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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↗

Permeability of covers over low-level radioactive-waste burial trenches, West Valley, Cattaraugus County, New York

Among the facilities at the Western New York Nuclear Service Center, near the hamlet of West Valley in the northern part of Cattaraugus County, N.Y., is a State-licensed burial ground for commercial low-level radioactive wastes. The 11-acre burial ground contains a series of trenches excavated in a silty-clay till of low permeability that contains scattered pods of silt, sand, and gravel. Gas pressure in the unsaturated parts of radioactive waste burial trenches responds to fluctuations in atmospheric pressure. Measurements of atmospheric pressure and the differential pressure between the trench gas and the atmosphere on several dates in 1977-78 were used to calculate hydraulic conductivity of the reworked silty-clay till that covers the trenches. Generally the hydraulic conductivity of covers over trenches that had a history of rapidly rising water levels are higher, at least seasonally, than covers over trenches in which the water level remained low. This supports the hypothesis that recharge occurs through the cover, presumably through fractures caused by desiccation and (or) subsidence. Hydraulic conductivities of the cover as calculated from gas- and air-pressure measurements at several trenches were 100 to 1,000 times greater than those calculated from the increase in water levels in the trenches. This difference suggests that the values obtained from the air- and gas-pressure measurements need to be adjusted and at present are not directly usable in ground-water flux calculations. The difference in magnitude of values may be caused by rapidly decreasing hydraulic conductivity during periods of recharge or by the clogging of fractures with sediment washed in by runoff. (USGS)

Water-Resources Investigations Report↗

Chemical and physical characteristics of precipitation at selected sites in Florida

Infrequent sampling of precipitation in Florida has been conducted by the U.S. Geological Survey since 1965. A summary of the historical data from 24 sites throughout Florida indicate that the principal ionic composition of atmospheric precipitation samples is calcium-sodium and bicarbonate-chloride with an average specific conductance of 32 micromhos per centimeter at 25 C. Historically, much of the sampling focused on primary nutrients and selected trace elements. Historical data indicate that nitrogen and phosphorus concentrations averaged 1.1 and 0.1 milligrams per liter, respectively. The limited trace metal data indicate that motor-vehicle activity may have a significant impact on local precipitation quality. Lead, for example, was measured in concentrations of as much as 2,400 micrograms per liter in samples collected in a highly populated, commerical area in south Florida. Statistical testing indicated that most major inorganic constituents, primary nutrients, and trace metals were significantly differnet among the sampling sites. The pH data indicated a range of about 5.0 to 7.0, but only limited pH data were collected and analyzed at the historical sites in such a timely manner as to represent pH conditions of the atmospheric precipitation during active rainfall. A critical review of the historical data suggested that while they may reflect local atmospheric quality conditions they likely do not define baseline conditions from a regional perspective. The application of these data were generally limited regarding regional extrapolation due to lack of standardization of sampling techniques, variable methods of sample preservation, nonuniform sampling intervals, variable sample sizes, and different periods of record. (USGS)

Water-Resources Investigations Report↗

Restoring dryland water cycles for precipitation feedback and climate stability; a review

Drylands across the globe are experiencing intensifying water scarcity, land degradation, and hydroclimatic extremes. This review integrates evidence from multidecadal field studies, hydrologic monitoring, geomorphic and ecological assessments, remote sensing, and land–atmosphere science to evaluate how restoration influences key components of the terrestrial water cycle. Low-tech natural infrastructure in dryland streams (NIDS)—including check dams, leaky weirs, one-rock dams, and gabions—has emerged as a promising but under-synthesized nature-based solution for restoring hydrologic function in these environments. We describe the mechanisms through which these interventions modify runoff detention, infiltration, sediment and alluvial storage, shallow-groundwater recharge, vegetation recovery, and surface-energy partitioning, and we summarize outcomes across diverse dryland settings. Findings consistently show increased water residence time, enhanced soil-moisture storage, expanded riparian vegetation, extended flow duration, and shifts toward greater latent-heat flux—producing localized cooling and strengthened ecohydrological feedbacks. Building on these localized effects, we articulate a hypothesis that links the spatial extent of restoration, the density of NIDS per unit drainage area, and the magnitude of the latent-to-sensible-heat contrast generated by wetter post-rainfall conditions. Specifically, we hypothesize that when NIDS are implemented at densities permitted by topography and across areas large enough to maintain elevated soil moisture after storm events, the resulting increases in latent heat flux, surface cooling, and boundary-layer moistening may enhance moisture convergence and boundary-layer development, potentially increasing the likelihood or stability of convective precipitation, analogous to how reductions in these processes have contributed to regional drought intensification. These land–atmosphere feedbacks remain untested at scale but represent an important research Frontier. By integrating hydrologic, geomorphic, ecological, and atmospheric perspectives, this review provides a comprehensive framework for considering how low-tech, landscape-scale interventions can strengthen watershed resilience and contribute to climate-relevant nature-based solutions.

Arizona↗

Long-term trends in regional wet mercury deposition and lacustrine mercury concentrations in four lakes in Voyageurs National Park

Although anthropogenic mercury (Hg) releases to the environment have been substantially lowered in the United States and Canada since 1990, concerns remain for contamination in fish from remote lakes and rivers where atmospheric deposition is the predominant source of mercury. How have aquatic ecosystems responded? We report on one of the longest known multimedia data sets for mercury in atmospheric deposition: aqueous total mercury (THg aq ), methylmercury (MeHg aq ), and sulfate from epilimnetic lake-water samples from four lakes in Voyageurs National Park (VNP) in northern Minnesota; and total mercury (THg) in aquatic biota from the same lakes from 2001–2018. Wet Hg deposition at two regional Mercury Deposition Network sites (Fernberg and Marcell, Minnesota) decreased by an average of 22 percent from 1998–2018; much of the decreases occurred prior to 2009, with relatively flat trends since 2009. In the four VNP lakes, epilimnetic MeHg aq concentrations declined by an average of 44 percent and THg aq by an average of 27 percent. For the three lakes with long-term biomonitoring, temporal patterns in biotic THg concentrations were similar to patterns in MeHg aq concentrations; however, biotic THg concentrations declined significantly in only one lake. Epilimnetic MeHg aq may be responding both to a decline in atmospheric Hg deposition as well as a decline in sulfate deposition, which is an important driver of mercury methylation in the environment. Results from this case study suggest that regional- to continental-scale decreases in both mercury and sulfate emissions have benefitted aquatic resources, even in the face of global increases in mercury emissions.

Minnesota↗

Potential underestimation of satellite fire radiative power retrievals over gas flares and wildland fires

Fire Radiative Power (FRP) is related to fire combustion rates and is used to quantify the atmospheric emissions of greenhouse gases and aerosols. FRP over gas flares and wildfires can be retrieved remotely using satellites that observe in shortwave infrared (SWIR) to middle infrared (MIR) wavelengths. Heritage techniques to retrieve FRP developed for wildland fires using the MIR 4 μm radiances have been adapted for the hotter burning gas flares using the SWIR 2 μm observations. Effects of atmosphere, including smoke and aerosols, are assumed to be minimal in these algorithms because of the use of longer than visual wavelengths. Here we use Moderate Resolution Imaging Spectroradiometer (MODIS), Visible Infrared Imaging Radiometer Suite (VIIRS) and Landsat 8 observations acquired before and during emergency oil and gas flaring in eastern Saudi Arabia to show that dark, sooty smoke affects both 4 μm and 2 μm observations. While the 2 μm observations used to retrieve gas FRP may be reliable during clear atmospheric conditions, performance is severely impacted by dark smoke. Global remote sensing-based inventories of wildfire and gas flaring need to consider the possibility that soot and dark smoke can potentially lead to an underestimation of FRP over fires.

Remote Sensing↗

Characterizing the scale of regional landslide triggering from storm hydrometeorology

Rainfall strongly affects landslide triggering; however, understanding how storm characteristics relate to the severity of landslides at the regional scale has thus far remained unclear, despite the societal benefits that would result from defining this relationship. As mapped landslide inventories typically cover a small region relative to a storm system, here we develop a dimensionless index for landslide-inducing rainfall, A * , based on extremes of modeled soil water relative to its local climatology. We calibrate A * using four landslide inventories, comprising over 11 000 individual landslides over four unique storm events, and find that a common threshold can be applied to estimate regional shallow-landslide-triggering potential across diverse climatic regimes in California (USA). We then use the spatial distribution of A * , along with topography, to calculate the landslide potential area (LPA) for nine landslide-inducing storm events over the past 20 years, and we test whether atmospheric metrics describing the strength of landfalling storms, such as integrated water vapor transport, correlate with the magnitude of hazardous landslide-inducing rainfall. We find that although the events with the largest LPA do occur during exceptional atmospheric river (AR) storms, the strength of landfalling atmospheric rivers does not scale neatly with landslide potential area, and even exceptionally strong ARs may yield minimal landslide impacts. Other factors, such as antecedent soil moisture driven by storm frequency and mesoscale precipitation features within storms, are instead more likely to dictate the patterns of landslide-generating rainfall throughout the state.

California↗

Tidal Wetlands and Estuaries

1. The top 1 m of tidal wetland soils and estuarine sediments of North America contains 1,886 ± 1046 teragrams of carbon (Tg C). [High confidence, Very likely] 2. Soil carbon accumulation rate (i.e., sediment burial) in North American tidal wetlands is currently 9 ± 5 Tg C per year and estuarine carbon burial is 5 ± 3 Tg C per year. [High confidence, Likely] 3. The lateral flux of carbon from tidal wetlands to estuaries is 16 ± 10 Tg C per year for North America. [Low confidence, Likely] 4. In North America, tidal wetlands remove 27 ± 13 Tg C per year from the atmosphere, estuaries outgas 10 ± 10 Tg C per year to the atmosphere, and the net uptake by the combined wetland-estuary system is 17 ± 16 Tg C per year. [Low confidence, Likely] 5. Research and modeling needs are greatest for understanding responses to accelerated sea level rise, mapping tidal wetland and estuarine extent and quantification of CO2 and CH4 exchange with the atmosphere, especially in large, under-sampled, and rapidly changing regions. [High confidence, Likely] Note: Confidence levels are provided as appropriate for quantitative, but not qualitative, Key Findings and statements.

Book chapter↗

Contributions of nitrogen to the Barnegat Bay-Little Egg Harbor Estuary: Updated loading estimates

Based on the most recent and most accurate data available through 2008, the total load of nitrogen to the Barnegat Bay‐Little Egg Harbor (BB‐LEH) estuary from the most substantial sources (surface water, including surface‐water discharge and direct storm runoff; ground‐water discharge; and atmospheric deposition) is estimated to be 650,000 kilograms of nitrogen per year (kg N/yr). Surface water contributes 66 percent (431,000 kg N/yr), direct ground‐ water discharge accounts for 12 percent (78,000 kg N/yr), and atmospheric deposition accounts for 22 percent (141,000 kg N/yr). This new loading estimate was compared to a previously published estimate produced by using similar methodology but less current data through 1997. Findings of the present study include a substantially lower estimate of atmospheric deposition of nitrogen to the estuary compared to the previous estimate. The study results also offer further support of the relation between land use and nitrogen levels, and indicate that the Toms and Metedeconk River basins account for more than 60 percent of the nitrogen load to the estuary from surface‐water discharge. Differences between the two estimates can be attributed to both the use of more accurate and more recent data in the revised estimate, and actual changes in the magnitude of nitrogen loads from various sources. Gaps in available water‐quality and hydrologic data are documented, and additional analysis and monitoring that may improve the reliability of future nitrogen loading estimates are presented.

New Jersey↗

Hydrologic influence on methane and carbon dioxide dynamics at two north-central Minnesota lakes

Annual emissions of (CH4 + CO2) to the atmosphere were proportional to net hydrologic inputs of C, mostly by groundwater, at two lakes in the Shingobee River watershed in north-central Minnesota. Williams Lake (WL), a closed basin lake near the top of the watershed, had a hydraulic residence time of 2-4 yr and groundwater exchange of about +2 mol dissolved inorganic carbon (DIC) and -0.1 mol dissolved organic carbon (DOC) m-2 lake area yr-1. The Shingobee River flows through Shingobee Lake (SL) that had a hydraulic residence of 0.3-0.4 yr and received net groundwater plus surface-water inputs of +5.3 to +7.3 mol DIC and fewer than +1.3 mol (DOC + particulate organic carbon) m-2 yr-1. Approximately 60-80% of net annual C input to SL was from groundwater. Lake storage of CH4 and CO2 was greatest in late winter, with maximum emissions to the atmosphere immediately following ice melt. The lakes emitted CH4 continuously during open water, having annual losses of -1.6 mol CH4 m-2 yr-1 at WL and -1.9 mol CH4 m-2 yr-1 at SL. Although the WL epilimnion was CO2 depleted throughout summer, net annual CO2 exchange with the atmosphere was near zero because springtime emission offset summertime uptake. CO2 supersaturation resulted in emission of -8.0 mol CO2 m-2 yr-1 at SL.

Limnology and Oceanography↗

Vegetation sensitivity to global anthropogenic carbon dioxide emissions in a topographically complex region

Anthropogenic increases in atmospheric carbon dioxide (CO2) concentrations may affect vegetation distribution both directly through changes in photosynthesis and water-use efficiency, and indirectly through CO2-induced climate change. Using an equilibrium vegetation model (BIOME4) driven by a regional climate model (RegCM2.5), we tested the sensitivity of vegetation in the western United States, a topographically complex region, to the direct, indirect, and combined effects of doubled preindustrial atmospheric CO2 concentrations. Those sensitivities were quantified using the kappa statistic. Simulated vegetation in the western United States was sensitive to changes in atmospheric CO2 concentrations, with woody biome types replacing less woody types throughout the domain. The simulated vegetation was also sensitive to climatic effects, particularly at high elevations, due to both warming throughout the domain and decreased precipitation in key mountain regions such as the Sierra Nevada of California and the Cascade and Blue Mountains of Oregon. Significantly, when the direct effects of CO2 on vegetation were tested in combination with the indirect effects of CO2-induced climate change, new vegetation patterns were created that were not seen in either of the individual cases. This result indicates that climatic and nonclimatic effects must be considered in tandem when assessing the potential impacts of elevated CO2 levels.

Global Biogeochemical Cycles↗