shallow and deep groundwater are vulnerable to naturally occurring salts and minerals, such as of total dissolved solids, major ions, nitrate, and trace elements. Effects of a changing climate on water resources and other ecological characteristics of the UMUR could include changes in evapotranspiration, a decrease in snowpack, decreased aquifer recharge and flow of springs, a decrease in soil moisture, and increased occurrence of wildfires and forest mortality. Of particular interest for the UMUT are possible effects of a changing climate on medicinal and culturally important plants and springs Several information needs were identified during this study that would aid in the understanding and protection of groundwater resources on the UMUR. These include well-completion information for bedrock wells, the collection of environmental tracer data at additional wells, the addition of methane and hydrocarbon analysis to well sampling plans, and the resampling of springs and wells that were last sampled in 2002 or earlier.

Colorado

Ground-water system, estimation of aquifer hydraulic properties, and effects of pumping on ground-water flow in Triassic sedimentary rocks in and near Lansdale, Pennsylvania

Ground water in Triassic-age sedimentary fractured-rock aquifers in the area of Lansdale, Pa., is used as drinking water and for industrial supply. In 1979, ground water in the Lansdale area was found to be contaminated with trichloroethylene, tetrachloroethylene, and other man-made organic compounds, and in 1989, the area was placed on the U.S. Environmental Protection Agency's (USEPA) National Priority List as the North Penn Area 6 site. To assist the USEPA in the hydrogeological assessment of the site, the U.S. Geological Survey began a study in 1995 to describe the ground-water system and to determine the effects of changes in the well pumping patterns on the direction of ground-water flow in the Lansdale area. This determination is based on hydrologic and geophysical data collected from 1995-98 and on results of the simulation of the regional ground-water-flow system by use of a numerical model. Correlation of natural-gamma logs indicate that the sedimentary rock beds strike generally northeast and dip at angles less than 30 degrees to the northwest. The ground-water system is confined or semi-confined, even at shallow depths; depth to bedrock commonly is less than 20 feet (6 meters); and depth to water commonly is about 15 to 60 feet (5 to 18 meters) below land surface. Single-well, aquifer-interval-isolation (packer) tests indicate that vertical permeability of the sedimentary rocks is low. Multiple-well aquifer tests indicate that the system is heterogeneous and that flow appears primarily in discrete zones parallel to bedding. Preferred horizontal flow along strike was not observed in the aquifer tests for wells open to the pumped interval. Water levels in wells that are open to the pumped interval, as projected along the dipping stratigraphy, are drawn down more than water levels in wells that do not intersect the pumped interval. A regional potentiometric map based on measured water levels indicates that ground water flows from Lansdale towards discharge areas in three drainages, the Wissahickon, Towamencin, and Neshaminy Creeks. Ground-water flow was simulated for different pumping patterns representing past and current conditions. The three-dimensional numerical flow model (MODFLOW) was automatically calibrated by use of a parameter estimation program (MODFLOWP). Steady-state conditions were assumed for the calibration period of 1996. Model calibration indicates that estimated recharge is 8.2 inches (208 millimeters) and the regional anisotropy ratio for the sedimentary-rock aquifer is about 11 to 1, with permeability greatest along strike. The regional anisotropy is caused by up- and down-dip termination of high-permeability bed-oriented features, which were not explicitly simulated in the regional-scale model. The calibrated flow model was used to compare flow directions and capture zones in Lansdale for conditions corresponding to relatively high pumping rates in 1994 and to lower pumping rates in 1997. Comparison of the 1994 and 1997 simulations indicates that wells pumped at the lower 1997 rates captured less ground water from known sites of contamination than wells pumped at the 1994 rates. Ground-water flow rates away from Lansdale increased as pumpage decreased in 1997. A preliminary evaluation of the relation between ground-water chemistry and conditions favorable for the degradation of chlorinated solvents was based on measurements of dissolved-oxygen concentration and other chemical constituents in water samples from 92 wells. About 18 percent of the samples contained less than or equal to 5 milligrams per liter dissolved oxygen, a concentration that indicates reducing conditions favorable for degradation of chlorinated solvents.

Water-Resources Investigations Report