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John W. Clune

Publications and source records attributed to John W. Clune.

15 recordsLinked to original sources

Sediment response to stream restoration in an agricultural watershed

Despite widespread implementation of stream restoration there is limited research of its effectiveness in impaired agricultural settings. To quantify the effects of stream restoration on sediment load, we investigated erosion and deposition along 9 stream reach sites (4 restored, 4 unrestored, and 1 downstream) in Turtle Creek, Pennsylvania, United States - a representative agricultural subbasin of the Chesapeake Bay. These stream restoration projects had the goal of reducing sediment load primarily by installing log structures and regrading streambanks in order to stabilize streambanks and reconnect floodplains. Floodplain and streambank sediment fluxes were quantified over a 3-year period through repeated measurement of clay pads and pins and measurement of sediment bulk density. Uncrewed aerial imagery was collected at 3 of the sites, then processed using structure from motion (SfM) to create high-resolution digital elevation models. Terrain analysis enabled three-dimensional understanding of the generality of the specific field flux measurement locations to the larger stream reach. Restored sites on average had deposition on streambanks compared to streambank erosion along unrestored sites, and approximately two times greater floodplain deposition than unrestored sites. Overall, restored stream had an average seven-fold increase in the net balance (sum of streambank and floodplain) of sediment flux, a 81.2 kg/m/yr increase in retention, compared to unrestored stream. The measured larger streambed particle size distribution (D 50 ) in restored streams also suggests additional improvements to instream habitat quality. Terrain analysis confirmed that the field-based measurements were representative of the larger reach. These results indicate that stream restoration in agricultural watersheds using less-engineered designs can reduce sediment loading and improve stream habitat and health goals.

Pennsylvania↗

Tracking status and trends in seven key indicators of river and stream condition in the Chesapeake Bay watershed

Freshwater streams and rivers are recognized as vital habitats within the Chesapeake Bay watershed, which has been undergoing extensive restoration efforts for more than 30 years. Resource managers need to understand stream and river condition and how these conditions are changing over time to determine whether regional long-term restoration and conservation goals are being met. The objective of this report was to document the spatial and temporal variability of conditions for seven indicators of river and stream health across the nontidal Chesapeake Bay watershed. The framework for the U.S. Geological Survey’s Nontidal Network (NTN), a network of more than 100 nutrient and suspended sediment monitoring locations, was extended to assess conditions for six additional indicators of stream health: temperature, salinity, toxic contaminants, streamflow, hydromorphology, and biological aquatic communities. For each indicator, the latest available data from multiple sources were compiled and harmonized, and key metrics were identified to describe indicator conditions across space and time. A status condition was defined for each indicator to describe overall spatial variability in recent condition, and trend analyses were used to describe changes in each indicator metric over time. The analysis revealed clear differences in spatial and temporal data coverage across the seven indicators, so individual indicator trend analyses were not constrained to a common time interval. However, a status snapshot was conducted across all indicators for the 2015–17 period to simultaneously explore spatial variability across all indicators. The status snapshot highlighted general degraded conditions across multiple indicators in large metropolitan regions, such as the Baltimore–Washington, D.C., metropolitan area. Regression analysis between indicator status metrics and major land cover for the sites suggest urbanization as a potential driver of degraded conditions for many of the indicator metrics, including total phosphorus, salinity, temperature, high-flow frequency, and metrics of habitat and biological assemblage quality. A final analysis exploring the spatial representation of each indicator network showed that some indicator monitoring networks did not cover certain settings, such as small watersheds. These results provided an initial assessment of stream health status and trends and will continue to be leveraged to describe conditions across the Chesapeake Bay watershed to help inform local and regional management decisions. These results also highlighted the need for improved coordination among monitoring organizations to support long-term multi-indicator monitoring and assessment.

Chesapeake Bay watershed↗

Complex hydrology and variability of nitrogen sources in a karst watershed

Streams draining karst areas with rapid groundwater transit times may respond relatively quickly to nitrogen reduction strategies, but the complex hydrologic network of interconnected sinkholes and springs is challenging for determining the placement and effectiveness of management practices. This study aims to inform nitrogen reduction strategies in a representative agricultural karst setting of the Chesapeake Bay watershed (Fishing Creek watershed, Pennsylvania) with known elevated nitrate contamination and a previous documented groundwater residence time of less than a decade. During baseflow conditions, streamflow did not increase with drainage area. Headwaters and the main stem lost substantial flow to sinkholes until eventually discharging along large springs downstream. Seasonal hydrologic conditions shift the flow and nitrogen load spatially among losing and gaining stream sections. A compilation of nitrogen source inputs with the geochemistry and the pattern of enrichment of δ 15 N and δ 18 O suggest that the nitrogen in streams and springs during baseflow represents a mixture of manure, fertilizer, and wastewater sources with low potential for denitrification. The pH and calcite saturation index increased along generalized flow paths from headwaters to springs and indicate shorter groundwater residence times in baseflow during the spring versus summer. Given the substantial investment in management practices, fixed monitoring sites could incorporate synoptic water sampling to properly monitor long-term progress and help inform management actions in karst watersheds. Although karst watersheds have the potential to respond to nitrogen reduction strategies due to shorter groundwater residence times, high nitrogen inputs, effectiveness of conservation practices, and release of legacy nutrients within the karst cavities could confound progress of water quality goals.

Pennsylvania↗

Evaluating water-quality trends in agricultural watersheds prioritized for management-practice implementation

Many agricultural watersheds rely on the voluntary use of management practices (MPs) to reduce nonpoint source nutrient and sediment loads; however, the water-quality effects of MPs are uncertain. We interpreted water-quality responses from as early as 1985 through 2020 in three agricultural Chesapeake Bay watersheds that were prioritized for MP implementation, namely, the Smith Creek (Virginia), Upper Chester River (Maryland), and Conewago Creek (Pennsylvania) watersheds. We synthesized patterns in MPs, climate, land use, and nutrient inputs to better understand factors affecting nutrient and sediment loads. Relations between MPs and expected water-quality improvements were not consistently identifiable. The number of MPs increased in all watersheds since the early 2010s, but most monitored nutrient and sediment loads did not decrease. Nutrient and sediment loads increased or remained stable in Smith Creek and the Upper Chester River. Sediment loads and some nutrient loads decreased in Conewago Creek. In Smith Creek, a 36-year time-series model suggests that changes in manure affected flow-normalized total nitrogen loads. We hypothesize that increases in nutrient applications may overshadow some expected MP effects. MPs might have stemmed further water-quality degradation, but improvements in nutrient loads may rely on reducing manure and fertilizer applications. Our results highlight the importance of assessing MP performance with long-term monitoring-based studies.

Journal of the American Water Resources Assocation↗

Legacy sediment as a potential source of orthophosphate: Preliminary conceptual and geochemical models for the Susquehanna River, Chesapeake Bay watershed, USA

Nutrient pollution from agriculture and urban areas plus acid mine drainage (AMD) from legacy coal mines are primary causes of water-quality impairment in the Susquehanna River, which is the predominant source of freshwater and nutrients entering the Chesapeake Bay. Recent increases in the delivery of dissolved orthophosphate (PO 4 ) from the river to the bay may be linked to long-term increases in pH, decreased acidity of precipitation, and decreased acidity, iron, and aluminum loading from widespread AMD. Since the 1950s, baseline pH increased from ~6.5 to ~8 in the West Branch and “North Branch” of the Susquehanna River, which drain bituminous and anthracite coalfields of Pennsylvania. A current baseline pH of ~8 and daily maxima exceeding 9 have been documented along the lower Susquehanna River. In response to improved river quality, bioavailable PO 4 now may be released into solution from legacy sediment that has filled major impoundments in lower reaches of the river. At typical pH (5–8) of natural water, aqueous PO 4 species tend to be adsorbed by hydrous iron, aluminum, and manganese oxides that coat soil and sediment particles; however, PO 4 may be substantially desorbed at pH >8. We created a geochemical model that simulates equilibrium aqueous/solid distributions of PO 4 as pH and other solution characteristics change. Considering current conditions in the lower Susquehanna River, the model demonstrates potential for extensive release of adsorbed PO 4 at pH >8. Empirical data from laboratory experiments corroborate model results. The transfer of PO 4 into the water column may increase algae growth, which removes CO 2 and drives pH to higher values, facilitating additional PO 4 release and exacerbating the potential for harmful algal blooms. Thus, legacy sediment is a currently unquantified source of PO 4 that warrants consideration by resource managers and programs collaborating to reduce phosphorus loads to the bay and similar settings worldwide.

Chesapeake Bay watershed↗

Your land, your water—Using research to guide conservation practices on local farms in the Chesapeake Bay watershed

Agricultural lands are an important part of the economy and heritage of the Chesapeake Bay watershed and are a focus of conservation activities. Streams and rivers around farms provide communities with drinking water and recreational opportunities, but these local benefits can be impaired by elevated nutrient and sediment concentrations. Compared to inputs from the atmosphere, wastewater, and urban and suburban areas, agricultural lands are the largest source of nutrients and sediment in many Chesapeake Bay streams. Farmers are voluntary conservation partners and have an important role in improving water-quality conditions. This fact sheet summarizes recent scientific insights from the U.S. Geological Survey (USGS) that can help farmers use conservation practices and their knowledge of local site conditions to achieve cleaner water.

Chesapeake Bay watershed↗

Tracking status and trends in seven key indicators of stream health in the Chesapeake Bay watershed

“The Bay Connects us, the Bay reflects us” writes Tom Horton in the book “Turning the Tide—Saving the Chesapeake Bay”. The Chesapeake Bay watershed contains the largest estuary in the United States. The watershed stretches north to Cooperstown, New York, south to Lynchburg and Virginia Beach, Virginia, west to Pendleton County, West Virginia, and east to Seaford, Delaware, and Scranton, Pennsylvania. The watershed is more than 64,000 square miles that contain 150 major rivers and streams, hereafter referred to collectively as streams, that total more than 100,000 miles in length. The watershed contains thousands of smaller creeks and tributaries, large numbers of plants and animals, and, in 2020, more than 18.4 million people. As changes occur in population, land use, and climate within the watershed, so too do the diversity and health of the Bay's ecosystems.

Chesapeake Bay watershed↗

Nitrogen in the Chesapeake Bay watershed—A century of change, 1950–2050

Foreword Sustaining the quality of the Nation’s water resources and the health of our diverse ecosystems depends on the availability of sound water-resources data and information to develop effective, science-based policies. Effective management of water resources also brings more certainty and efficiency to important economic sectors. Taken together, these actions lead to immediate and long-term economic, social, and environmental benefits that will make a difference to the lives of the almost 400 million people projected to live in the United States by 2050. The Chesapeake Bay is the largest and most productive estuary in the United States and is a vital environmental and economic resource. Approximately half of the water volume of the Chesapeake Bay originates from streams and rivers that drain the 64,243 mi 2 Chesapeake Bay watershed. The Bay and its tributaries have been degraded by excessive nutrients, such as nitrogen, from contributing watersheds. Inputs of nitrogen to the Bay lead to increased algal growth, decreased dissolved oxygen, and declining fisheries. In 2000, the Chesapeake Bay was listed as impaired under the Clean Water Act and Total Maximum Daily Loads (TMDLs) for nutrients and sediment have been established to assist with management actions aimed at nutrient reductions. Effective nutrient management requires an understanding of past, present, and future nutrient sources, fate, and transport in the watershed. The Chesapeake Bay community has been a pioneer in science, management, and regulation to improve water quality. Factors like climate, hydrology, source inputs, and management controls play a vital role in determining the delivery and magnitude of nitrogen inputs to the Bay. Science in the form of monitoring data, predictive tools, and interpretive reports can help inform decisions to better balance the use and control of nitrogen in coastal areas. The findings in this report can contribute to effective management of the Bay and its watershed by providing a synthesis of the understanding of how human activities and environmental change in the watershed in the past, present, and future will influence the export of nitrogen to the Bay. We hope this publication will provide you with insights and information to meet your water resource needs and will foster increased civilian awareness and involvement in the protection and restoration of our Nation’s waters. The information in this report is intended primarily for those interested or involved in resource management and protection, conservation, regulation, and policymaking at the regional and national levels.

Chesapeake Bay watershed↗

Groundwater quality in relation to drinking water health standards and geochemical characteristics for 54 domestic wells in Clinton County, Pennsylvania, 2017

Despite the reliance on groundwater by approximately 2.4 million rural Pennsylvania residents, publicly available data to characterize the quality of private well water are limited. As part of a regional effort to characterize groundwater in rural areas of Pennsylvania, samples from 54 domestic wells in Clinton County were collected and analyzed in 2017. The samples were evaluated for a wide range of constituents and compared to drinking-water health standards and geochemical characteristics. The sampled wells were completed to depths ranging from 46 to 500 feet in bedrock that was of predominantly sandstone, shale, or carbonate lithology. Results of this study show that the sampled groundwater quality in Clinton County generally met most drinking-water standards that apply to public water supplies. However, a percentage of samples exceeded drinking-water maximum contaminant levels (MCLs) for total coliform bacteria (57.4 percent), Escherichia coli ( E. coli ) (25.9 percent), nitrate (1.9 percent), and arsenic (1.9 percent); and secondary maximum contaminant levels (SMCLs) for pH (31.5 percent), manganese (29.6 percent), iron (13 percent), total dissolved solids (7.4 percent), aluminum (1.9 percent), and chloride (1.9 percent). Sodium concentrations exceeded the U.S. Environmental Protection Agency drinking-water advisory recommendation in 16.7 percent of the samples. Radon-222 activities exceeded the proposed drinking-water standard of 300 picocuries per liter (pCi/L) in 59.3 percent of the samples. The only volatile organic compounds (VOCs) detected were acetone and methyl ethyl ketone in two separate samples; neither constituent exceeded drinking-water standards. Higher median nitrate concentrations were found in the carbonate (3.26 milligrams per liter [mg/L]) versus shale (less than 0.04 mg/L) and sandstone (0.27 mg/L) aquifer subsets. Most of the elevated nitrate concentrations were associated with E. coli detections in the carbonate aquifers, where transmissive bedrock can facilitate groundwater contamination by human activities at the land surface. The median pH of groundwater from the sandstone aquifers (6.53) was less than those for the shale aquifers (7.31) and carbonate aquifers (7.43). Generally, the lower pH samples had greater potential for elevated concentrations of dissolved metals, including beryllium, copper, lead, nickel, and zinc, whereas the higher pH samples had greater potential for elevated concentrations of total dissolved solids, sodium, fluoride, boron, and uranium. Near-neutral samples (pH 6.5 to 7.5) had greater hardness and alkalinity concentrations than other samples with pH outside this range. Many samples from the shale or sandstone aquifers, particularly those with pH less than 6.5, were identified as having serious potential corrosivity based on the combination of the calcite saturation index and the chloride to sulfate mass ratio; however, none of the samples from the carbonate aquifers was identified as seriously corrosive. Groundwater from 3.7 percent of the wells had concentrations of methane greater than the Pennsylvania action level of 7 mg/L, and 48 of the 54 wells (88.9 percent) had detectable concentrations of methane greater than the 0.0002 mg/L detection limit. Greater methane concentrations were found more frequently in groundwater sampled from the shale aquifers than the carbonate or sandstone aquifers in the study area. Most of the samples containing elevated methane (greater than 0.2 mg/L) were located outside the area of the Appalachian Plateaus. The elevated concentrations of methane generally were associated with suboxic groundwater (dissolved oxygen less than 0.5 mg/L) that had near-neutral to alkaline pH and were correlated with concentrations of iron, manganese, ammonia, sodium, lithium, barium, fluoride, and boron. The stable carbon and hydrogen isotopic compositions of methane in two of four samples analyzed for isotopes were consistent with compositions reported for mud-gas logging samples from gas-bearing geologic units (thermogenic gas) in the Appalachian Plateaus region, whereas two others were consistent with methane of microbial origin or a mixture of microbial and thermogenic gas. Forty-two percent of samples had chloride concentrations greater than 20 mg/L with variable bromide concentrations. Corresponding chloride/bromide ratios are consistent with low-bromide sources such as road-deicing salt and septic effluent or animal waste, or, in a few cases, high-bromide brine. Brines characterized by relatively high bromide are naturally present in deeper parts of the regional groundwater system and, in some cases, may be mobilized by gas drilling. The chloride, bromide, and other constituents in road-deicing salt or brine solutions tend to be diluted by mixing with fresh groundwater in shallow aquifers used for water supply. One of the four groundwater samples with methane concentrations greater than 4 mg/L had chloride and bromide concentrations and a chloride/bromide ratio that indicates mixing with a salinity source such as road-deicing salt, whereas the chloride and bromide concentrations and ratios for the other three high-methane samples indicate mixing with a small amount of brine (0.03 percent or less). In two other eastern Pennsylvania county studies where gas drilling is absent, groundwater with comparable chloride/bromide ratios, bromide, and chloride concentrations plus other element associations have been reported. Additional sampling and analysis, such as isotopic analysis of the dissolved gas, fracture analysis, and more detailed evaluation of surrounding land uses, may be warranted to better understand the origin of the methane and brine constituents in groundwater at specific locations.

Pennsylvania↗

Drinking water health standards comparison and chemical analysis of groundwater for 72 domestic wells in Bradford County, Pennsylvania, 2016

Pennsylvania has the second highest number of residential wells of any state in the Nation with approximately 2.4 million residents that depend on groundwater for their domestic water supply. Despite the widespread reliance on groundwater in rural areas of the state, publicly available data to characterize the quality of private well water are limited. In Bradford County, more than half of the residents use groundwater from private domestic-supply wells as their primary drinking source. The quality of private well water is influenced by the regional and local setting, including the surrounding soil, geology, land use, household plumbing, and well construction. The groundwater used for domestic water supply in Bradford County is obtained primarily from shallow bedrock and from unconsolidated (glacial) deposits that overlie the bedrock. Historical land use has been predominately forested, agricultural, and residential, but more recently unconventional oil/gas development has been distributed throughout the landscape. Pennsylvania is one of only two states in the Nation without statewide water-well construction standards. To better assess the quality of groundwater used for drinking water supply in Bradford County, data for 72 domestic wells were collected and analyzed for a wide range of constituents that could be evaluated in relation to drinking water health standards, geology, land use, and other environmental factors. Groundwater samples were collected from May through August 2016 and analyzed for physical and chemical properties, including major ions, nutrients, trace elements, volatile organic compounds, ethylene and propylene glycol, alcohols, gross-alpha/beta-particle activity, uranium, radon-222, and dissolved gases. A subset of samples was analyzed for radium isotopes (radium-226 and -228) and for the isotopic composition of methane. This study was conducted by the U.S. Geological Survey in cooperation with the Northern Tier Regional Planning and Development Commission and is part of a regional effort to characterize groundwater in rural areas of Pennsylvania. Results of the 2016 study show that groundwater quality generally met most drinking-water standards. However, a percentage of samples failed to meet maximum contaminant levels (MCLs) for total coliform bacteria (49.3 percent), Escherichia coli (8.5 percent), barium (2.8 percent), and arsenic (2.8 percent); and secondary maximum contaminant levels (SMCL) for sodium (48.6 percent), manganese (30.6 percent), gross alpha and beta activity (16.7 percent), iron (11.1 percent), pH (8.3 percent), total dissolved solids (5.6 percent), chloride (1.4 percent), and aluminum (1.4 percent). Radon-222 activities exceeded the proposed drinking-water standard of 300 picocuries per liter (pCi/L) in 70.4 percent of the samples. There were no exceedances of drinking water health standards for any volatile organic compounds, and the only detections were for three trihalomethanes in one sample. The pH of the groundwater had a large influence on chemical characteristics and ranged from 6.18 to 9.31. Generally, the higher pH samples had higher potential for elevated concentrations of several constituents, including total dissolved solids, sodium, lithium, chloride, fluoride, boron, arsenic, and methane. For the Bradford County well-water samples, calcium/bicarbonate type waters were most abundant, with others classified as sodium/bicarbonate or mixed water types including calcium-sodium/bicarbonate, calcium-sodium/bicarbonate-chloride, sodium/bicarbonate-chloride, sodium/bicarbonate-sulfate, or sodium/chloride types. Six principal components (pH, redox, hardness, chloride-bromide, strontium-barium, and molybdenum-arsenic) explained nearly 78.3 percent of the variance in the groundwater dataset. Groundwater from 12.5 percent of the wells had concentrations of methane greater than the Pennsylvania action level of 7 milligrams per liter (mg/L); detectable methane concentrations ranged from 0.01 to 77 mg/L. In addition, low levels of ethane (as much as 0.13 mg/L) were present in seven samples with the highest methane concentrations. The isotopic composition of methane in five of these groundwater samples was consistent with the isotopic compositions reported for mud-gas logging samples from these geologic units and a thermogenic source. Isotopic composition from a sixth sample suggested the methane in that sample may be of microbial origin. Well-water samples with the higher methane concentrations also had higher pH values and elevated concentrations of sodium, lithium, boron, fluoride, arsenic, and bromide. Relatively elevated concentrations of some other constituents, such as barium and chloride, commonly were present in, but not limited to, those well-water samples with elevated methane. Four of the six groundwater samples with the highest methane concentrations had chloride/bromide ratios that indicate mixing with a small amount of brine (0.02 percent or less) similar in composition to those reported for gas and oil well brines in Pennsylvania. In several other eastern Pennsylvania counties where gas drilling is absent, groundwater with comparable chloride/bromide ratios and chloride concentrations have been reported, implying a potential natural source of brine. Most of Bradford County well-water samples have chloride concentrations less than 20 mg/L, and those with higher chloride concentrations have chloride/bromide ratios that indicate anthropogenic sources (such as road-deicing salt and septic effluent) or brine. Brines that are naturally present may originate from deeper parts of the aquifer system, whereas anthropogenic sources are more likely to affect shallow groundwater because they occur on or near the land surface. The available data for this study indicate that no one physical factor, such as the topographic setting, well depth, or altitude at the bottom of the well, was particularly useful for predicting those well locations with an elevated dissolved concentration of methane. The 2016 assessment of groundwater quality in Bradford County shows groundwater is generally of good quality, but methane and some constituents that occur in high concentration in naturally occurring brine and also in produced waters may be present at low to moderate concentrations in groundwater in various parts of the aquifer.

Pennsylvania↗

Comparison of regression relations of bankfull discharge and channel geometry for the glaciated and nonglaciated settings of Pennsylvania and southern New York

Streambank erosion in areas of past glacial deposition has been shown to be a dominant source of sediment to streams. Water resource managers are faced with the challenge of developing long and short term (emergency) stream restoration efforts that rely on the most suitable channel geometry for project design. A geomorphic dataset of new (2016, n=5) and previous (1999–2006, n=96) estimates of bankfull discharge and channel dimensions at U.S. Geological Survey streamflow-gaging stations was compiled to present and contrast the glaciated and unglaciated noncarbonate settings of southern New York and Pennsylvania that included selected areas of Maryland. Empirical models were developed by using simple linear regressions that relate bankfull discharge and channel geometry to drainage area (regional curves). Significant relations (p<0.05) were able to explain variability with coefficient of determination (R2 ) values of 0.89 for bankfull discharge, 0.94 for cross-sectional area, 0.87 for bankfull width, and 0.83 for bankfull depth. These regression relations for the glaciated noncarbonate settings of northern Pennsylvania and southern New York were able to provide a slightly better fit than regional curve models developed previously for the entire noncarbonate region of Pennsylvania. Although, the analysis of covariance (ANCOVA) results for comparison between regression equations for the glaciated and unglaciated settings showed that except for the significant intercept of bankfull discharge versus drainage area (F=8.26, p-value<0.005), the regression equations are not significantly different between the glaciated and unglaciated setting of Pennsylvania and southern New York. Therefore, data stratification by glaciation does not improve regional curves relations developed previously for the noncarbonate (glaciated and unglaciated) and carbonate settings of Pennsylvania and Maryland. Further analysis that incorporates data stratification or multivariate approaches based on mean annual runoff, precipitation, slope, stream classification, or other relevant parameters may optimize the accuracy and utility of statewide models. The new estimates of bankfull discharge and channel dimensions at streamflowgaging sites and updated drainage areas from StreamStats were incorporated into previously developed regional curves to produce an updated set of regression relations of bankfull discharge and channel geometry for the noncarbonate and carbonate settings of Pennsylvania and Maryland.

New York, Pennsylvania↗

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↗

Sources of fine-grained sediment in the Linganore Creek watershed, Frederick and Carroll Counties, Maryland, 2008-10

Sediment fingerprinting quantifies the delivery of fine-grained sediment from a watershed and sediment-budget measurements quantify the erosion and deposition of fine-grained sediment. Both approaches were used in the agricultural and forested 147-square-kilometer (km 2 ) Linganore Creek watershed in Maryland from August 1, 2008 through December 31, 2010, to determine the sources of fine-grained (less than 63 microns) sediment, and the amount of fine-grained sediment eroded from and deposited on streambanks, flood plains, channel beds, and agricultural and forested uplands. Sediment-weighted results of sediment fingerprinting for 194 suspended-sediment samples collected during 36 storms indicate that streambanks contributed 52 percent of the annual fine-grained suspended-sediment load, agriculture (cropland and pasture) contributed 45 percent, and forests contributed 3 percent. Fifty-four percent of the Linganore Creek watershed is agriculture and 27 percent is forest. Sediment-budget calculations were based on field measurements and photogrammetric analyses and indicated that the highest percentage of fine-grained sediment was eroded from agriculture (86 percent), followed by streambanks (10 percent), forests (3 percent), and the channel bed (less than 1 percent). Results of the sediment budget indicated that the highest percentage of fine-grained sediment was stored in ponds (57 percent), followed by flood plains (32 percent), streambanks (6 percent), and the channel bed (5 percent). Typical of most sediment budgets, the final sediment budget indicated erosion of 4.70 x 10 7 kilograms per year (kg/yr), which is higher than the fine-grained suspended-sediment load leaving the watershed (5.45 x 10 6 kg/yr). The differences in the sediment budget and the measured mass leaving the watershed could be due to an overestimation of erosion using the Cesium-137 method and (or) not adequately defining and measuring storage areas. Management implications of this study indicate that both agriculture and streambanks are important sources of sediment in Linganore Creek where the delivery of agriculture sediment was 4 percent and the delivery of streambank sediment was 44 percent. Fourth order streambanks, on average, had the highest rates of bank erosion. Combining the sediment fingerprinting and sediment budget results indicates that 96 percent of the eroded fine-grained sediment from agriculture went into storage. Flood plains and ponds are effective storage sites of sediment in the Linganore Creek watershed. Flood plains stored 8 percent of all eroded sediment with 4th and 5th order flood plains, on average, storing the most sediment. Small ponds in the Linganore Creek watershed, which drained 16 percent of the total watershed area, stored 15 percent of all eroded sediment. Channel beds were relatively stable with the greatest erosion generally occurring in 4th and 5th order streams.

Maryland↗

Residence time, chemical and isotopic analysis of nitrate in the groundwater and surface water of a small agricultural watershed in the Coastal Plain, Bucks Branch, Sussex County, Delaware

Nitrate is a common contaminant in groundwater and surface water throughout the Nation, and water-resource managers need more detailed small-scale watershed research to guide conservation efforts aimed at improving water quality. Concentrations of nitrate in Bucks Branch are among the highest in the state of Delaware and a scientific investigation was performed to provide water-quality information to assist with the management of agriculture and water resources. A combination of major-ion chemistry, nitrogen isotopic composition and age-dating techniques was used to estimate the residence time and provide a chemical and isotopic analysis of nitrate in the groundwater in the surficial aquifer of the Bucks Branch watershed in Sussex County, Delaware. The land use was more than 90 percent agricultural and most nitrogen inputs were from manure and fertilizer. The apparent median age of sampled groundwater is 18 years and the estimated residence time of groundwater contributing to the streamflow for the entire Bucks Branch watershed at the outlet is approximately 19 years. Concentrations of nitrate exceeded the U.S. Environmental Protection Agency drinking-water standard of 10 milligrams per liter (as nitrogen) in 60 percent of groundwater samples and 42 percent of surface-water samples. The overall geochemistry in the Bucks Branch watershed indicates that agriculture is the predominant source of nitrate contamination and the observed patterns in major-ion chemistry are similar to those observed in other studies on the Mid-Atlantic Coastal Plain. The pattern of enrichment in nitrogen and oxygen isotopes (δ15N and δ18O) of nitrate in groundwater and surface water indicates there is some loss of nitrate through denitrification, but this process is not sufficient to remove all of the nitrate from groundwater discharging to streams, and concentrations of nitrate in streams remain elevated.

Delaware↗

Pesticides in ground water in selected agricultural land-use areas and hydrogeologic settings in Pennsylvania, 2003-07

This report was prepared by the U.S. Geological Survey (USGS) in cooperation with the Pennsylvania Department of Agriculture (PDA) as part of the Pennsylvania Pesticides and Ground Water Strategy (PPGWS). Monitoring data and extensive quality-assurance data on the occurrence of pesticides in ground water during 2003–07 are presented and evaluated; decreases in the land area used for agriculture and corresponding changes in the use of pesticides also are documented. In the Pennsylvania ground waters assessed since 2003, concentrations of pesticides did not exceed any maximum contaminant or health advisory levels established by the U.S. Environmental Protection Agency; PPGWS actions are invoked by the PDA at fractions of these levels and were needed only in areas designated by the PDA for special ground-water protection. Previous investigations through 1998 of pesticides in Pennsylvania ground water identified land use, as a surrogate for pesticide use, and rock type of the aquifer combined with physiography as key hydrogeologic setting variables for understanding aquifer vulnerability to contamination and the common occurrence of atrazine and metolachlor in ground water. Of 20 major hydrogeologic settings in a framework established in 1999 for pesticide monitoring in Pennsylvania, 9 were identified as priorities for data collection in order to change the monitoring status from "inadequate" to "adequate" for the PPGWS. Agricultural and forested land-use areas are decreasing because of urban and suburban growth. In the nine hydrogeologic settings evaluated using 1992 and 2001 data, decreases of up to 12 percent for agricultural land and 10 percent for forested land corresponded to increases of up to 11 percent for urban land. Changes in agricultural pesticide use were computed from crop data. For example, from 1996 to 2004–05, atrazine use declined by about 15 percent to 1,314,000 lb/yr (pounds per year) and metolachlor use increased by about 20 percent to 895,000 lb/yr; these compounds are the two most-used agricultural pesticides statewide. In 2003–07, a baseline assessment of pesticides was conducted in five of nine hydrogeologic settings with inadequate monitoring data—the Blue Ridge crystalline and Triassic Lowland siliciclastic, Eastern Lake surficial, Devonian-Silurian carbonate, Great Valley siliciclastic, and Northeastern Glaciated surficial settings. Between 20 and 30 wells in each setting were monitored. Of the 126 wells sampled, 96 well-water samples were analyzed for at least 52 pesticide compounds at the USGS National Water Quality Laboratory (NWQL) using a method with a minimum reporting level (MRL) at or above 0.002 µg/L (micrograms per liter). Of the 96 well waters analyzed by NWQL, 43 had measureable concentrations of one or more pesticides. Atrazine and (or) deethylatrazine (CIAT), a degradation product of atrazine, were reported at or above the MRL in 39 of the 43 well waters. Neither atrazine nor CIAT were reported at concentrations exceeding 0.10 µg/L; all measured concentrations in these five settings were below PPGWS action levels. Metolachlor was present in 7 of the 43 well waters with measureable concentrations of 1 or more pesticides; however, concentrations were below the MRL. The other 30 samples (10 of 20 wells in the Blue Ridge crystalline and Triassic Lowland siliciclastic setting and all 20 wells in the Eastern Lake surficial setting) were analyzed for at least 19 pesticide compounds at the Pennsylvania Department of Environmental Protection Laboratory (PADEPL); the PADEPL reported no concentrations of pesticides at or above an MRL of 0.10 µg/L. Statistical tests using the NWQL analytical results showed correlations between pesticide occurrence and two indicators of water-quality degradation—the occurrence of total coliform bacteria and nitrate concentration. A 2 × 2 contingency-table test indicated a relation between presence or absence of atrazine or metolachlor and presence or absence of bacteria only for the 10 wells representing the Blue Ridge crystalline and Triassic Lowland siliciclastic setting. Results of Spearman’s rank test showed strong positive correlations in the Devonian-Silurian carbonate setting between 1) the number of pesticides above the MRLs and nitrate concentration, and 2) concentrations of atrazine and nitrate. Atrazine concentration and nitrate concentration also showed a statistically significant positive correlation in the Great Valley siliciclastic setting. An additional component of baseline monitoring was to evaluate changes in pesticide concentration in water from wells representing hydrogeologic settings most vulnerable to contamination from pesticides. In 2003, 16 wells originally sampled in the 1990s were resampled—4 each in the Appalachian Mountain carbonate, Triassic Lowland siliciclastic, Great Valley carbonate, and Piedmont carbonate settings. Nine of these wells, where pesticide concentrations from 1993 and 2003 were analyzed at the NWQL, were chosen for a paired-sample analysis using concentrations of atrazine and metolachlor. A statistically significant decrease in atrazine concentration was identified using the Wilcoxon signed-rank test (p = 0.004); significant temporal changes in metolachlor concentrations were not observed (p = 0.625). Monitoring in three areas of special ground-water protection, where selected pesticide concentrations in well water were at or above the PPGWS action levels, was done at wells BE 1370 (Berks County, Oley Township), BA 437 (Blair County, North Woodbury Township), and LN 1842 (Lancaster County, Earl Township). Co-occurrence of pesticide-degradation products with parent compounds was documented for the first time in ground-water samples collected from these three wells. Degradation products of atrazine, cyanazine, acetochlor, alachlor, and metolachlor were commonly at larger concentrations than the parent compound in the same water sample. Pesticide occurrence in water from wells neighboring the hot-spot wells was highly variable; however, the same sets of pesticide compounds that were present in wells BA 437, BE 1370, and LN 1842 were present to some degree in water from neighboring wells. To evaluate temporal changes in concentration, nonparametric statistical tests were used to determine overall and seasonal monotonic trends. Concentrations of alachlor, atrazine, metolachlor, and nitrate were examined using the 5-year (2003–07) and the long-term data from wells BA 437 and LN 1842 (1996–2007 and 1995–2007, respectively), and the long-term data for well BE 1370 (1998–2007); results showed either downward trends or no trends. Trends in acetochlor concentrations were tested only at well LN 1842 using the 5-year data; no trends were observed. Homogeneity of trend tests indicated statistically significant downward concentration trends in the long-term data were due to seasonal trends as follows: BA 437—alachlor and atrazine (summer); BE 1370—atrazine and metolachlor (winter) and alachlor (winter and spring); LN 1842—alachlor (summer and fall) and atrazine (spring and fall).

Pennsylvania↗