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Hydrogeologic setting and potential for denitrification in ground water, Coastal Plain of southern Maryland

The types and distribution of Coastal Plain sediments in the Patuxent River Basin may contribute to relatively low concentrations of nitrate (typically less than 1 milligram per liter) in stream base flow because of the chemical reduction of dissolved nitrate (denitrification) in ground water. Water chemistry data from synoptic stream base-flow surveys in the Patuxent River Basin show higher dissolved nitrate concentrations in the Piedmont than in the Coastal Plain section of the watershed. Stream base flow reflects closely the chemistry of ground water discharging from the surficial (unconfined) aquifer to the stream. Because land use in the sampled subbasins is virtually the same in each section, differences in the physical and geochemical characteristics of the surficial aquifer may explain the observed differences in water chemistry. One possible cause of lower nitrate concentrations in the Coastal Plain is denitrification within marine sediments that contain chemically reduced compounds. During denitrification, the oxygen atoms on the nitrate (N0 3 -) molecule are transferred to a reduced compound and N gas is produced. Organic carbon and ferrous iron (Fe 2+ ), derived from the dissolution of minerals such as pyrite (FeS 2 ) and glauconite (an iron aluminosilicate clay), can act as reducing substrates; these reduced chemical species are common in the marine and estuarine deposits in Southern Maryland. The spatial distribution of geologic units and their lithology (sediment type) has been used to create a map of the potential for denitrification of ground water in the surficial aquifer of the Coastal Plain in Southern Maryland.

Maryland

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

Ground-water-quality assessment of the Delmarva Peninsula, Delaware, Maryland, and Virginia; project description

In April 1986, the U.S. Geological Survey began a pilot program to assess the quality of the Nation 's surface water and groundwater resources. This National Water-Quality Assessment (NAWQA) program is designed to acquire and interpret information about a wide range of water quality issues. Three groundwater pilot projects have been started, including the project on the Delmarva Peninsula, which covers eastern Maryland and Virginia and most of Delaware. The objectives of the Delmarva project are to: (1) investigate regional groundwater quality on the Delmarva Peninsula, emphasizing a description of the occurrence of trace elements and manmade organic compounds; (2) relate groundwater quality to land use and geohydrologic conditions; and (3) provide a general description of the location, nature, and possible causes of selected water quality problems prevalent in the study area. The shallow aquifer system and the deeper aquifers used for public water supply will be addressed. The shallow aquifer system in the Delmarva Peninsula consists of permeable unconsolidated sand and gravel. Flow systems are localized and small-scale. Farming is common on the peninsula, and the migration of agricultural chemicals to the groundwater system is a local water quality concern. To assess the water quality of the groundwater resources, a regional survey for a wide range of constituents will be conducted in all of the pilot projects to provide a representative sample of groundwater analyses for a national assessment of groundwater quality. Results of this survey may be used as a baseline to monitor future water quality trends. (Lantz-PTT)

Open-File Report

Temporal and vertical variation of hydraulic head in aquifers in the Edgewood area, Aberdeen Proving Ground, Maryland

Water-level data and interpretations from previous hydrogeological studies conducted by the U.S. Geological Survey in the Edgewood Area of Aberdeen Proving Ground (APG), Maryland, were compared to determine similarities and differences among the aquifers. Because the sediments that comprise the shallow aquifers are discontinuous, the shallow ground-water-flow systems are local rather than extensive across the Edgewood Area. Hydrogeologic cross sections, hydrographs of water levels, and vertical gradients calculated from previous studies in the Canal Creek area, Graces Quarters, the O-Field area, Carroll Island, and the J-Field area, over periods of record ranging from 1 to 10 years during 1986-97, were used to determine recharge and discharge areas, connections between aquifers, and hydrologic responses of aquifers to natural and anthropogenic stress. Each of the aquifers in the study areas exhibited variation of hydraulic head that was attributed to seasonal changes in recharge. Upward hydraulic gradients and seasonal reversals of vertical hydraulic gradients between aquifers indicate the potential for local ground-water discharge from most of the aquifers that were studied in the Edgewood Area. Hydraulic head in individual aquifers in Graces Quarters and Carroll Island responded to offsite pumping during part of the period of record. Hydraulic head in most of the confined aquifers responded to tidal loading effects from nearby estuaries.

Water-Resources Investigations Report

Changes in streamflow and water quality in selected nontidal sites in the Chesapeake Bay Basin, 1985-2003

Water-quality and streamflow data from 33 sites in nontidal portions of the Chesapeake Bay Basin were analyzed to document annual nutrient and sediment loads and trends for 1985 through 2003 as part of an annual evaluation of water-quality conditions by the Chesapeake Bay Program. As part of this study, different trend tests and methodologies were evaluated for future use in assessment of the effectiveness of management actions in reducing nutrients and sediments to the Chesapeake Bay. Trends in streamflow were tested at multiple time scales (daily, monthly, seasonal, and annual), resulting in only one significant trend (annual flow for Choptank River near Greensboro, Md.). Data summaries for observed concentrations indicate higher ranges in total-nitrogen concentrations in the northern five major river basins in Pennsylvania, Maryland, and Virginia compared to the southern five basins in Virginia. Similar comparisons showed no distinct differences for total phosphorus. Flow-weighted concentration is useful in evaluating changes through time for the Susquehanna, Potomac, and James Rivers. Results indicate the Potomac River had the highest flow-weighted concentrations (2.5 milligrams per liter) for total nitrogen, and the Potomac and James Rivers averaged about the same (0.15 milligram per liter) for total-phosphorus concentrations. Flow-weighted concentrations were lowest in the Susquehanna River for phosphorus and sediment because of the trapping efficiency of three large reservoirs upstream from the sampling point. Annual loads were estimated by use of the U.S. Geological Surveys ESTIMATOR model. Annual nutrient and sediment loads in 2003 were the second highest total nitrogen, total phosphorus, and sediment loads for the River Input Monitoring sites since 1990. Trends in concentrations, when adjusted for flow, can be used as an indicator of human activity and management actions. The flow-adjusted trends indicated significant decreasing trends at approximately 55, 75, and 48 percent of the sites for total nitrogen, total phosphorus, and sediment, respectively. This suggests management actions are having some effect in reducing nutrients and sediments. Sampling protocols for the river inputs to the bay have targeted high flows. Because this sampling strategy creates the potential for bias in estimated loads and trends, calculations are limited to flow-adjusted loads and trends in this report.

Scientific Investigations Report

Relation of land use to nitrogen concentration in ground water in the Patuxent River basin, Maryland

A decrease in nitrogen inputs could improve water quality in the Chesapeake Bay. In order to provide information about nitrogen transport to the bay, the U.S. Geological Survey examined historical land use associated with nonpoint sources of nitrogen and nitrogen concentrations in ground water in the Patuxent River Basin, Maryland; The Patuxent River is a major tributary to the bay. Most nitrogen in ground water was present as nitrate. In the Piedmont Physiographic Province part of the Patuxent River basin, nitrate concentrations in ground water were higher in agricultural areas than in forested and urban areas. Nitrate concentrations were related to land use at well sites because wells yielded water that infiltrated within the same contributing area where the wells are located. Agricultural activities possibly were a source for the transport of large amounts of nitrogen to ground water and probably also to base flow in nearby streams. The high nitrate concentrations were not attributed to sampling bias. In the Coastal Plain Physiographic Province, most nitrate concentrations were low and were unrelated to land use at the well site because the wells were screened in deep, regional aquifers. Ground water in a few shallow wells had high nitrate concentrations, possibly related to nearby agricultural and urban land use. Increased nitrate concentrations in shallow ground water could increase concentrations in stream base flow and eventually could increase concentrations in regional aquifers and ground water that discharges directly to the Chesapeake Bay.

Water-Resources Investigations Report

Precipitation, peak streamflow, and inundation in the Bynum Run and Winters Run watersheds in Harford County, Maryland

The Harford County Department of Public Works and the U.S. Geological Survey have been working cooperatively to monitor continuous streamflow at several streamgages in Harford County, Maryland, including Bynum Run and Winters Run. A perceived recent uptick in the number of flooding events in the Bynum Run and Winters Run watersheds have led to questions about the relative frequency and magnitude of floods experienced by county residents. Precipitation, stage (water elevation), and peak flow analyses and trends were evaluated. Although there was no one contributor to point to for the perceived increase in flooding, it is most likely attributable to a combination of precipitation, stage, and peak flow. There have been numerous rainfall events with exceedingly long return intervals, but none were statistically out of the ordinary. The stages of the streams at higher flows are slightly higher (less than 0.5 feet) than historical stages, but likely are not great enough to cause a significant increase in flooding. The ratings (stage discharge relationship) for the streams have changed slightly. The latest ratings indicate erosion and deposition in the streambed over the years of observation, but again these alone do not result in more flooding. These factors taken together may point to an observational bias for incidental flooding. With the increase in land development, there may simply be more observations of flooding in the county.

Maryland

Preliminary assessment of microbial communities and biodegradation of chlorinated volatile organic compounds in wetlands at Cluster 13, Lauderick Creek area, Aberdeen Proving Ground, Maryland

A preliminary assessment of the microbial communities and biodegradation processes for chlorinated volatile organic compounds was con-ducted by the U.S. Geological Survey in wetlands at the Cluster 13, Lauderick Creek area at Aberdeen Proving Ground, Maryland. The U.S. Geological Survey collected wetland sediment samples from 11 sites in the Lauderick Creek area for microbial analyses, and used existing data to evaluate biodegradation processes and rates. The bacterial and methanogen communities in the Lauderick Creek wetland sediments were similar to those observed in a previous U.S. Geological Survey study at the West Branch Canal Creek wet-land area, Aberdeen Proving Ground. Evaluation of the degradation rate of 1,1,2,2-tetrachloroethane and the daughter compounds produced also showed similar results for the two wetlands. How-ever, a vertical profile of contaminant concentra-tions in the wetlands was available at only one site in the Lauderick Creek area, and flow velocities in the wetland sediment are unknown. To better evaluate natural attenuation processes and rates in the wetland sediments at Lauderick Creek, chemi-cal and hydrologic measurements are needed along ground-water flowpaths in the wetland at additional sites and during different seasons. Nat-ural attenuation in the wetlands, enhanced biore-mediation, and constructed wetlands could be feasible remediation methods for the chlorinated volatile organic compounds discharging in the Lauderick Creek area. The similarities in the microbial communities and biodegradation pro-cesses at the Lauderick Creek and West Branch Canal Creek areas indicate that enhanced bioreme-diation techniques currently being developed for the West Branch Canal Creek wetland area would be transferable to this area.

Maryland

Assessment of volatile organic compounds in surface water at West Branch Canal Creek, Aberdeen Proving Ground, Maryland, 1999

The U.S. Geological Survey (USGS) collected 13 surface-water samples and 3 replicates from 5 sites in the West Branch Canal Creek area at Aberdeen Proving Ground from February through August 1999, as a part of an investigation of ground-water contamination and natural attenuation processes. The samples were analyzed for volatile organic compounds, including trichloroethylene, 1,1,2,2-tetrachloroethane, carbon tetrachloride, and chloroform, which are the four major contaminants that were detected in ground water in the Canal Creek area in earlier USGS studies. Field blanks were collected during the sampling period to assess sample bias. Field replicates were used to assess sample variability, which was expressed as relative percent difference. The mean variability of the surface-water replicate analyses was larger (35.4 percent) than the mean variability of ground-water replicate analyses (14.6 percent) determined for West Branch Canal Creek from 1995 through 1996. The higher variability in surface-water analyses is probably due to heterogeneities in the composition of the surface water rather than differences in sampling or analytical procedures. The most frequently detected volatile organic compound was 1,1,2,2- tetrachloroethane, which was detected in every sample and in two of the replicates. The surface-water contamination is likely the result of cross-media transfer of contaminants from the ground water and sediments along the West Branch Canal Creek. The full extent of surface-water contamination in West Branch Canal Creek and the locations of probable contaminant sources cannot be determined from this limited set of data. Tidal mixing, creek flow patterns, and potential effects of a drought that occurred during the sampling period also complicate the evaluation of surface-water contamination.

Open-File Report

Hydrologic study at Farm Creek Marsh, Dorchester County, Maryland, from April 2015 to April 2016

In 2015, the U.S. Geological Survey began a 1-year hydrologic study to investigate the extent and cause of inundation at Farm Creek Marsh, in Dorchester County, Maryland. In combination with a tide and precipitation gage, a representative section of the marsh was instrumented with surface-water monitors and shallow groundwater piezometers to capture the spatial and temporal extent of inundation. In addition, water-quality data (major ions and nutrients) were collected to help discern the cause of inundation. Results indicate that during the year-long study, all sites were periodically inundated, ranging from a total of 108 days to the entire study period of 353 days. The depth of inundation was typically between 0 and 0.2 feet (ft) (above land surface), with the exception of large storm events. Less than 0.5 ft of elevation was the difference between a site being inundated during the entire study period of 353 days and a site being inundated for 36 consecutive days out of 108 total days of inundation during the study period. Water-quality data showed a large difference in pH between marsh surface water (6.1 to 6.9 standard pH units) and shallow groundwater (3.0 to 3.6 standard pH units), with differences also observed in concentrations of silica, iron, manganese, and potassium. Collectively, the combination of water-quality, hydrologic, and soils data indicate that inundation is caused by tide and storm events rather than groundwater discharge.

Maryland

Flux of nitrogen, phosphorus, and suspended sediment from the Susquehanna River Basin to the Chesapeake Bay during Tropical Storm Lee, September 2011, as an indicator of the effects of reservoir sedimentation on water quality

Concentrations of nitrogen, phosphorus, and suspended sediment are measured at the U.S. Geological Survey streamgage at Conowingo Dam at the downstream end of the Susquehanna River Basin in Maryland, where the river flows into the Chesapeake Bay. During the period September 7-15, 2011, in the aftermath of Tropical Storm Lee, concentrations of these three constituents were among the highest ever measured at this site. These measurements indicate that sediment-storage processes behind the three dams on the lower Susquehanna River are evolving. In particular, they indicate that scouring of sediment (and the nitrogen and phosphorus attached to that sediment) may be increasing with time. Trends in flow-normalized fluxes at the Susquehanna River at Conowingo, Maryland, streamgage during 1996-2011 indicate a 3.2-percent decrease in total nitrogen, but a 55-percent increase in total phosphorus and a 97-percent increase in suspended sediment. These large increases in the flux of phosphorus and sediment from the Susquehanna River to the Chesapeake Bay have occurred despite reductions in the fluxes of these constituents from the Susquehanna River watershed upstream from the reservoirs. Although the Tropical Storm Lee flood event contributed about 1.8 percent of the total streamflow from the Susquehanna River to the Chesapeake Bay over the past decade (water years 2002-11), it contributed about 5 percent of the nitrogen, 22 percent of the phosphorus, and 39 percent of the suspended sediment during the same period. These results highlight the importance of brief high-flow events in releasing nitrogen, phosphorus, and sediment derived from the Susquehanna River watershed and stored in the Conowingo Reservoir to the Chesapeake Bay.

Delaware;Maryl;New York;Pennsylvania;Virginia;West

Effects of Withdrawals on Ground-Water Levels in Southern Maryland and the Adjacent Eastern Shore, 1980-2005

Ground water is the primary source of water supply in most areas of Maryland?s Atlantic Coastal Plain, including Southern Maryland. The counties in this area are experiencing some of the most rapid growth and development in the State, resulting in an increased demand for ground-water production. The cooperative, basic water-data program of the U.S. Geological Survey and the Maryland Geological Survey has collected long-term observations of ground-water levels in Southern Maryland and parts of the Eastern Shore for many decades. Additional water-level observations were made by both agencies beginning in the 1970s, under the Power Plant Research Program of the Maryland Department of Natural Resources. These long-term water levels commonly show significant declines over several decades, which are attributed to ground-water withdrawals. Ground-water-level trends since 1980 in major Coastal Plain aquifers such as the Piney Point-Nanjemoy, Aquia, Magothy, upper Patapsco, lower Patapsco, and Patuxent were compared to water use and withdrawal data. Potentiometric surface maps show that most of the declines in ground-water levels can be directly related to effects from major pumping centers. There is also evidence that deep drawdowns in some pumped aquifers may be causing declines in adjacent, unpumped aquifers. Water-level hydrographs of many wells in Southern Maryland show linear declines in levels year after year, instead of the gradual leveling-off that would be expected as the aquifers equilibrate with pumping. A continual increase in the volumes of water being withdrawn from the aquifers is one explanation for why they are not reaching equilibrium. Although reported ground-water production in Southern Maryland has increased somewhat over the past several decades, the reported increases are often not large enough to account for the observed water-level declines. Numerical modeling simulations indicate that a steady, annual increase in the number of small wells could account for the observed aquifer behavior. Such wells, being pumped at rates below the minimum legal reporting threshold of 10,000 gallons per day, might be the source of the additional withdrawals. More detailed water-use data, especially from domestic wells, central-pivot irrigation wells, and other small users not currently reporting withdrawals to the State, may help to determine the cause of the aquifer declines.

Scientific Investigations Report

Development of land segmentation, stream-reach network, and watersheds in support of hydrological simulation program: Fortran (HSPF) modeling, Chesapeake Bay watershed, and adjacent parts of Maryland, Delaware, and Virginia

The U.S. Geological Survey, U.S. Environmental Protection Agency Chesapeake Bay Program Office, Interstate Commission on the Potomac River Basin, Maryland Department of the Environment, Virginia Department of Conservation and Recreation, Virginia Department of Environmental Quality, and the University of Maryland Center for Environmental Science are collaborating on the Chesapeake Bay Regional Watershed Model, using Hydrological Simulation Program - FORTRAN to simulate streamflow and concentrations and loads of nutrients and sediment to Chesapeake Bay. The model will be used to provide information for resource managers. In order to establish a framework for model simulation, digital spatial datasets were created defining the discretization of the model region (including the Chesapeake Bay watershed, as well as the adjacent parts of Maryland, Delaware, and Virginia outside the watershed) into land segments, a stream-reach network, and associated watersheds. Land segmentation was based on county boundaries represented by a 1:100,000-scale digital dataset. Fifty of the 254 counties and incorporated cities in the model region were divided on the basis of physiography and topography, producing a total of 309 land segments. The stream-reach network for the Chesapeake Bay watershed part of the model region was based on the U.S. Geological Survey Chesapeake Bay SPARROW (SPAtially Referenced Regressions On Watershed attributes) model stream-reach network. Because that network was created only for the Chesapeake Bay watershed, the rest of the model region uses a 1:500,000-scale stream-reach network. Streams with mean annual streamflow of less than 100 cubic feet per second were excluded based on attributes from the dataset. Additional changes were made to enhance the data and to allow for inclusion of stream reaches with monitoring data that were not part of the original network. Thirty-meter-resolution Digital Elevation Model data were used to delineate watersheds for each stream reach. State watershed boundaries replaced the Digital Elevation Model-derived watersheds where coincident. After a number of corrections, the watersheds were coded to indicate major and minor basin, mean annual streamflow, and each watershed's unique identifier as well as that of the downstream watershed. Land segments and watersheds were intersected to create land-watershed segments for the model.

Delaware, Maryland, Virginia

Ground-water flow and the possible effects of remedial actions at J-Field, Aberdeen Proving Ground, Maryland

J-Field, located in the Edgewood Area of Aberdeen Proving Ground, Md, has been used since World War II to test and dispose of explosives, chemical warfare agents, and industrial chemicals resulting in ground-water, surface-water, and soil contami- nation. The U.S. Geological Survey finite-difference model was used to better understand ground-water flow at the site and to simulate the effects of remedial actions. A surficial aquifer and a confined aquifer were simulated with the model. A confining unit separates these units and is represented by leakance between the layers. The area modeled is 3.65 mi2; the model was constructed with a variably spaced 40 X 38 grid. The horizontal and lower boundaries of the model are all no-flow boundaries. Steady-state conditions were used. Ground water at the areas under investigation flows from disposal pit areas toward discharge areas in adjacent estuaries or wetlands. Simulations indicate that capping disposal areas with an impermeable cover effectively slows advective ground water flow by 0.7 to 0.5 times. Barriers to lateral ground-water flow were simulated and effectively prevented the movement of ground water toward discharge areas. Extraction wells were simulated as a way to contain ground-water contamination and to extract ground water for treatment. Two wells pumping 5 gallons per minute each at the toxic-materials disposal area and a single well pumping 2.5 gallons per minute at the riot-control-agent disposal area effectively contained contamination at these sites. A combi- nation of barriers to horizontal flow east and south of the toxic-materials disposal area, and a single extraction well pumping at 5 gallons per minute can extract contaminated ground water and prevent pumpage of marsh water.

Water-Resources Investigations Report

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

Ground-water vulnerability to nitrate contamination at multiple thresholds in the mid-Atlantic region using spatial probability models

The U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency?s Regional Vulnerability Assessment Program, has developed a set of statistical tools to support regional-scale, ground-water quality and vulnerability assessments. The Regional Vulnerability Assessment Program?s goals are to develop and demonstrate approaches to comprehensive, regional-scale assessments that effectively inform managers and decision-makers as to the magnitude, extent, distribution, and uncertainty of current and anticipated environmental risks. The U.S. Geological Survey is developing and exploring the use of statistical probability models to characterize the relation between ground-water quality and geographic factors in the Mid-Atlantic Region. Available water-quality data obtained from U.S. Geological Survey National Water-Quality Assessment Program studies conducted in the Mid-Atlantic Region were used in association with geographic data (land cover, geology, soils, and others) to develop logistic-regression equations that use explanatory variables to predict the presence of a selected water-quality parameter exceeding a specified management concentration threshold. The resulting logistic-regression equations were transformed to determine the probability, P(X), of a water-quality parameter exceeding a specified management threshold. Additional statistical procedures modified by the U.S. Geological Survey were used to compare the observed values to model-predicted values at each sample point. In addition, procedures to evaluate the confidence of the model predictions and estimate the uncertainty of the probability value were developed and applied. The resulting logistic-regression models were applied to the Mid-Atlantic Region to predict the spatial probability of nitrate concentrations exceeding specified management thresholds. These thresholds are usually set or established by regulators or managers at National or local levels. At management thresholds of 1 milligram per liter and 3 milligrams per liter as nitrogen, the probability of nitrate concentrations exceeding these levels is greater than 50 percent (0.50) throughout much of the Mid-Atlantic Region. This includes extensive areas throughout central Maryland, southeastern Pennsylvania, northwestern Pennsylvania, and the Delmarva Peninsula. In addition, extensive areas in North Carolina and Virginia also have high probabilities of nitrate concentrations in ground water exceeding management thresholds of 1 milligram per liter and 3 milligrams per liter. The mapped areas showing a high predicted probability of nitrate concentrations in ground water exceeding 1 milligram per liter and 3 milligrams per liter correspond to areas that are mapped as cultivated land cover and/or overlying carbonate rocks. At a management threshold of 10 milligrams per liter (corresponding to the U.S. Environmental Protection Agency standard for nitrate in drinking water of 10 milligrams per liter), the predicted probability of nitrate concentrations in ground water exceeding this level is low for most of the Mid-Atlantic Region, except for the Delmarva Peninsula, southeastern Pennsylvania, and areas mapped as carbonate rocks in Virginia, Maryland, and Pennsylvania.

Scientific Investigations Report

Hydrogeologic setting, hydraulic properties, and ground-water flow at the O-Field area of Aberdeen Proving Ground, Maryland

The U.S. Army disposed chemical agents, laboratory materials, and unexploded ordnance at O-Field in the Edgewood Area of Aberdeen Proving Ground, Maryland, from before World War II until at least the 1950's. Soil, ground water, surface water, and wetland sediments in the O-Field area were contaminated from the disposal activity. A ground-water-flow model of the O-Field area was constructed by the U.S. Geological Survey (USGS) in 1989 to simulate flow in the central and southern part of Gunpowder Neck. The USGS began an additional study of the contamination in the O-Field area in cooperation with the U.S. Army in 1990 to (1) further define the hydrogeologic framework of the O-Field area, (2) characterize the hydraulic properties of the aquifers and confining unit, and (3) define ground-water flow paths at O-Field on the basis of the current data and simulations of ground-water flow. A water-table aquifer, an upper confining unit, and an upper confined aquifer comprise the shallow ground-water system of the O-Field area. A lower confining unit, through which ground-water movement is negligible, is considered a lower boundary to the shallow system. These units are all part of the Pleistocene Talbot Formation. The model developed in the previous study was redesigned using the data collected during this study and emphasized New O-Field. The current steady-state model was calibrated to water levels of June 1993. The rate of ground-water flow calculated by the model was approximately 0.48 feet per day and the rate determined from chlorofluorocarbon dates was approximately 0.39 feet per day.

Maryland

Characterization of Preferential Ground-Water Seepage From a Chlorinated Hydrocarbon-Contaminated Aquifer to West Branch Canal Creek, Aberdeen Proving Ground, Maryland, 2002-04

Wetlands act as natural transition zones between ground water and surface water, characterized by the complex interdependency of hydrology, chemical and physical properties, and biotic effects. Although field and laboratory demonstrations have shown efficient natural attenuation processes in the non-seep wetland areas and stream bottom sediments of West Branch Canal Creek, chlorinated volatile organic compounds are present in a freshwater tidal creek at Aberdeen Proving Ground, Maryland. Volatile organic compound concentrations in surface water indicate that in some areas of the wetland, preferential flow paths or seeps allow transport of organic compounds from the contaminated sand aquifer to the overlying surface water without undergoing natural attenuation. From 2002 through 2004, the U.S. Geological Survey, in cooperation with the Environmental Conservation and Restoration Division of the U.S. Army Garrison, Aberdeen Proving Ground, characterized preferential ground-water seepage as part of an ongoing investigation of contaminant distribution and natural attenuation processes in wetlands at this site. Seep areas were discrete and spatially consistent during thermal infrared surveys in 2002, 2003, and 2004 throughout West Branch Canal Creek wetlands. In these seep areas, temperature measurements in shallow pore water and sediment more closely resembled those in ground water than those in nearby surface water. Generally, pore water in seep areas contaminated with chlorinated volatile organic compounds had lower methane and greater volatile organic compound concentrations than pore water in non-seep wetland sediments. The volatile organic compounds detected in shallow pore water in seeps were spatially similar to the dominant volatile organic compounds in the underlying Canal Creek aquifer, with both parent and anaerobic daughter compounds detected. Seep locations characterized as focused seeps contained the highest concentrations of chlorinated parent compounds, relatively low concentrations of chlorinated daughter compounds, and insignificant concentrations of methane in shallow pore water samples. These seeps were primarily along the creek edge or formed a dendritic-like pattern between the wetland and creek channel. In contrast, seep locations characterized as diffuse seeps contained relatively high concentrations of chlorinated daughter compounds (or a mixture of daughter and parent compounds) and detectable methane concentrations in shallow pore water samples. These seeps were primarily along the wetland boundary. Qualitative thermal infrared surveys coupled with quantitative verification of temperature differences, and screening for volatile organic compound and methane concentrations proved to be effective tools in determining the overall extent of preferential seepage. Hydrologic and physical properties of wetland sediments were characterized at two focused and one diffuse seep location. In the seeps with focused discharge, measured seepage was consistent over the tidal cycle, whereas more variability with tidal fluctuation was measured in the diffuse seep location. At all locations, areas were identified within the general seep boundaries where discharge was minimal. In all cases, the geometric mean of non-zero vertical flux measurements was greater than those previously reported in the non-seep wetland sediments using flow-net analysis. Flux was greater in the focused discharge areas than in the diffuse discharge area, and all fluxes were within the range reported in the literature for wetland discharge. Vertical hydraulic conductivity estimated from seepage flux and a mean vertical gradient at seeps with focused discharge resulted in a minimum hydraulic conductivity two orders of magnitude greater than those estimated in the non-seep sediment. In contrast, vertical conductivity estimates at a diffuse seep were similar to estimates along a nearby line of section through a non-seep area.

Scientific Investigations Report