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The U.S. Geological Survey Monthly Water Balance Model Futures Portal

The U.S. Geological Survey Monthly Water Balance Model Futures Portal ( https://my.usgs.gov/mows/ ) is a user-friendly interface that summarizes monthly historical and simulated future conditions for seven hydrologic and meteorological variables (actual evapotranspiration, potential evapotranspiration, precipitation, runoff, snow water equivalent, atmospheric temperature, and streamflow) at locations across the conterminous United States (CONUS). The estimates of these hydrologic and meteorological variables were derived using a Monthly Water Balance Model (MWBM), a modular system that simulates monthly estimates of components of the hydrologic cycle using monthly precipitation and atmospheric temperature inputs. Precipitation and atmospheric temperature from 222 climate datasets spanning historical conditions (1952 through 2005) and simulated future conditions (2020 through 2099) were summarized for hydrographic features and used to drive the MWBM for the CONUS. The MWBM input and output variables were organized into an open-access database. An Open Geospatial Consortium, Inc., Web Feature Service allows the querying and identification of hydrographic features across the CONUS. To connect the Web Feature Service to the open-access database, a user interface—the Monthly Water Balance Model Futures Portal—was developed to allow the dynamic generation of summary files and plots based on plot type, geographic location, specific climate datasets, period of record, MWBM variable, and other options. Both the plots and the data files are made available to the user for download

Open-File Report↗

The influences of land use and land cover on climate; an analysis of the Washington-Baltimore area that couples remote sensing with numerical simulation

The Sun drives the atmospheric heat engine by warming the terrestrial surface which in turn warms the atmosphere above. Climate, therefore, is significantly controlled by complex interaction of energy flows near and at the terrestrial surface. When man alters this delicate energy balance by his use of the land, he may alter his climatic environment as well. Land use climatology has emerged as a discipline in which these energy interactions are studied; first, by viewing the spatial distributions of their surface manifestations, and second, by analyzing the energy exchange processes involved. Two new tools for accomplishing this study are presented: one that can interpret surface energy exchange processes from space, and another that can simulate the complex of energy transfers by a numerical simulation model. Use of a satellite-borne multispectral scanner as an imaging radiometer was made feasible by devising a gray-window model that corrects measurements made in space for the effects of the atmosphere in the optical path. The simulation model is a combination of mathematical models of energy transfer processes at or near the surface. Integration of these two analytical approaches was applied to the Washington-Baltimore area to coincide with the August 5, 1973, Skylab 3 overpass which provided data for constructing maps of the energy characteristics of the Earth's surface. The use of the two techniques provides insights into the relationship of climate to land use and land cover and in predicting alterations of climate that may result from alterations of the land surface.

Professional Paper↗

Geochemical Exploration Techniques Applicable in the Search for Copper Deposits

Geochemical exploration is an important part of copper-resource evaluation. A large number of geochemical exploration techniques, both proved and untried, are available to the geochemist to use in the search for new copper deposits. Analyses of whole-rock samples have been used in both regional and local geochemical exploration surveys in the search for copper. Analyses of mineral separates, such as biotite, magnetite, and sulfides, have also been used. Analyses of soil samples are widely used in geochemical exploration, especially for localized surveys. It is important to distinguish between residual and transported soil types. Orientation studies should always be conducted prior to a geochemical investigation in a given area in order to determine the best soil horizon and the best size of soil material for sampling in that area. Silty frost boils, caliche, and desert varnish are specialized types of soil samples that might be useful sampling media. Soil gas is a new and potentially valuable geochemical sampling medium, especially in exploring for buried mineral deposits in arid regions. Gaseous products in samples of soil may be related to base-metal deposits and include mercury vapor, sulfur dioxide, hydrogen sulfide, carbon oxysulfide, carbon dioxide, hydrogen, oxygen, nitrogen, the noble gases, the halogens, and many hydrocarbon compounds. Transported materials that have been used in geochemical sampling programs include glacial float boulders, glacial till, esker gravels, stream sediments, stream-sediment concentrates, and lake sediments. Stream-sediment sampling is probably the most widely used and most successful geochemical exploration technique. Hydrogeochemical exploration programs have utilized hot- and cold-spring waters and their precipitates as well as waters from lakes, streams, and wells. Organic gel found in lakes and at stream mouths is an unproved sampling medium. Suspended material and dissolved gases in any type of water may also be useful media. Samples of ice and snow have been used for limited geochemical surveys. Both geobotanical and biogeochemical surveys have been successful in locating copper deposits in many parts of the world. Micro-organisms, including bacteria and algae, are other unproved media that should be studied. Animals can be used in geochemical-prospecting programs. Dogs have been used quite successfully to sniff out hidden and exposed sulfide minerals. Tennite mounds are commonly composed of subsurface material, but have not as yet proved to be useful in locating buried mineral deposits. Animal tissue and waste products are essentially unproved but potentially valuable sampling media. Knowledge of the location of areas where trace-element-associated diseases in animals and man are endemic as well as a better understanding of these diseases, may aid in identifying regions that are enriched in or depleted of various elements, including copper. Results of analyses of gases in the atmosphere are proving valuable in mineral-exploration surveys. Studies involving metallic compounds exhaled by plants into the atmosphere, and of particulate matter suspended in the atmosphere are reviewed these methods may become important in the future. Remote-sensing techniques are useful for making indirect measurements of geochemical responses. Two techniques applicable to geochemical exploration are neutron-activation analysis and gamma-ray spectrometry. Aerial photography is especially useful in vegetation surveys. Radar imagery is an unproved but potentially valuable method for use in studies of vegetation in perpetually clouded regions. With the advent of modern computers, many new techniques, such as correlation analysis, regression analysis, discriminant analysis, factor analysis, cluster analysis, trend-surface analysis, and moving-average analysis can be applied to geochemical data sets. Selective use of these techniques can provide new insights into the interpretatio

Professional Paper↗

Sources of mercury in sediments, water, and fish of the lakes of Whatcom County, Washington

Concerns about mercury (Hg) contamination in Lake Whatcom, Washington, were raised in the late 1990s after a watershed protection survey reported elevated concentrations of Hg in smallmouth bass. The U.S. Geological Survey, the Whatcom County Health Department, and the Washington State Department of Ecology (Ecology) cooperated to develop a study to review existing data and collect new data that would lead to a better understanding of Hg deposition to Lake Whatcom and other lakes in Whatcom County, Washington. A simple atmospheric deposition model was developed that allowed comparisons of the deposition of Hg to the surfaces of each lake. Estimates of Hg deposition derived from the model indicated that the most significant deposition of Hg would have occurred to the lakes north of the City of Bellingham. These lakes were in the primary wind pattern of two municipal waste incinerators. Of all the lakes examined, basin 1 of Lake Whatcom would have been most affected by the Hg emissions from the chlor-alkali plant and the municipal sewage-sludge incinerator in the City of Bellingham. The length-adjusted concentrations of Hg in largemouth and smallmouth bass were not related to estimated deposition rates of Hg to the lakes from local atmospheric sources. Total Hg concentrations in the surface sediments of Lake Whatcom are affected by the sedimentation of fine-grained particles, whereas organic carbon regulates the concentration of methyl-Hg in the surface sediments of the lake. Hg concentrations in dated sediment core samples indicate that increases in Hg sedimentation were largest during the first half of the 20th century. Increases in Hg sedimentation were smaller after the chlor-alkali plant and the incinerators began operating between 1964 and 1984. Analysis of sediments recently deposited in basin 1 of Lake Whatcom, Lake Terrell, and Lake Samish indicates a decrease in Hg sedimentation. Concentrations of Hg in Seattle precipitation and in tributary waters were used to calculate current (2002-03) loadings of Hg to Lake Whatcom. Hg in tributaries contributed 59 percent of the total Hg, whereas non-local atmospheric deposition was estimated to have contributed 41 percent of the 303 grams of Hg entering Lake Whatcom each year. However, these inputs cannot be verified without a better understanding of the sources of sediment to Lake Whatcom.

Scientific Investigations Report↗

Trends in streamflow, sedimentation, and sediment chemistry for the Wolf River, Menominee Indian Reservation, Wisconsin, 1850-1999

Historical trends in streamflow, sedimentation, and sediment chemistry of the Wolf River were examined for a 6-mile reach that flows through the southern part of the Menominee Indian Reservation and the northern part of Shawano County, Wis. Trends were examined in the context of effects from dams, climate, and land-cover change. Annual flood peaks and mean monthly flow for the Wolf River were examined for 1907-96 and compared to mean annual and mean monthly precipitation. Analysis of trends in sedimentation (from before about 1850 through 1999) involved collection of cores and elevation data along nine valley transects spanning the Wolf River channel, flood plain, and backwater and impounded areas; radioisotope analyses of impounded sediment cores; and analysis of General Land Office Survey Notes (1853-91). Trends in sediment chemistry were examined by analyzing samples from an impoundment core for minor and trace elements. Annual flood peaks for the Wolf River decreased during 1907-49 but increased during 1950-96, most likely reflecting general changes in upper-atmospheric circulation patterns from more zonal before 1950 to more meridional after 1950. The decrease in flood peaks during 1907-49 may also, in part, be due to forest regrowth. Mean monthly streamflow during 1912-96 increased for the months of February and March but decreased for June and July, suggesting that spring snowmelt occurs earlier in the season than it did in the past. Decreases in early summer flows may be a reflection earlier spring snowmelt and large rainstorms in early spring rather than early summer. These trends also may reflect upper-atmospheric circulation patterns. The Balsam Row Dam impoundment contains up to 10 feet of organic-rich silty clay and has lost much of its storage capacity. Fine sediment has accumulated for 1.8 miles upstream from the Balsam Row Dam. Historical average linear and mass sedimentation rates in the Balsam Row impoundment were 0.09 feet per year and 1.15 pounds per square foot per year for 1927-62 and 0.10 feet per year and 1.04 pounds per square foot per year for 1963-99. Sedimentation in the impoundment was episodic and was associated with large floods, especially the flood-related failure of the Keshena Falls Dam in 1972 and a large flood in 1973. Sand deposition is common in the Wolf River upstream from the impounded reach for 2.5 miles and is caused by the base-level increase associated with the Balsam Row Dam. Some sand deposition also may have been associated with logging and log drives in the late 1800s and the failure of the Keshena Falls Dam. In the upstream 1.5-mile part of the studied reach, the substrate is mainly rocky; however, about 2,000 feet downstream from Keshena Falls, the channel has narrowed and incised since the 1890s, likely related to human alterations associated with logging, log drives, and (or) changes in hydraulics and sediment characteristics associated with completion of the Keshena Falls Dam and head race in 1908. Minor- and trace-element concentrations in sediment from Balsam Row impoundment and other depositional areas along the Wolf River generally reflect background conditions as affected by watershed geology and historical inputs from regional and local atmospheric deposition.

Wisconsin↗

Freshwater and saline loads of dissolved inorganic nitrogen to Hood Canal and Lynch Cove, western Washington

Hood Canal is a long (110 kilometers), deep (175 meters) and narrow (2 to 4 kilometers wide) fjord of Puget Sound in western Washington. The stratification of a less dense, fresh upper layer of the water column causes the cold, saltier lower layer of the water column to be isolated from the atmosphere in the late summer and autumn, which limits reaeration of the lower layer. In the upper layer of Hood Canal, the production of organic matter that settles and consumes dissolved oxygen in the lower layer appears to be limited by the load of dissolved inorganic nitrogen (DIN): nitrate, nitrite, and ammonia. Freshwater and saline loads of DIN to Hood Canal were estimated from available historical data. The freshwater load of DIN to the upper layer of Hood Canal, which could be taken up by phytoplankton, came mostly from surface and ground water from subbasins, which accounts for 92 percent of total load of DIN to the upper layer of Hood Canal. Although DIN in rain falling on land surfaces amounts to about one-half of the DIN entering Hood Canal from subbasins, rain falling directly on the surface of marine waters contributed only 4 percent of the load to the upper layer. Point-source discharges and subsurface flow from shallow shoreline septic systems contributed less than 4 percent of the DIN load to the upper layer. DIN in saline water flowing over the sill into Hood Canal from Admiralty Inlet was at least 17 times the total load to the upper layer of Hood Canal. In September and October 2004, field data were collected to estimate DIN loads to Lynch Cove - the most inland marine waters of Hood Canal that routinely contain low dissolved-oxygen waters. Based on measured streamflow and DIN concentrations, surface discharge was estimated to have contributed about one-fourth of DIN loads to the upper layer of Lynch Cove. Ground-water flow from subbasins was estimated to have contributed about one-half of total DIN loads to the upper layer. In autumn 2004, the relative contribution of DIN from shallow shoreline septic systems to the upper layer was higher in Lynch Cove (23 percent) than in the entire Hood Canal. Net transport of DIN into Lynch Cove by marine currents was measured during August and October 2004-a time of high biological productivity. The net transport of lower-layer water into Lynch Cove was significantly diminished relative to the flow entering Hood Canal at its entrance. Even though the net transport of saline water into the lower layer of Lynch Cove was only 119 cubic meters per second, estuarine currents between 33 and 47 m were estimated to have carried more than 35 times the total freshwater load of DIN to the upper layer from surface and ground water, shallow shoreline septic systems, and direct atmospheric rainfall. The subsurface maximums in measured turbidity, chlorophyll a, particulate organic carbon, and particulate organic nitrogen strongly suggest that the upward mixing of nitrate-rich deeper water is a limiting factor in supplying DIN to the upper layer that enhances marine productivity in Lynch Cove. The presence of phosphate in the upper layer in the absence of dissolved inorganic nitrogen also suggests that the biological productivity that leads to low dissolved-oxygen concentrations in the lower layer of Lynch Cove is limited by the supply of nitrogen rather than by phosphate loads. Although the near-shore zones of the shallow parts of Lynch Cove were sampled, a biogeochemical signal from terrestrial nitrogen was not found. Reversals in the normal estuarine circulation suggest that if the relative importance of the DIN load of freshwater terrestrial and atmospheric sources and the DIN load from transport of saline water by the estuarine circulation in controlling dissolved-oxygen concentrations in Lynch Cove is to be better understood, then the physical forces driving Hood Canal circulation must be better defined.

Scientific Investigations Report↗

Relation of Chlorofluorocarbon Ground-Water Age Dates to Water Quality in Aquifers of West Virginia

The average apparent age of ground water in fractured-bedrock aquifers in West Virginia was determined using chlorofluorocarbon (CFC) dating methods. Since the introduction of CFC gases as refrigerants in the late 1930s, atmospheric concentrations have increased until production ceased in the mid-1990s. CFC dating methods are based on production records that date to the early 1940s, and the preservation of atmospheric CFC concentrations in ground water at the time of recharge. As part of the U.S. Geological Survey (USGS) National Water-Quality Assessment (NAWQA) and Ambient Ground-Water Monitoring Network (AGN) programs in West Virginia from 1997 to 2005, 80 samples from the Appalachian Plateaus Physiographic Province, 27 samples from the Valley and Ridge Physiographic Province, and 5 samples from the Ohio River alluvial aquifers were collected to estimate ground-water ages in aquifers of West Virginia. Apparent CFC ages of water samples from West Virginia aquifers ranged from 5.8 to 56 years. In the Appalachian Plateaus, topographically driven ground-water flow is evident from apparent ages of water samples from hilltop, hillside, and valley settings (median apparent ages of 12, 14, and 25 years, respectively). Topographic setting was the only factor that was found to be related to apparent ground-water age in the Plateaus at the scale of this study. Similar relations were not found in Valley and Ridge aquifers, indicating that other factors such as bedding or geologic structure may serve larger roles in controlling ground-water flow in that physiographic province. Degradation of CFCs was common in samples collected from methanogenic/anoxic aquifers in the Appalachian Plateaus and suboxic to anoxic aquifers in the Valley and Ridge. CFC contamination was most common in Ohio River alluvial aquifers and carbonate units of the Valley and Ridge, indicating that these highly transmissive surficial aquifers are the most vulnerable to water-quality degradation and may contain wastewater from domestic or industrial sources with CFC concentrations greater than modern atmospheric levels. However, based on a lack of detections of the volatile organic compounds analyzed for in most of the water samples collected for this and similar USGS investigations, ground-water resources of West Virginia used for public and private consumption do not appear to be routinely affected by anthropogenic activities despite their young apparent age.

Scientific Investigations Report↗

Water Quality and Hydrology of Whitefish (Bardon) Lake, Douglas County, Wisconsin, With Special Emphasis on Responses of an Oligotrophic Seepage Lake to Changes in Phosphorus Loading and Water Level

Whitefish Lake, which is officially named Bardon Lake, is an oligotrophic, soft-water seepage lake in northwestern Wisconsin, and classified by the Wisconsin Department of Natural Resources as an Outstanding Resource Water. Ongoing monitoring of the lake demonstrated that its water quality began to degrade (increased phosphorus and chlorophyll a concentrations) around 2002 following a period of high water level. To provide a better understanding of what caused the degradation in water quality, and provide information to better understand the lake and protect it from future degradation, the U.S. Geological Survey did a detailed study from 2004 to 2008. The goals of the study were to describe the past and present water quality of the lake, quantify water and phosphorus budgets for the lake, simulate the potential effects of changes in phosphorus inputs on the lake's water quality, analyze changes in the water level in the lake since 1900, and relate the importance of changes in climate and changes in anthropogenic (human-induced) factors in the watershed to the water quality of the lake. Since 1998, total phosphorus concentrations increased from near the 0.005-milligrams per liter (mg/L) detection limit to about 0.010 mg/L in 2006, and then decreased slightly in 2007-08. During this time, chlorophyll a concentrations and Secchi depths remained relatively stable at about 1.5 micrograms per liter (ug/L) and 26 feet, respectively. Whitefish Lake is typically classified as oligotrophic. Because the productivity in Whitefish Lake is limited by phosphorus, phosphorus budgets were constructed for the lake. Because it was believed that much of its phosphorus comes from the atmosphere, phosphorus deposition was measured in this study. Phosphorus input from the atmosphere was greater than computed based on previously reported wetfall phosphorus concentrations. The concentrations and deposition rates can be used to estimate atmospheric loading in future lake studies. The average annual load of phosphorus to the lake was 232 pounds: 56 percent from precipitation, 27 percent from groundwater, and 16 percent from septic systems. During a series of dry years (low water levels) and wet years (high water levels), the inputs of water and phosphorus ranged by only 10-13 percent. Results from the Canfield and Bachmann eutrophication model and Carlson trophic-state-index equations demonstrated that the lake directly responds to changes in external phosphorus loading, with percent change in chlorophyll a being similar to the percent change in loading and the change in total phosphorus and Secchi depth being slightly smaller. Therefore, changes in phosphorus loading should affect the water quality of the lake. Specific scenarios that simulated the effects of anthropogenic (human-induced) and climatic (water level) changes demonstrated that: surface-water inflow (runoff) based on current development has little effect on pelagic water quality, changes in the inputs from septic systems and development in the watershed could have a large effect on water quality, and decreases in water and phosphorus loading during periods of low water level had little effect on water quality. Sustained high water levels, resulting from several wet years with relatively high water and phosphorus input, however, could cause a small degradation in water quality. Although high water levels may be associated with a degradation in water quality, it appears that anthropogenic changes in the watershed may be more important in affecting the future water quality of the lake. Fluctuations in water levels since 1998 are representative of what has occurred since 1900, with fluctuations of about 3 feet occurring about every 15 years. Based on total phosphorus concentrations inferred from sediment core analysis, there has been little long-term change in water quality and there has been a slight deterioration in water quality following most periods of high water levels. There

Scientific Investigations Report↗

DayCent-Chem simulations of ecological and biogeochemical processes of eight mountain ecosystems in the United States

Atmospheric deposition of nitrogen (N) and sulfur (S) cause complex responses in ecosystems, from fertilization to forest ecosystem decline, freshwater eutrophication to acidification, loss of soil base cations, and alterations of disturbance regimes. DayCent-Chem, an ecosystem simulation model that combines ecosystem nutrient cycling and plant dynamics with aqueous geochemical equilibrium calculations, was developed to address ecosystem responses to combined atmospheric N and S deposition. It is unique among geochemically-based models in its dynamic biological cycling of N and its daily timestep for investigating ecosystem and surface water chemical response to episodic events. The model was applied to eight mountainous watersheds in the United States. The sites represent a gradient of N deposition across locales, from relatively pristine to N-saturated, and a variety of ecosystem types and climates. Overall, the model performed best in predicting stream chemistry for snowmelt-dominated sites. It was more difficult to predict daily stream chemistry for watersheds with deep soils, high amounts of atmospheric deposition, and a large degree of spatial heterogeneity. DayCent-Chem did well in representing plant and soil carbon and nitrogen pools and fluxes. Modeled stream nitrate (NO 3 - ) and ammonium (NH 4 + ) concentrations compared well with measurements at all sites, with few exceptions. Simulated daily stream sulfate (SO 4 2- ) concentrations compared well to measured values for sites where SO 4 2- deposition has been low and where SO 4 2- adsorption/desorption reactions did not seem to be important. The concentrations of base cations and silica in streams are highly dependent on the geochemistry and weathering rates of minerals in each catchment, yet these were rarely, if ever, known. Thus, DayCent-Chem could not accurately predict weathering products for some catchments. Additionally, few data were available for exchangeable soil cations or the magnitude of base cation deposition as a result of dry and fog inputs. The uncertainties related to weathering reactions, deposition, soil cation exchange capacity, and groundwater contributions influenced how well the simulated acid neutralizing capacity (ANC) and pH estimates compared to observed values. Daily discharge was well represented by the model for most sites. The chapters of this report describe the parameterization for each site and summarize model results for ecosystem variables, stream discharge, and stream chemistry. This intersite comparison exercise provided insight about important and possibly not well understood processes.

Scientific Investigations Report↗

Impact of wildfire on levels of mercury in forested watershed systems: Voyageurs National Park, Minnesota

Atmospheric deposition of mercury to remote lakes in mid-continental and eastern North America has increased approximately threefold since the mid-1800s (Swain and others, 1992; Fitzgerald and others, 1998; Engstrom and others, 2007). As a result, concerns for human and wildlife health related to mercury contamination have become widespread. Despite an apparent recent decline in atmospheric deposition of mercury in many areas of the Upper Midwest (Engstrom and Swain, 1997; Engstrom and others, 2007), lakes in which fish contain levels of mercury deemed unacceptable for human consumption and possibly unacceptable for fish-consuming wildlife are being detected with increasing frequency. In northern Minnesota, Voyageurs National Park (VNP) (fig. 1) protects a series of southern boreal lakes and wetlands situated on bedrock of the Precambrian Canadian Shield. Mercury contamination has become a significant resource issue within VNP as high concentrations of mercury in loons, bald eagle eaglets, grebes, northern pike, and other species of wildlife and fish have been found. The two most mercury-contaminated lakes in Minnesota, measured as methylmercury in northern pike ( Esox lucius ), are in VNP. Recent multidisciplinary U.S. Geological Survey (USGS) research demonstrated that the bulk of the mercury in lake waters, soils, and fish in VNP results from atmospheric deposition (Wiener and others, 2006). The study by Wiener and others (2006) showed that the spatial distribution of mercury in watershed soils, lake waters, and age-1 yellow perch ( Perca flavescens ) within the Park was highly variable. The majority of factors correlated for this earlier study suggested that mercury concentrations in lake waters and age-1 yellow perch reflected the influence of ecosystem processes that affected within-lake microbial production and abundance of methylmercury (Wiener and others, 2006), while the distribution of mercury in watershed soils seemed to be partially dependent on forest disturbance, especially the historic forest fire pattern (Woodruff and Cannon, 2002). Forest fire has an essential role in the forest ecosystems of VNP (Heinselman, 1996). Because resource and land managers need to integrate both natural wildfire and prescribed fire in management plans, the potential influence of fire on an element as sensitive to the environment as mercury becomes a critical part of their decisionmaking. A number of recent studies have shown that while fire does have a significant impact on mercury at the landscape level, the observed effects of fire on aquatic environments are highly variable and unpredictable (Caldwell and others, 2000; Garcia and Carrigan, 2000; Kelly and others, 2006; Nelson and others, 2007). Caldwell and others (2000) described an increase in methylmercury in reservoir sediments resulting from mobilization and transport of charred vegetative matter following a fire in New Mexico. Krabbenhoft and Fink (2000) attributed increases in total mercury concentrations in young-of-the-year fish in the Florida Everglades to release of mercury resulting from peat oxidation following fires. A fivefold increase in whole-body mercury accumulation by rainbow trout ( Oncorhynchus mykiss ) following a fire in Alberta, Canada, apparently resulted from increased nutrient concentrations that enhanced productivity and restructured the food web of a lake within the fire’s burn footprint (Kelly and others, 2006). For this study, we determined the short-term effects of forest fire on mercury concentrations in terrestrial and aquatic environments in VNP by comparing and contrasting mercury concentrations in forest soils, lake waters, and age-1 yellow perch for a burned watershed and an adjacent lake, with similar samples from watersheds and lakes with no fire activity (control watersheds and lakes). The concentration of total mercury in whole, 1-year-old yellow perch serves as a good biological indicator for monitoring trends in methylmercury concentrations in food webs of lakes in North America (Wiener and others, 2007). With a limited gape, age-1 yellow perch that hatched the previous year and resided in a lake for 1 year feed largely on zooplankton and small benthic invertebrates. Thus, age-1 yellow perch provide a baseline for methylmercury concentrations for individual lakes that can be compared across spatial areas. The nine appendixes that accompany this report contain the complete datasets for soils, lake waters, and age-1 yellow perch collected for this study. This report uses data from these three media to provide a framework for evaluating short-term effects of fire on mercury in forested soils and possible effects of the mobilization of mercury from soils on lake water quality and aquatic health.

Minnesota↗

Estimates of tracer-based piston-flow ages of groundwater from selected sites: National Water-Quality Assessment Program, 1992–2005

This report documents selected age data interpreted from measured concentrations of environmental tracers in groundwater from 1,399 National Water-Quality Assessment (NAWQA) Program groundwater sites across the United States. The tracers of interest were chlorofluorocarbons (CFCs), sulfur hexafluoride (SF 6 ), and tritium/helium-3 ( 3 H/ 3 He). Tracer data compiled for this analysis primarily were from wells representing two types of NAWQA groundwater studies—Land-Use Studies (shallow wells, usually monitoring wells, in recharge areas under dominant land-use settings) and Major-Aquifer Studies (wells, usually domestic supply wells, in principal aquifers and representing the shallow, used resource). Reference wells (wells representing groundwater minimally impacted by anthropogenic activities) associated with Land-Use Studies also were included. Tracer samples were collected between 1992 and 2005, although two networks sampled from 2006 to 2007 were included because of network-specific needs. Tracer data from other NAWQA Program components (Flow System Studies, which are assessments of processes and trends along groundwater flow paths, and various topical studies) were not compiled herein. Tracer data from NAWQA Land-Use Studies and Major-Aquifer Studies that previously had been interpreted and published are compiled herein (as piston-flow ages), but have not been reinterpreted. Tracer data that previously had not been interpreted and published are evaluated using documented methods and compiled with aqueous concentrations, equivalent atmospheric concentrations (for CFCs and SF 6 ), estimates of tracer-based piston-flow ages, and selected ancillary data, such as redox indicators, well construction, and major dissolved gases (N 2 , O 2 , Ar, CH 4 , and CO 2 ). Tracer-based piston-flow ages documented in this report are simplistic representations of the tracer data. Tracer-based piston-flow ages are a convenient means of conceptualizing groundwater age. However, the piston-flow model is based on the potentially limiting assumptions that tracer transport is advective and that no mixing occurs. Additional uncertainties can arise from tracer degradation, sorption, contamination, or fractionation; terrigenic (natural) sources of tracers; spatially variable atmospheric tracer concentrations; and incomplete understanding of mechanisms of recharge or of the conditions under which atmospheric tracers were partitioned to recharge. The effects of some of these uncertainties are considered herein. For example, degradation, contamination, or fractionation often can be identified or inferred. However, detailed analysis of the effects of such uncertainties on the tracer-based piston-flow ages is constrained by sparse data and an absence of complementary lines of evidence, such as detailed solute transport simulations. Thus, the tracer-based piston-flow ages compiled in this report represent only an initial interpretation of the tracer data.

Scientific Investigations Report↗

Hydrologic budget and conditions of Permian, Pennsylvanian, and Mississippian aquifers in the Appalachian Plateaus physiographic province

In response to challenges to groundwater availability posed by historic land-use practices, expanding development of hydrocarbon resources, and drought, the U.S. Geological Survey Groundwater Resources Program began a regional assessment of the Appalachian Plateaus aquifers in 2013 that incorporated a hydrologic landscape approach to estimate all components of the hydrologic system: surface runoff, base flow from groundwater, and interaction with atmospheric water (precipitation and evapotranspiration). This assessment was intended to complement other Federal and State investigations and provide foundational groundwater-related datasets in the Appalachian Plateaus. A regional Soil-Water-Balance model was constructed for a 160,000-square-mile study area that extended to the topographic divide of all streams originating outside but flowing into areas underlain by Appalachian Plateaus aquifers. The model incorporated soil, landscape, and climate variables to estimate an annual water budget for the 32-year period from 1980 to 2011 and was calibrated using base-flow data estimated by hydrograph separation techniques from 20 streamflow gaging stations across the study area. Over this period, an average of 47 inches per year (in/yr) of precipitation fell on Appalachian Plateaus aquifers. Simulations from the regional Soil-Water-Balance model indicate that only 19 percent of the precipitation or an average 9 in/yr recharged aquifers, and 19 percent resulted in surface runoff to streams. The remaining 62 percent, an average of 27 in/yr of water, was returned to the atmosphere via evapotranspiration. Because withdrawals from aquifers due to pumping equated to less than 1 percent of the water budget, differences in predevelopment and postdevelopment regional water budgets of the Appalachian Plateaus were minimal. Storage changes caused by filling of abandoned coal-mine aquifers and long-term differences in aquifer storage resulting from climate fluctuations constitute a small portion of the overall water budget. The percentage of precipitation that results in recharge, runoff, or evapotranspiration from the landscape varies annually by up to a factor of two depending on temporal changes in prevailing climate conditions and spatial changes in basin characteristics, precipitation patterns, and sources of atmospheric moisture over a large study area. A comparison of water-budget estimates from the regional Soil-Water-Balance model for a dry year (1988) and wet year (2004) showed that evapotranspiration accounts for most of the annual differences in precipitation. As a portion of annual precipitation, evapotranspiration ranged from 69 percent (dry year) to 52 percent (wet year), a range four times greater than the 15 percent (dry year) to 18 percent (wet year) range estimated for recharge. Evapotranspiration as a percentage of precipitation peaks during dry periods, whereas base flow and runoff tend to reach minimum values. During wet periods, this relationship is reversed and base flow and runoff as a percentage of precipitation generally peak while evapotranspiration percentages reach minimum values. Annual recharge in the Appalachian Plateaus reaches a maximum at near 20 percent of annual precipitation, regardless of the severity of wet conditions. Hydrograph separation data from 849 streamflow gaging stations in the study area were used to assess trends in streamflow, base flow, surface runoff, and base-flow index, or ratio of base flow to streamflow, in the Appalachian Plateaus for the period from 1930 to 2011. Annual data anomalies for each of the four variables were individually defined as the annual standard deviation from the mean at all 849 streamflow gaging stations. Annual data anomalies confirm the close relation of annual precipitation to both base flow and runoff components of streamflow, and both components increased during the period of analysis. Around 1970, conditions shifted streamflow from values generally below to above long-term means. At a regional scale, increases in base flow account for most of these observed increases in mean annual streamflow. The independence of the base-flow index to annual climate trends indicate that changes in the components of streamflow of the Appalachian Plateaus are probably in response to shifts in seasonal precipitation or widespread land-use practices. A subset of 77 index streamgages, defined as having 60 or more years of complete record between the years 1930 and 2011 with no more than 20 percent missing data, was selected to show spatial patterns of change in the water budget. Data from the index streamgages showed that the overall trends in base flow are dependent upon the period of evaluation. Long-term (1930–2011) increases in base flow were observed throughout the study area. For two shorter periods (1930–1969 and 1970–2011) trends in base flow were largely negative. In general, spatial patterns of change in streamflow, base flow, and runoff were mixed but generally consistent with prevailing climate patterns and land-use changes.

Alabama, Kentucky, Maryland, Ohio, Pennslyvania, V↗

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↗

Nitrogen load estimates from six nonpoint sources on Long Island, New York, from 1900 to 2019

Estimates of nitrogen loading from nonpoint sources on Long Island, New York, at or just below the land surface, are essential for assessing the current and future effects of nitrogen on the island’s drinking water and fresh and marine surface receiving waters. Annual estimates of nitrogen loading for the 120 years from 1900 to 2019 for major nonpoint nitrogen sources—septic systems, residential fertilizer, agricultural fertilizer, livestock waste, pet waste, and atmospheric deposition—were made by using a geographic information system to analyze, visualize, and process data sources, and format output data. This analysis provided spatial and temporal estimates of nitrogen loading derived from each nonpoint source at a 500- by 500-foot gridded resolution and represents the total mass of nitrogen applied on, or just below, the land surface annually from 1900 to 2019. These mass estimates are considered unattenuated as they do not reflect the various mechanisms of nitrogen loss, such as plant uptake, overland runoff, and chemical transformations in the soil and unsaturated zones that likely reduce the amount of nitrogen that reaches the water table. Island-wide and countywide summaries of the estimated nitrogen loading were analyzed to describe the long-term average nitrogen totals and the contributions from the six nonpoint sources. The island-wide average annual nitrogen load from 1900 to 2019 was 14.92 million kilograms (Mkg) nitrogen, which represents the aggregate of individual contributions from septic systems (4.15 Mkg), residential fertilizer (3.28 Mkg), agricultural fertilizer (3.19 Mkg), livestock waste (1.22 Mkg), pet waste (0.98 Mkg), and atmospheric deposition (2.10 Mkg). The island-wide average annual nitrogen load, normalized by area, was 4,100 kilograms nitrogen per square kilometer (kg N/km 2 ), which represents the aggregate of individual contributions from septic systems (1,100 kg N/km 2 ), residential fertilizer (910 kg N/km 2 ), agricultural fertilizer (880 kg N/km 2 ), livestock waste (340 kg N/km 2 ), pet waste (270 kg N/km 2 ), and atmospheric deposition (580 kg N/km 2 ).

New York↗

DGMETA (version 1)—Dissolved gas modeling and environmental tracer analysis computer program

DGMETA (Dissolved Gas Modeling and Environmental Tracer Analysis) is a Microsoft Excel-based computer program that is used for modeling air-water equilibrium conditions from measurements of dissolved gases and for computing concentrations of environmental tracers that rely on air-water equilibrium model results. DGMETA can solve for the temperature, salinity, excess air, fractionation of gases, or pressure/elevation of water when it is equilibrated with the atmosphere. Models are calibrated inversely using one or more measurements of dissolved gases such as helium, neon, argon, krypton, xenon, and nitrogen. Excess nitrogen gas, originating from denitrification or other sources, also can be included as a fitted parameter or as a separate calculation from the dissolved gas modeling results. DGMETA uses the air-water equilibrium models to separate measured concentrations of gases and isotopes of gases into components that are used for tracing water in the environment. DGMETA calculates atmospheric dry-air mole fractions (mixing ratios) for transient atmospheric gas tracers such as chlorofluorocarbons, sulfur hexafluoride, and bromotrifluoromethane (Halon-1301); and concentrations of tritiogenic helium-3 and radiogenic helium-4, which accumulate from the decay of tritium in water and the decay of uranium and thorium in rocks, respectively. Sample data can be graphed to identify applicable models of excess air, samples that contain excess nitrogen gas, or samples that have partially degassed, for example. Monte Carlo analysis of errors associated with dissolved gas equilibrium model results can be carried through computations of environmental tracer concentrations to provide robust estimates of error. In addition, graphical routines for separating helium sources using helium isotopes are included to refine estimates of tritiogenic helium-3 when terrigenic helium from mantle or crustal sources is present in samples. Environmental tracer concentrations and their errors computed from DGMETA can be used with other programs, such as TracerLPM (Jurgens and others, 2012), to determine groundwater ages and biogeochemical reaction rates. DGMETA also produces output files in a format that meets the U.S. Geological Survey open data requirements for documentation of model inputs and outputs. DGMETA is a versatile and adaptable program that allows users to add solubility data for new gases, modify the existing set of gas solubility data, modify the default set of gases used for modeling, choose calculations based on real (non-ideal) gas behavior, and select various concentration units for data entry and results to match laboratory reports and study objectives. DGMETA comes with a set of gases widely used in hydrology and oceanography and many gases include multiple solubilities from previous work. Seventeen dissolved gases are included in the default version of the program: noble gases (helium, neon, argon, krypton, and xenon), reactive gases (nitrogen, oxygen, methane, carbon dioxide, carbon monoxide, hydrogen, and nitrous oxide), and environmental tracers (chlorofluorocarbon-11, chlorofluorocarbon-12, chlorofluorocarbon-113, sulfur hexafluoride, and Halon-1301).

Techniques and Methods↗

Nitrate source indicators in ground water of the Scimitar Subdivision, Peters Creek area, Anchorage, Alaska

A combination of aqueous chemistry, isotopic measurement, and in situ tracers were used to study the possible nitrate sources, the factors contributing to the spatial distribution of nitrate, and possible septic system influence in the ground water in the Scimitar Subdivision, Municipality of Anchorage, Alaska. Two water types were distinguished on the basis of the major ion chemistry: (1) a calcium sodium carbonate water, which was associated with isotopically heavier boron and with chlorofluorocarbons (CFC's) that were in the range expected from equilibration with the atmosphere (group A water) and (2) a calcium magnesium carbonate water, which was associated with elevated nitrate, chloride, and magnesium concentrations, generally isotopically lighter boron, and CFC's concentrations that were generally in excess of that expected from equilibration with the atmosphere (group B water). Water from wells in group B had nitrate concentrations that were greater than 3 milligrams per liter, whereas those in group A had nitrate concentrations of 0.2 milligram per liter or less. Nitrate does not appear to be undergoing extensive transformation in the ground-water system and behaves as a conservative ion. The major ion chemistry trends and the presence of CFC's in excess of an atmospheric source for group B wells are consistent with waste-water influences. The spatial distribution of the nitrate among wells is likely due to the magnitude of this influence on any given well. Using an expanded data set composed of 16 wells sampled only for nitrate concentration, a significant difference in the static water level relative to bedrock was found. Well water samples with less than 1 milligram per liter nitrate had static water levels within the bedrock, whereas those samples with greater than 1 milligram per liter nitrate had static water levels near or above the top of the bedrock. This observation would be consistent with a conceptual model of a low-nitrate fractured bedrock aquifer that receives slow recharge from an overlying nitrate-enriched surficial aquifer.

Water-Resources Investigations Report↗

Interdecadal changes in the hydrometeorological regime of the Pacific Northwest and in the regional-to-hemispheric climate regimes, and their linkages

Selected hydrometeorological (HM) data for the Pacific Northwest, and regional-to-hemispheric atmospheric-circulation data and sea-surface temperature (SST) data for the North Pacific, are examined for three successive interdecadal periods that are subsets of the instrumental record in order to estimate if their characteristics have changed. The HM data included monthly precipitation totals for 50 sites in western Washington and 29 climate divisions of the Pacific Northwest, and streamflow averages for 112 sites in Washington, Oregon, and Idaho. The atmospheric data included the Southern Oscillation Index (SOI), an index of the Pacific/North America (PNA) circulation pattern, measures of the westerly and northerly components of geostrophic flow, and a subset of the Northern Hemisphere 700-millibar geopotential height data; this subset of 162 grid points includes the area between 15 degrees and 75 degrees N, 110 degrees W and 130 degrees E. The SST data are for a 5-degree grid between 20 degrees N and 60 degrees N, 110 degrees W and 130 degrees E. The atmospheric and SST data were examined not only because the HM regime is linked to regional-to-hemispheric climate regimes, but also to estimate the extent of climate shifts displayed by these data. Three subsets of the record were identified as pre-1947 (PRE), 1947-76 (BASE), and post-1976 (POST) water years, based on an analysis of the HM data and previous studies. For each subset, means were calculated for the water year (October-September), the runoff season (March-August), the winter season (October-February), and a baseflow season (August-September). Differences in means and in ratios of the means between the BASE period and the PRE and POST periods were examined for changes. Winter-season mean precipitation during both the PRE and POST periods was smaller than the BASE period, indicating a spatially consistent and distinct change in the HM regime during winter during the PRE and POST periods. For the runoff season, mean precipitation at most sites, in comparison to the BASE period, was smaller during the PRE period and larger during POST period, indicating that different HM regimes occurred during the runoff season for the PRE and POST periods. Water-year mean precipitation was less for both the PRE and POST periods because of decreases in winter-season precipitation; however, the water-year values for the POST period were not as small as those of the PRE period because more precipitation was concentrated in the runoff season. During both the PRE and POST periods, the mean water-year discharge was less than the BASE period for all but 15 of the 112 sites. Fourteen of the 15 sites were in a well-defined region (southern Idaho and southeastern Oregon), and 13 of the 14 had larger means only during the POST period. Winter-season streamflow was less for all but 11 sites during both PRE and POST periods; the largest decreases in the mean, more than 30 percent, were for an area in central Oregon. Except for the sites that had larger mean water-year discharge, runoff-season means also were less than those during the BASE period. Changes in the SOI and PNA index from the BASE period were generally similar to and consistent with those of the majority of the hydrologic data; dissimilarities were in well-defined regions and are attributed to the evolutionary nature of the regime shifts. Negative values of the SOI for the POST period were more persistent than those that have occurred during both the PRE and BASE periods. The changes in the PNA index and the geostrophic flow components during the POST period are consistent with drier and warmer conditions in the Pacific Northwest. The 700-millibar data display trends and differences between the BASE and POST periods; differences in composite anomalies for selected winter months between these periods show a well-defined PNA pattern. For many areas of the North Pacific, the record of SSTs shows a significant long-term trend

Water-Resources Investigations Report↗

MTBE concentrations in ground water in Pennsylvania

The distribution, concentrations, and detection frequency of methyl tert-butyl-ether (MTBE), a gasoline additive used in reformulated gasoline to improve air quality, were characterized in Pennsylvania's ground water. Two sources of MTBE in ground water, the atmosphere and storage-tank release sites, were examined. An analysis of atmospheric MTBE concentrations shows that MTBE detections (MTBE greater than or equal to 0.2 micrograms per liter) in ground water are more likely the result of storage-tank releases than atmospheric deposition. A comparison of 86 ground-water samples near storage-tank releases and 359 samples from ambient ground water (not thought to be affected by point-source releases of MTBE or BTEX compounds) shows that samples within about 0.5 mile downgradient of storagetank release sites have significantly greater MTBE detection frequency than ambient ground-water samples. Aquifer type, land use, and the use of Reformulated Gasoline (RFG) are associated with high rates of occurrence of MTBE in ground water in Pennsylvania. Ground-water samples from wells in crystalline-rock aquifers near storage- tank release sites have a significantly greater MTBE detection frequency (57 percent) compared to other aquifers. Samples from wells in urban areas have a significantly greater MTBE detection frequency compared to ambient samples in agricultural and forested areas. Samples from the RFG-use areas in the five southeastern counties of Pennsylvania have a significantly greater MTBE detection frequency than samples outside of the RFG-use area. MTBE detection frequency of samples near storage-tank release sites in the RFG-use area (45 percent) are significantly greater than ambient samples in the RFG-use area.

Pennsylvania↗