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Refining sources of polychlorinated biphenyls in the Back River watershed, Baltimore, Maryland, 2018–2020

Older urban landscapes present unique and complex stressors to urban streams and their habitats through the introduction of legacy and emerging toxic contaminants. Contaminant sources are often associated with various developed land uses such as older residential areas, active and former industrial sites, contaminated sites, and effluents from municipal wastewater treatment plant discharges. These landscapes have a history of legacy contaminant use such as polychlorinated biphenyls (PCBs) resulting in impacts to sediment and water in these complex environments. Despite the ban of PCBs in new commercial use in 1979, PCB contamination is still widespread in the environment, with many fish consumption advisories throughout the Chesapeake Bay region based on elevated PCBs. Several watersheds in the Baltimore region have mandated reductions in PCBs per total maximum daily loads in tidal waters of the watersheds in order to promote compliance with water quality standards. Some of these mandated reductions (for example, regulated watershed runoff) specified in the total maximum daily loads are the responsibility of the local jurisdictions as part of their phase 1 National Pollutant Discharge Elimination System municipal separate storm sewer system permit. In cooperation with the Baltimore City Department of Public Works and Maryland Department of the Environment, the U.S. Geological Survey and University of Maryland, Baltimore County conducted a study from 2018 to 2020 to refine the sources of PCBs from the City of Baltimore into Back River and to use the results to improve the conceptual site model of PCBs in the Back River watershed. PCB concentrations in the water column of the nontidal streams in Back River watershed are relatively consistent throughout both tributaries, with greater concentrations detected in samples collected from Moores Run but greater loads estimated in samples collected from Herring Run. PCB concentrations measured in the bed sediments and analysis of the flux between sediment porewater (hereafter porewater) and surface water within the tributaries suggest that there are no stationary legacy sources within the stream channels. The bulk of PCB mass entering the system from these nontidal tributaries appears to be introduced primarily during storm events. While only one storm event was sampled and concentrations were quantified only in Herring Run, solids captured during the storm were characterized by increases in PCB mass and overall suspended solids concentrations. Although the bioavailability of the PCB-associated sediment is unknown, this mechanism appears to warrant additional attention to better understand how concentrations vary under different storm conditions and temporally. The importance of contaminated stormwater in loading to Herring Run is further supported by the PCB concentrations in storm drain sediments collected near the tributary, which were present in higher concentrations and were characterized by different homolog signatures compared to that in bed sediments. The observations in the tributaries differed from PCB concentrations and sediment characteristics downstream from the City of Baltimore boundary, in the upper tidal area of the main stem of Back River, particularly at the passive sampler locations BRT–1 and BRT–3. This depositional environment is characterized by higher organic content in sediments and higher concentrations of PCBs in porewater, which result in the possible flux of contaminants from sediment to the water column. This flux is generally opposite of that observed in the nontidal tributaries and the farthest upstream tidal site (BRT–2) and may be a result of the possible settling of sediment particles introduced via suspended solids in stormwater. Despite an observed considerable reduction in overall PCB mass loading to and from the Back River Wastewater Treatment Plant (BRWWTP) (and similar reductions observed in biosolids) compared to the estimates previously reported from 2015, effluent from the BRWWTP continues to be a primary source of PCBs to Back River. The current study confirmed the likeliness of fat, oil, and grease deposits within the miles of sewer pipe as a source of PCBs to the BRWWTP influent. The differences between PCB concentrations in fat, oil, and grease deposits found in pipes (during replacement) compared to that of the BRWWTP suggest that legacy deposits may contain higher PCB concentrations and may act as a source of PCBs to passing sewage, eventually entering the BRWWTP. Variation in freely dissolved concentrations in the sewer system was apparent through the analysis of PCBs in the primary pump stations using passive sampling, with the largest contribution to the influent attributed to a single pump station and associated piping. The contribution of PCBs to Herring Run and Moores Run via sanitary sewer overflows compared to the BRWWTP effluent is negligible, similar to reports from another large urban wastewater treatment plant. Therefore, decreased occurrence of sanitary sewer overflows is not expected to largely decrease PCB loads. Results of this study suggest that targeted, sediment-capture best management practices in Back River watershed could be an effective way to reduce PCB mass loading assuming that deposited contaminated sediments are effectively isolated. Recent studies of some common urban best management practices such as bioretention have shown removal of PCBs within the stormwater control structures. In addition, appropriately timed street sweeping practices with appropriate collection equipment may be an effective way to reduce contaminants such as PCBs from road runoff sources. Reductions in concentrations and mass loading within the sewer system measured in this study compared to that estimated 5 years prior reflect the possible success of ongoing gray infrastructure management actions. Reductions may be attributable to enhanced nutrient reduction upgrades to the BRWWTP and extensive capital improvements and maintenance to the sewer system. This study employed a combined sampling approach and a variety of sampling methods to include low-density polyethylene passive samplers, high-volume water samples, and grab samples of both water and sediment to characterize the PCB inputs to Herring Run, Moores Run, and Back River. Incorporating the passive samplers provided a time-weighted average of the freely dissolved concentration in the surface water, porewater, WWTP influent and effluent, and pump station influent over the deployment period with picogram per liter detection limits. A similar monitoring approach from this study could be implemented within other subwatersheds or municipal separate storm sewer system jurisdictions to assist in refining primary sources of PCBs in order to inform appropriate mitigation approaches.

Maryland↗

Updates to the regional groundwater-flow model of the New Jersey Coastal Plain, 1980–2013

A 21-layer three-dimensional transient groundwater-flow model of the New Jersey Coastal Plain was developed and calibrated by the U.S. Geological Survey (USGS) in cooperation with the New Jersey Department of Environmental Protection to simulate groundwater-flow conditions during 1980–2013, incorporating average annual groundwater withdrawals and average annual groundwater recharge. This model is the third version of the New Jersey Coastal Plain regional groundwater-flow model that was initially developed as part of the USGS Regional Aquifer System Analysis (RASA) program. The model simulates groundwater flow in 11 aquifers and 10 intervening confining units of the New Jersey Coastal Plain to provide a regional overview of groundwater conditions. Averaged groundwater withdrawal data for 1980 to 2013 were used in the model. The 11 aquifers in New Jersey are, from shallowest to deepest, the Holly Beach water-bearing zone and the confined Cohansey aquifer in Cape May County; the Rio Grande water-bearing zone; the Atlantic City 800-foot sand; the Piney Point, Vincentown, and Wenonah-Mount Laurel aquifers; the Englishtown aquifer system; and the upper, middle, and lower aquifers of the Potomac-Raritan-Magothy (PRM) aquifer system. The model was developed with the MODFLOW–2005 numerical code and the UCODE parameter estimation technique and calibrated using water-level and base-flow observations. A total of 3,453 water-level observations from 392 wells in New Jersey and 48 wells in Delaware from 1983 to 2013 were used in model calibration, which includes historical water-level trends for 29 wells in New Jersey during 1980–2013 presented in time-series hydrographs. In addition, derived observations also were included by calculating the vertical gradient at 33 pairs of nested observation wells in New Jersey, for a total of 210 observations. Changes in water levels over time were calculated for 134 wells in New Jersey and four wells in Delaware where water levels had varied substantially (approximately 10 ft) over the 30-year span of synoptic water-level measurements, for a total of 767 observations. A total of 1,485 base-flow observations in 47 surface-water basins in New Jersey from 1980 to 2013 were used in model calibration. Updates to the groundwater-flow model include the conversion to a fully three-dimensional model from the previous quasi-three-dimensional model. The new model will allow for potential future uses such as particle tracking or simulation of variable-density groundwater flow that could not be accomplished with earlier versions of the model. Spatially and temporally variable recharge estimated by using a soil-water balance model resulted in a spatially and temporally finer discretization. The Rio Grande water-bearing zone was added to the model as an aquifer layer to refine estimates of simulated flow in Atlantic and Cape May Counties, New Jersey. Hydrogeologic parameters were updated to include the confining units in New Jersey and corresponding hydrogeologic units in Delaware and eastern Maryland. The simulated water levels for the New Jersey Coastal Plain aquifers were compared to water-level measurements made during 1980–2013. The average residual for 4,243 water-level observations for New Jersey (simulated water levels minus measured water levels) is 1.5 feet. The simulated water-level contours for the confined aquifers for 2013 were compared to potentiometric surfaces produced from water levels measured during 2013. Simulated water levels generally matched the 2013 potentiometric surfaces of the confined aquifers in the areas of large withdrawals. Hydrographs of wells in the confined Coastal Plain aquifers of New Jersey show that simulated water levels generally match the magnitude and seasonal variation of the observed water levels. Hydrographs of base flow for the 47 streamgaging stations in New Jersey indicate that most of the simulated and estimated data match reasonably well. Groundwater withdrawals are an important resource for water supply, agricultural, industrial, and commercial needs in the New Jersey Coastal Plain. Groundwater withdrawals from the New Jersey Coastal Plain aquifers have resulted in persistent, regionally extensive cones of depression in the Englishtown aquifer system and Wenonah-Mount Laurel aquifer in Ocean and Monmouth Counties; Wenonah-Mount Laurel and upper, middle, and lower PRM aquifers in Camden County; and Atlantic City 800-foot sand in Atlantic County. Because hydrologic stresses and water-management needs change with time, periodic updates to the groundwater-flow model are required to provide current information about hydrologic conditions in the New Jersey Coastal Plain and to maintain its usefulness as a tool to manage water resources and develop water-resource strategies. The current updates will support the continued application of this model as a tool for evaluating the regional effects of changes in groundwater withdrawals and of current and potential future water-management strategies on groundwater levels in the New Jersey Coastal Plain.

New Jersey Coastal Plain↗

Simulation of streamflow and water quality in the Christina River subbasin and overview of simulations in other subbasins of the Christina River Basin, Pennsylvania, Maryland, and Delaware, 1994-98

The Christina River Basin drains 565 square miles (mi 2 ) in Pennsylvania and Delaware and includes the major subbasins of Brandywine Creek, Red Clay Creek, White Clay Creek, and Christina River. The Christina River subbasin (exclusive of the Brandywine, Red Clay, and White Clay Creek subbasins) drains an area of 76 mi 2 . Streams in the Christina River Basin are used for recreation, drinking water supply, and support of aquatic life. Water quality in some parts of the Christina River Basin is impaired and does not support designated uses of the stream. A multi-agency water-quality management strategy included a modeling component to evaluate the effects of point- and nonpoint-source contributions of nutrients and suspended sediment on stream water quality. To assist in nonpoint-source evaluation, four independent models, one for each of the four main subbasins of the Christina River Basin, were developed and calibrated using the model code Hydrological Simulation Program–Fortran (HSPF). Water-quality data for model calibration were collected in each of the four main subbasins and in small subbasins predominantly covered by one land use following a nonpoint- source monitoring plan. Under this plan, stormflow and base-flow samples were collected during 1998 at two sites in the Christina River subbasin and nine sites elsewhere in the Christina River Basin. The HSPF model for the Christina River subbasin simulates streamflow, suspended sediment, and the nutrients, nitrogen and phosphorus. In addition, the model simulates water temperature, dissolved oxygen, biochemical oxygen demand, and plankton as secondary objectives needed to support the sediment and nutrient simulations. For the model, the basin was subdivided into nine reaches draining areas that ranged from 3.8 to 21.9 mi 2 . Ten different pervious land uses and two impervious land uses were selected for simulation. Land-use areas were determined from 1995 land-use data. The predominant land uses in the Christina River subbasin are residential, urban, forested, agricultural, and open. The hydrologic component of the model was run at an hourly time step and calibrated using streamflow data from two U.S. Geological Survey (USGS) streamflow-measurement stations for the period of October 1, 1994, through October 29, 1998. Daily precipitation data from one National Oceanic and Atmospheric Administration (NOAA) meteorologic station and hourly data from one NOAA meteorologic station were used for model input. The difference between observed and simulated streamflow volume ranged from -2.3 to 5.3 percent for a 10-month portion of the calibration period at the two calibration sites. Annual differences between observed and simulated streamflow generally were greater than the overall error for the 4-year period. For example, at Christina River at Coochs Bridge, near the bottom of the free-flowing part of the subbasin (drainage area of 21 mi 2 ), annual differences between observed and simulated streamflow ranged from -6.9 to 6.5 percent and the overall error for the 4-year period was -1.1 percent. Calibration errors for 36 storm periods at the three calibration sites for total volume, low-flow recession rate, 50-percent lowest flows, 10-percent highest flows, and storm peaks were within the recommended criteria of 20 percent or less. Much of the error in simulating storm events on an hourly time step can be attributed to uncertainty in the rainfall data. The water-quality component of the model was calibrated using nonpoint-source monitoring data collected at two USGS streamflow-measurement stations and other water-quality monitoring data. The period of record for water-quality monitoring was variable at the stations, with a start date ranging from October 1994 to January 1998 and an end date of October 1998. Because of availability, monitoring data for suspended-solids concentrations were used as surrogates for suspended-sediment concentrations, although suspended-solids data may underestimate suspended sediment and affect apparent accuracy of the suspended-sediment simulaion. Comparison of observed to simulated loads for up to six storms in 1998 at the two nonpoint-source monitoring sites (Little Mill Creek near Newport and Christina River at Coochs Bridge, Del.) indicate that simulation error is commonly as large as an order of magnitude for suspended sediment and nutrients. The simulation error tends to be smaller for dissolved nutrients than for particulate nutrients. Errors of 40 percent or less for monthly or annual values indicate a fair to good water-quality calibration according to recommended criteria; much larger errors are possible for individual events. Assessment of the water-quality calibration under stormflow conditions is limited by the relatively small amount of available water-quality data in the subbasin. Users of the Christina River subbasin HSPF model and HSPF models for other subbasins in the Christina River Basin should be aware of model limitations and consider the following if the model is used for predictive purposes: streamflow-duration curves suggest the model simulates streamflow reasonably well when measured over a broad range of conditions and time although streamflow and the corresponding water quality for individual storm events may not be well simulated; streamflow-duration curves for the simulation period compare well with duration curves for the 8-year period ending in 2001 at Christina River at Coochs Bridge, Del., and include all but the extreme high-flow and low-flow events; and calibration for water quality was based on limited data, with the result of increasing uncertainty in the water-quality simulation.

Water-Resources Investigations Report↗

Simulation of streamflow and water quality in the White Clay Creek subbasin of the Christina River Basin, Pennsylvania and Delaware, 1994-98

The Christina River Basin drains 565 square miles (mi 2 ) in Pennsylvania, Maryland, and Delaware. Water from the basin is used for recreation, drinking water supply, and to support aquatic life. The Christina River Basin includes the major subbasins of Brandywine Creek, White Clay Creek, and Red Clay Creek. The White Clay Creek is the second largest of the subbasins and drains an area of 108 mi 2 . Water quality in some parts of the Christina River Basin is impaired and does not support designated uses of the streams. A multi-agency water-quality management strategy included a modeling component to evaluate the effects of point and nonpoint-source contributions of nutrients and suspended sediment on stream water quality. To assist in non point-source evaluation, four independent models, one for each of the three major subbasins and for the Christina River, were developed and calibrated using the model code Hydrological Simulation Program—Fortran (HSPF). Water-quality data for model calibration were collected in each of the four main subbasins and in smaller subbasins predominantly covered by one land use following a nonpoint-source monitoring plan. Under this plan, stormflow and base- flow samples were collected during 1998 at two sites in the White Clay Creek subbasin and at nine sites in the other subbasins. The HSPF model for the White Clay Creek Basin simulates streamflow, suspended sediment, and the nutrients, nitrogen and phosphorus. In addition, the model simulates water temperature, dissolved oxygen, biochemical oxygen demand, and plankton as secondary objectives needed to support the sediment and nutrient simulations. For the model, the basin was subdivided into 17 reaches draining areas that ranged from 1.37 to 13 mi 2 . Ten different pervious land uses and two impervious land uses were selected for simulation. Land-use areas were determined from 1995 land-use data. The predominant land uses in the White Clay Creek Basin are agricultural, forested, residential, and urban. The hydrologic component of the model was run at an hourly time step and primarily calibrated using streamflow data from two U.S. Geological Survey (USGS) streamflow-measurement stations for the period of October 1, 1994, through October 29, 1998. Additional calibration was done using data from two other USGS streamflow-measurement stations with periods of record shorter than the calibration period. Daily precipitation data from two National Oceanic and Atmospheric Administration (NOAA) gages and hourly precipitation and other meteorological data for one NOAA gage were used for model input. The difference between simulated and observed streamflow volume ranged from -0.9 to 1.8 percent for the 4-year period at the two calibration sites with 4-year records. Annual differences between observed and simulated streamflow generally were greater than the overall error. For example, at a site near the bottom of the basin (drainage area of 89.1 mi 2 ), annual differences between observed and simulated streamflow ranged from -5.8 to 14.4 percent and the overall error for the 4-year period was -0.9 percent. Calibration errors for 36 storm periods at the two calibration sites for total volume, low-flowrecession rate, 50-percent lowest flows, 10-percent highest flows, and storm peaks were within the recommended criteria of 20 percent or less. Much of the error in simulating storm events on an hourly time step can be attributed to uncertainty in the hourly rainfall data. The water-quality component of the model was calibrated using data collected by the USGS and state agencies at three USGS streamflow-measurement stations with variable water-quality monitoring periods ending October 1998. Because of availability, monitoring data for suspended-solids concentrations were used as surrogates for suspended-sediment concentrations, although suspended solids may underestimate suspended sediment and affect apparent accuracy of the suspended-sediment simulation. Comparison of observed to simulated loads for up to five storms in 1998 at each of the two nonpoint-source monitoring sites in the White Clay Creek Basin indicate that simulation error is commonly as large as an order of magnitude for suspended sediment and nutrients. The simulation error tends to be smaller for dissolved nutrients than for particulate nutrients. Errors of 40 percent or less for monthly or annual values indicate a fair to good water-quality calibration according to recommended criteria, with much larger errors possible for individual events. The accuracy of the water-quality calibration under stormflow conditions is limited by the relatively small amount of water-quality data available for the White Clay Creek Basin. Users of the White Clay Creek HSPF model should be aware of model limitations and consider the following if the model is used for predictive purposes: streamflow and water quality for individual storm events may not be well simulated, but the model performance is reasonable when evaluated over longer periods of time; the observed flow-duration curve for the simulation period is similar to the long-term flow-duration curve at White Clay Creek near Newark, Del., indicating that the calibration period is representative of all but highest 0.1 percent and lowest 0.1 percent of flows at that site; relative errors in streamflow and water-quality simulations are greater for smaller drainage areas than for larger areas; and calibration for water-quality was based on sparse data.

Water-Resources Investigations Report↗

Anaerobic degradation of 1,1,2,2-tetrachloroethane and association with microbial communities in a freshwater tidal wetland, Aberdeen Proving Ground, Maryland: Laboratory experiments and comparisons to field data

Defining biodegradation rates and processes is a critical part of assessing the feasibility of monitored natural attenuation as a remediation method for ground water containing organic contaminants. During 1998–2001, the U.S. Geological Survey conducted a microbial study at a freshwater tidal wetland along the West Branch Canal Creek, Aberdeen Proving Ground, Maryland, as part of an investigation of natural attenuation of chlorinated volatile organic compounds (VOCs) in the wetland sediments. Geochemical analyses and molecular biology techniques were used to investigate factors controlling anaerobic degradation of 1,1,2,2-tetrachloroethane (TeCA), and to characterize the microbial communities that potentially are important in its degradation. Rapid TeCA and daughter product degradation observed in laboratory experiments and estimated with field data confirm that natural attenuation is a feasible remediation method at this site. The diverse microbial community that seems to be involved in TeCA degradation in the wetland sediments varies with changing spatial and seasonal conditions, allowing continued effective natural attenuation throughout the year. Rates of TeCA degradation in anaerobic microcosm experiments conducted with wetland sediment collected from two different sites (WB23 and WB30) and during three different seasons (March–April 1999, July–August 1999, and October–November 2000) showed little spatial variability but high seasonal variability. Initial first-order degradation rate constants for TeCA ranged from 0.10±0.01 to 0.16±0.05 per day (halflives of 4.3 to 6.9 days) for March–April 1999 and October–November 2000 microcosms incubated at 19 degrees Celsius, whereas lower rate constants of 0±0.03 and 0.06±0.03 per day were obtained in July–August 1999 microcosms incubated at 19 degrees Celsius. Microbial community profiles showed that low microbial biomass and microbial diversity in the summer, possibly due to competition for nutrients by the wetland vegetation, could account for these unexpectedly low degradation rates. In microcosms incubated at 5 degrees Celsius, about 50 percent of the initial TeCA in solution was converted to daughter products within a 35-day incubation period, indicating that biodegradation in the wetland sediments can continue during cold winter temperatures. Initial pathways of TeCA degradation were the same in the wetland sediment microcosms regardless of the season or sediment collection site, the reduction-oxidation conditions, and the previous exposure of the sediment to contamination. Immediate and simultaneous dichloroelimination and hydrogenolysis, producing 1,2-dichloroethene (12DCE) and 1,1,2-trichloroethane (112TCA), respectively, were the initial TeCA degradation pathways in all live microcosm experiments. The production and degradation of vinyl chloride (VC), which is the most toxic of the TeCA daughter compounds, was affected by spatial and seasonal variability, reduction-oxidation condition, and pre-exposure of the wetland sediment. TeCA-amended microcosms constructed with WB30 sediment showed approximately twice as much VC production as those constructed with WB23 sediment. Results of 112TCA-amended microcosms indicated that the greater production of VC in the WB30 sediment resulted from a greater predominance of the 112TCA dichloro elimination pathway in these sediments. VC degradation also was substantially higher in microcosms constructed with WB30 sediment than those constructed with WB23 sediment, resulting in lower VC concentrations at the end of WB30 microcosms. Enrichment experiments in which microcosm slurry was amended with high initial VC concentrations showed that the spatial difference in VC degradation was negligible after prolonged incubation under methanogenic conditions. Inhibition of methanogenic activity in microcosms by addition of sulfate or of 2-bromoethanesulfonic acid inhibited production and degradation of VC. Inhibition of methanogenesis by addition of ferric iron or of 2-bromoethanesulfonic acid also completely inhibited VC degradation in VC-amended enrichment experiments. Pre-exposure to VC substantially increased degradation in VC-amended enrichment experiments. A microbial consortium, rather than one microbial species or group, likely is involved in the degradation of TeCA, as indicated by the occurrence of multiple degradation pathways and the variability in VC production and degradation. A bacterial peak at 90 base pair (bp) fragment length in terminal- restriction fragment length polymorphism (TRFLP) profiles was associated with TeCA hydrogenolysis to 112TCA, and bacterial species represented by 198 and 170 bp fragment lengths were associated with TeCA dichloroelimination to 12DCE. Dichloroelimination of 112TCA to VC was associated with increasing dominance of the 198 bp bacterial peak in March–April 1999 and October–November 2000 microcosms, whereas an 86 bp or the 170 bp bacterial peak was associated with 112TCA dichloroelimination in the summer experiment. Hydrogenolysis of 12DCE to VC was associated with a carbon dioxide-utilizing methanogen at 307 bp in the March–April 1999 and October–November 2000 microcosm experiments, whereas production of VC occurred despite low methanogen biomass and methane production in the July–August 1999 experiments. Production of VC in the absence of methane production also occurred in 12DCE-amended enrichment cultures. The exponential production of VC in the 12DCE-amended enrichment cultures after an initial lag indicated growth of a microbial species or group, possibly one of the known dehalorespiring bacteria. Molecular analyses using specific primers targeting dehalorespiring bacteria of the Dehalococcoides group (Dehalococcoides ethenogenes and Dehalococcoides sp. strain FL2) and of the acetate-oxidizing Desulfuromonas group (Desulfuromonas sp. strain BB1 and Desulfuromonas chloroethenica) showed the presence of these bacteria in microcosm slurry from site WB30 but not from site WB23. Addition of hydrogen, which is the favored substrate of Dehalococcoides, tripled VC production in 12DCE-amended enrichment cultures. VC degradation showed a marked association with an increase in the relative proportion of Methanosarcinaceae, a family of methanogens that includes all those capable of utilizing acetate as a substrate, in the total methanogen community. Half-lives for TeCA and TCE estimated from field data were in the range of 60 to 100 days, which agrees well with laboratory estimates of degradation rates considering the inherent differences in the laboratory and field systems. Both laboratory microcosm experiments and field data showed that 12DCE and VC are the predominant, persistent daughter compounds from TeCA degradation. In addition, porewater chemistry showed higher accumulation of VC in the wetland sediment at site WB30 than at site WB23, as was observed in the microcosm experiments. Molecular analyses of grab samples of surficial wetland sediment showed that all the microbial species or groups linked to TeCA degradation in the microcosm experiments were present in all sediment samples. Microbial biomass and diversity were lowest in an area of the wetland (transect C-C') where porewater VOC concentrations are highest, indicating that the higher VOC concentrations could result from lower degradation rates. The lower microbial biomass and diversity in this area could be caused by toxic effects of the contaminants, or possibly from differences in frequency and duration of tidal inundation.

Maryland↗

Nutrient concentrations and loads in the northeastern United States - Status and trends, 1975-2003

The U.S. Geological Survey (USGS) National Water-Quality Assessment Program (NAWQA) began regional studies in 2003 to synthesize information on nutrient concentrations, trends, stream loads, and sources. In the northeastern United States, a study area that extends from Maine to central Virginia, nutrient data were evaluated for 130 USGS water-quality monitoring stations. Nutrient data were analyzed for trends in flow-adjusted concentrations, modeled instream (non-flow-adjusted) concentrations, and stream loads for 32 stations with 22 to 29 years of water-quality and daily mean streamflow record during 1975-2003 (termed the long-term period), and for 46 stations during 1993-2003 (termed the recent period), by using a coupled statistical model of streamflow and water quality developed by the USGS. Recent trends in flow-adjusted concentrations of one or more nutrients also were analyzed for 90 stations by using Tobit regression. Annual stream nutrient loads were estimated, and annual nutrient yields were calculated, for 47 stations for the long-term and recent periods, and for 37 additional stations that did not have a complete streamflow and water-quality record for 1993-2003. Nutrient yield information was incorporated for 9 drainage basins evaluated in a national NAWQA study, for a total of 93 stations evaluated for nutrient yields. Long-term downward trends in flow-adjusted concentrations of total nitrogen and total phosphorus (18 and 19 of 32 stations, respectively) indicate regional improvements in nutrient-related water-quality conditions. Most of the recent trends detected for total phosphorus were upward (17 of 83 stations), indicating possible reversals to the long-term improvements. Concentrations of nutrients in many streams persist at levels that are likely to affect aquatic habitat adversely and promote freshwater or coastal eutrophication. Recent trends for modeled instream concentrations, and modeled reference concentrations, were evaluated relative to ecoregion-based nutrient criteria proposed by the U.S. Environmental Protection Agency. Instream concentrations of total nitrogen and total phosphorus persist at levels higher than proposed criteria at more than one-third and about one-half, respectively, of the 46 stations analyzed. Long-term trends in nutrient loads were primarily downward, with downward trends in total nitrogen and total phosphorus loads detected at 12 and 17 of 32 stations, respectively. Upward trends were rare, with one upward trend for total nitrogen loads and none for total phosphorus. Trends in loads of nitrite-plus-nitrate nitrogen included 7 upward and 8 downward trends among 32 stations. Downward trends in loads of ammonia nitrogen and total Kjeldahl nitrogen were detected at all six stations evaluated. Long-term downward trends detected in four of the five largest drainage basins evaluated include: total nitrogen loads for the Connecticut, Delaware, and James Rivers; total Kjeldahl nitrogen and ammonia nitrogen loads for the Susquehanna River; ammonia nitrogen and nitrite-plus-nitrate nitrogen loads for the James River; and total phosphorus loads for the Connecticut and Delaware Rivers. No trends in load were detected for the Potomac River. Nutrient yields were evaluated relative to the extent of land development in 93 drainage basins. The undeveloped land-use category included forested drainage basins with undeveloped land ranging from 75 to 100 percent of basin area. Median total nitrogen yields for the 27 undeveloped drainage basins evaluated, including 9 basins evaluated in a national NAWQA study, ranged from 290 to 4,800 pounds per square mile per year (lb/mi 2 /yr). Total nitrogen yields even in the most pristine drainage basins may be elevated relative to natural conditions, because of high rates of atmospheric deposition of nitrogen in parts of the northeastern United States. Median total phosphorus yields ranged from 12 to 330 lb/mi 2 /yr for the 26 undeveloped basins evaluated. The undeveloped category includes some large drainage basins with point-source discharges and small percentages of developed land; in these basins, streamflow from undeveloped headwater areas dilutes streamflow in more urbanized reaches, and dampens but does not eliminate the point-source "signal" of higher nutrient loads. Median total nitrogen yields generally do not exceed 1,700 lb/mi 2 /yr, and median total phosphorus yields generally do not exceed 100 lb/mi 2 /yr, in the drainage basins that are least affected by human land-use and waste-disposal practices. Agricultural and urban land use has increased nutrient yields substantially relative to undeveloped drainage basins. Median total nitrogen yields for 24 agricultural basins ranged from 1,700 to 26,000 lb/mi 2 /yr, and median total phosphorus yields ranged from 94 to 1,000 lb/mi 2 /yr. The maximum estimated total nitrogen and total phosphorus yields, 32,000 and 16,000 lb/mi 2 /yr, respectively, for all stations in the region were in small (less than 50 square miles (mi 2 )) agricultural drainage basins. Median total nitrogen yields ranged from 1,400 to 17,000 lb/mi 2 /yr in 26 urbanized drainage basins, and median total phosphorus yields ranged from 43 to 1,900 lb/mi 2 /yr. Urbanized drainage basins with the highest nutrient yields are generally small (less than 300 mi2) and are drained by streams that receive major point-source discharges. Instream nutrient loads were evaluated relative to loads from point-source discharges in four drainage basins: the Quinebaug River Basin in Connecticut, Massachusetts, and Rhode Island; the Raritan River Basin in New Jersey; the Patuxent River Basin in Maryland; and the James River Basin in Virginia. Long-term downward trends in nutrient loads, coupled with similar trends in flow-adjusted nutrient concentrations, indicate long-term reductions in the delivery of most nutrients to these streams. However, the absence of recent downward trends in load for most nutrients, coupled with instream concentrations that exceed proposed nutrient criteria in several of these waste-receiving streams, indicates that challenges remain in reducing delivery of nutrients to streams from point sources. During dry years, the total nutrient load from point sources in some of the drainage basins approached or equaled the nutrient load transported by the stream.

Connecticut;Delaware;Maine;Maryl;Massachusetts;New↗

Pesticides in groundwater in the Anacostia River and Rock Creek watersheds in Washington, D.C., 2005 and 2008

The U.S. Geological Survey (USGS), in cooperation with the District Department of the Environment, conducted a groundwater-quality investigation to (a) determine the presence, concentrations, and distribution of selected pesticides in groundwater, and (b) assess the presence of pesticides in groundwater in relation to selected landscape, hydrogeologic, and groundwater-quality characteristics in the shallow groundwater underlying the Anacostia River and Rock Creek watersheds in Washington, D.C. With one exception, well depths were 100 feet or less below land surface. The USGS obtained or compiled ancillary data and information on land use (2001), subsurface sediments, and groundwater samples from 17 wells in the lower Anacostia River watershed from September through December 2005, and from 14 wells in the lower Anacostia River and lower Rock Creek watersheds from August through September 2008. Twenty-seven pesticide compounds, reflecting at least 19 different types of pesticides, were detected in the groundwater samples obtained in 2005 and 2008. No fungicides were detected. In relation to the pesticides detected, degradate compounds were as or more likely to be detected than applied (parent) compounds. The detected pesticides chiefly reflected herbicides commonly used in urban settings for non-specific weed control or insecticides used for nonspecific haustellate insects (insects with specialized mouthparts for sucking liquid) or termite-specific control. Detected pesticides included a combination of pesticides currently (2008) in use, banned or under highly restricted use, and some that had replaced the banned or restricted-use pesticides. The presence of banned and restricted-use pesticides illustrates their continued persistence and resistance to complete degradation in the environment. The presence of the replacement pesticides indicates the susceptibility of the surficial aquifer to contamination irrespective of the changes in the pesticides used. A preliminary review of the data collected in 2005 and 2008 indicated that differences in the surficial geology, land use (as a surrogate for pesticide use), and above-average precipitation for most of 2004 through 2008, as well as differences in the number and performance of USGS laboratory methods used, could have led to more pesticides detected in groundwater samples collected in 2008 than in groundwater samples collected in 2005. Thus, although data from both years of collection were used for interpretive analysis, emphasis was placed on the analysis of the data obtained in 2008. The presence of pesticides in shallow groundwater (less than approximately 100 ft (feet), or 30 m (meters), below land surface) indicated at least the upper surficial aquifer in Washington, D.C. was susceptible to contamination. One or more herbicides or insecticides were detected in groundwater samples collected from 50 percent of the shallow wells sampled in 2005, and from 62 percent of the shallow wells sampled in 2008. Differences among types of pesticides in shallow groundwater were apparent. The most frequently detected class of herbicides was the s-triazine compounds—atrazine, simazine, or prometon, or the atrazine-degradate compounds—2-chloro-4-ethylamino-6-amino-s-triazine (desethylatrazine or CIAT) and 2-chloro-4-isopropylamino-6-amino-s-triazine (hydroxyatrazine or OIET). The next most frequently detected classes of herbicides were the chloroacetanilides, including metolachlor and acetochlor, and the ureic herbicides, including diuron (and degradate, 3,4-dichloroaniline), fluometuron, metsulfuron methyl, sulfameturon, bromacil, and tebuthiuron. Insecticides also were detected, but less frequently than herbicides, with one or more insecticides present in groundwater samples from 38 percent of shallow wells sampled in 2008. Detected insecticides included parent or degradate compounds commonly used for either nonspecific or haustellate (sucking) insects, including chlorpyrifos and dichlorodiphenyldichloroethane (p,p’-DDD; a degradate of dichlorodiphenyltrichloroethane, DDT), and for termite control, including dieldrin, chlordane, heptachlor epoxide, (a degradate of heptachlor), fipronil, and the sulfone and sulfide degradates of fipronil. The concentrations of individual pesticides in shallow groundwater in both years were low. Maximum concentrations were no greater than a few tenths of a microgram per liter (μg/L); typical concentrations often were less than 0.1 μg/L. Multiple pesticides, however, commonly were present in groundwater. For example, in 2008, approximately 88 percent (7 of 8) of the wells that yielded a sample with at least one detectable pesticide contained five or more pesticides. The highest number of detections occurred in a groundwater sample from well WE Ca 32, which is located in a highly developed urban area; this sample contained 15 different pesticide residues. In relation to human and aquatic health, no pesticide concentration in either 2005 or 2008 exceeded Federal drinking-water standards. Groundwater samples from a few sites, however, contained levels of chiefly banned or restricted-use pesticides that exceeded other human-health and (or) aquatic-health guidelines. For example, concentrations of dieldrin in 2008 groundwater samples from three wells—WE Ca 32 (0.028 μg/L), WE Ba 11 (0.016 μg/L), and WW Ac 8 (0.014 μg/L)—fell within the range of concern for 2004 Federally approved non-regulatory USGS Health-Based Assessment benchmarks (0.002 to 0.2 μg/L), and exceeded earlier (1999) Federal criteria for drinking water (0.000052 μg/L). Other individual compounds whose concentrations exceeded 1999 Federal guidelines for samples from one or more of these three sites, or another site, included p,p’-DDD, dichlorodiphenyldichloroethylene (p,p’-DDE; another degradate of DDT), chlordane, and heptachlor epoxide. Pesticide concentrations in groundwater also were compared to three aquatic-health guidelines for freshwater (United States, Great Lakes, or Canada). One or more of these guidelines were exceeded in groundwater samples obtained in 2005 or 2008 for one or more of the compounds chlordane, dieldrin, heptachlor epoxide, p,p’-DDE, p,p’-DDD, and chlorpyrifos. The spatial distribution of pesticides in the shallow groundwater appeared to be related, in part, to land use, a surrogate for pesticide use. Although most of the wells sampled in this study are in parklands or other relatively open and accessible space, multiple pesticides most often were detected in 2008 groundwater samples collected from wells where a considerable percentage (in excess of 60 percent) of the land within a 500-m radius is developed space (residential, commercial, or other urban infrastructure). Insecticides were detected in wells surrounded by at least 50 percent, and most commonly by more than 80 percent, development. Well WE Ca 32, the site associated with the highest number of pesticide residues in groundwater (8 herbicides and 7 insecticides), is in a small residential park, where 99 percent of the surrounding land is well-maintained residential and commercial development. The vertical distribution of detected pesticides in shallow groundwater appeared to be related, in part, to depth below land surface, surficial-bedrock type, and differences in the chemistry of shallow groundwater. Pesticides were detected at relatively shallow depths in wells that may not have fully penetrated the shallow aquifer. For wells in which at least one pesticide was detected, the median depth below land surface to the top of the well screen was 5.8 m, and the maximum depth was 8.5 m. Among the types of surficial materials in which wells were completed—alluvium, terrace deposits, or Potomac Formation sub- or outcrops in the Coastal Plain Province, and saprolite or fractured bedrock (Laurel and Sykesville Formations) underlying saprolite in the Piedmont Province—no pesticides were detected in groundwater associated with wells completed in the alluvium or fractured bedrock. Detections occurred in some but not all wells completed in the other surficial materials. Overall, the pattern in occurrence appeared related to the local permeability of these sediments and groundwater chemistry. Groundwater with multiple pesticide detections tended to occur in permeable sediments (absent any appreciable overlying clay, silt, or clay-silt layers), in conjunction with other common urban contaminants (elevated chloride in excess of tens to hundreds of milligrams per liter (mg/L), and oxic, rather than reduced, groundwater as evidenced by elevated (in excess of 5 mg/L) concentrations of nitrate). The results of this investigation were compared to results from two other similar and recent studies on pesticide occurrence in the shallow aquifer. These included a study in the nearby Maryland and Delaware Coastal Plain Physiographic Province and one in the Maryland and Virginia Piedmont Physiographic Province. Results from these studies were similar to the current study in relation to (a) the types, frequencies, concentrations, and mixtures of pesticides detected; (b) compounds that exceeded human-and aquatic-health criteria; and (c) the occurrence and distribution of pesticides within the surficial aquifer in relation to depths, sediment types, and groundwater chemistries.

Washington D.C.↗

Assessment of groundwater availability in the Northern Atlantic Coastal Plain aquifer system From Long Island, New York, to North Carolina

Executive Summary The U.S. Geological Survey began a multiyear regional assessment of groundwater availability in the Northern Atlantic Coastal Plain (NACP) aquifer system in 2010 as part of its ongoing regional assessments of groundwater availability of the principal aquifers of the Nation. The goals of this national assessment are to document effects of human activities on water levels and groundwater storage, explore climate variability effects on the regional water budget, and provide consistent and integrated information that is useful to those who use and manage the groundwater resource. As part of this nationwide assessment, the USGS evaluated available groundwater resources within the NACP aquifer system from Long Island, New York, to northeastern North Carolina. The northern Atlantic Coastal Plain physiographic province depends heavily on groundwater to meet agricultural, industrial, and municipal needs. The groundwater assessment of the NACP aquifer system included an evaluation of how water use has changed over time; this evaluation primarily used groundwater budgets and development of a numerical modeling tool to assess system responses to stresses from future human uses and climate trends. This assessment focused on multiple spatial and temporal scales to examine changes in groundwater pumping, storage, and water levels. The regional scale provides a broad view of the sources and demands on the system with time. The sub-regional scale provides an evaluation of the differing response of the aquifer system across geographic areas allowing for closer examination of the interaction between different aquifers and confining units and the changes in these interactions under pumping and recharge conditions in 2013 and hydrologic stresses as much as 45 years in the future. By focusing on multiple scales, water-resource managers may utilize this study to understand system response to changes as they affect the system as a whole. The NACP aquifer system extends from Long Island to northeastern North Carolina, and includes aquifers primarily within New York, New Jersey, Delaware, Maryland, Virginia, and North Carolina. The seaward-dipping sedimentary wedge that underlies the northern Atlantic Coastal Plain physiographic province forms a complex groundwater system. Although the NACP aquifer system is recognized by the U.S. Geological Survey as one of the smallest of the 66 principal aquifer systems in the Nation, it ranks 13th overall in terms of total groundwater withdrawals and is 7th in population served. Despite abundant precipitation [about 45 inches per year (in/yr)], the supply of fresh surface water in this region is limited because many of the surface waters in this area are brackish estuaries, contributing to why many communities in the northern Atlantic Coastal Plain physiographic province rely heavily on groundwater to meet their water needs. Increases in population and changes in land use during the past 100 years have resulted in diverse increased demands for freshwater throughout the northern Atlantic Coastal Plain physiographic province with groundwater serving as a vital source of drinking water for the nearly 20 million people who live in the region. Total groundwater withdrawal in 2013 was estimated to be about 1,300 million gallons per day (Mgal/d) and accounts for about 40 percent of the drinking water supply with the densely populated areas tending to have the highest rates of withdrawals and, therefore, being most susceptible to effects from these withdrawals over time. Water levels in many of the confined aquifers are decreasing by as much as 2 feet per year (ft/yr) in response to extensive development and subsequent increased withdrawals throughout the region. Total water-level decreases (drawdowns) are more than 100 feet (ft) in some aquifers from their predevelopment (before 1900) levels. These drawdowns extend across state lines and under the Chesapeake and Delaware Bays, creating the potential for interstate aquifer management issues. Regional water-resources managers in the northern Atlantic Coastal Plain physiographic province face challenges beyond competing local domestic, industrial, agricultural, and environmental demands for water. Large changes in regional water use have made the State-level management of aquifer resources more difficult because of hydrologic effects that extend beyond State boundaries. The northern Atlantic Coastal Plain physiographic province is underlain by a wedge of unconsolidated to partially consolidated sediments that are typically thousands of feet thick along the coastline with a maximum thickness of about 10,000 ft near the edge of the continental shelf. The NACP aquifer system consists of nine confined aquifers and nine confining units capped by an unconfined surficial aquifer that is bounded laterally from the west by the contact between Coastal Plain sediments and the upland Piedmont bedrock. This aquifer system extends to the east to the limit of the Continental Shelf, however, the boundary between fresh and saline groundwater is considered to be much closer to the shoreline and varies vertically by aquifer. Precipitation over the region for average conditions from 2005 to 2009 is about 61,800 Mgal/d, but about 70 percent of it is lost to evapotranspiration resulting in an inflow of about 19,600 Mgal/d entering the groundwater system as aquifer recharge. Most of this recharge enters the aquifer system and flows through the shallow unconfined aquifer and either discharges to streams or directly to coastal waters without reaching the deep, confined aquifer system. In addition to recharge from precipitation, other sources of water include the return of wastewater from domestic septic systems of about 240 Mgal/d, about 60 Mgal/d of water released from storage in the confined system, and about 30 Mgal/d of lateral inflow at the boundary between freshwater and saltwater in response to pumping for conditions in 2013. The outflow needed to balance the inflows was subdivided between streamflow, discharge to tidal portions of streams, and coastal discharge. The hydrologic budget developed for current [2013] conditions determined that 93 percent of the total outflow was to surface waters with about 70 percent divided evenly between streamflow and shallow coastal discharge and 23 percent as discharge to tidal waters. The remaining 7 percent of the total outflow components include withdrawals from both the surficial and confined aquifers of the groundwater system. The groundwater availability assessment of the NACP aquifer system highlights the importance of analyses at both the regional and local scales to understand how changes in land use, water use, and climate have affected groundwater resources and how these resources may change in the future. The investigation included assessments of the regional changes in water levels and budgets across State lines, the importance of considering storage change in the confining units, the response of the aquifer system to a continuation of current [2013] hydrologic stresses into the future, and the potential effects of climate change and sea-level rise on the aquifer system. The Potomac aquifer group includes two of the most widely used aquifers in the NACP aquifer system, the Potomac-Patapsco and Potomac-Patuxent regional aquifers, providing about 24 percent of the total groundwater used in the region. Withdrawals from large pumping centers in this deep, confined aquifer group have resulted in substantial decreases in water-levels across state lines, particularly between southern Virginia and northeastern North Carolina as well as between southern New Jersey and northern Delaware where water levels in the Potomac-Patapsco aquifer have decreased by as much as 200 ft and 50 ft, respectively from predevelopment to current [2013] conditions. This response in water levels also is reflected in changes in water budgets where, for example, about 20 percent of the total response to pumping in Virginia is met by inducing flow from adjacent States. Understanding and quantifying these hydrologic effects that extend beyond State boundaries is critical for the State- and regional-level management of aquifer resources. The cumulative storage loss from the intervening confining units throughout the entire NACP aquifer system was about 35 percent of the total storage loss from predevelopment to current [2013] conditions. In geographic areas such as Delmarva Peninsula, Maryland, and New Jersey, the water released from storage in the confining units makes up the majority of the total storage release from the groundwater system and is becoming proportionally more important over time as the surficial aquifer approaches equilibrium with respect to pumping and recharge stresses as of 2013. Storage loss from the confining units is of particular concern because, unlike in the sands that comprise the confined aquifers, water removed from the clayey confining unit sediments cannot be replenished as these units gradually compress. This non-recoverable storage loss, if great enough, can result in land subsidence where these units are thick and the release from storage is relatively large and contributes to increased concerns for sea-level rise in areas such as the lower portion of the Chesapeake Bay. Groundwater usage increased dramatically in the NACP aquifer system during post-World War II era from the mid-1940s to early the 1980s, with withdrawals increasing from about 400 Mgal/d to more than 1,300 Mgal/d. Although groundwater withdrawals have been relatively constant since the early 1980s, about half of the total groundwater withdrawn from the NACP aquifer system since 1900 was withdrawn in the past 30 years. An analysis of the response of the groundwater system to a continuation of the current [2013] pumping for an additional 30 years into the future shows that the flow system continues to adjust in terms of changes in water budget components, water levels, and the boundary between freshwater and saltwater as it approaches equilibrium. The largest change in water budget components is the reduction in the amount of water released from storage. Across the entire NACP aquifer system, the reduction of storage release from 7 to 4 percent of the total water budget change is accounted for by reductions in groundwater discharge to streams and coastal waters. Locally, a similar response is calculated for each of the geographic areas except for Virginia where the amount of water released from storage accounts for about 25 percent of the total change in water budget. This finding suggests that the groundwater flow system in Virginia is not approaching equilibrium under the current [2013] stresses and, therefore, water levels will continue to decrease even if the pumping remains constant. An analysis of the change in water levels in the Potomac-Patapsco aquifer as pumping is continued 30 years into the future reveals that the largest decreases in water levels throughout the NACP aquifer system will occur in the southern Virginia and northeastern North Carolina parts of the study area. It is these areas that also see the greatest potential for increased lateral movement of saline groundwater in the deep, confined portion of the groundwater flow system in response to a continuation of the current [2013] pumping rates. The potential effects of long-term climate change and variability on the hydrologic system and availability of water resources in the NACP aquifer system continue to be of serious societal concern. These concerns include the effects of changes in aquifer recharge and in sea-level rise on the groundwater flow system. An assessment of the potential effects of a prolonged drought during current [2013] pumping conditions indicated that the reductions in recharge associated with droughts, including additional irrigation withdrawals required to meet increased crop water demand, have the greatest effects on water levels and streamflows in the surficial aquifer, and changes in water levels in the confined aquifers primarily resulted from the increased withdrawals associated with increased irrigation pumping; this response was most apparent in the Delmarva Peninsula. These results suggest that water levels may not be susceptible to the effects of droughts in the confined aquifers of the NACP aquifer system not used for irrigation, unlike in the unconfined surficial aquifer. A second analysis also was conducted to assess the effects of sea-level rise on the groundwater system throughout the northern Atlantic Coastal Plain physiographic province because recent analyses of the relative rates of sea-level rise along the Atlantic coast indicate that the Mid-Atlantic region represents a hot spot with anomalously higher rates of sea-level rise than observed elsewhere in the United States. Groundwater levels rose from 0 to 3 ft in response to a 3-ft simulated change in sea-level position, with the largest response occurring along the shoreline and away from non-tidal streams. About 37 percent (or 10,000 square miles) of the area of the northern Atlantic Coastal Plain physiographic province may experience about a 0.5-ft or more increase in water levels with the 3-ft increase in sea-level position, whereas about 18 percent (almost 5,000 square miles) of land of the northern Atlantic Coastal Plain physiographic province may experience a 2-ft or more increase in water levels with the 3-ft increase in sea-level position. These increases in the water table are of particular concern in low-lying areas where the unsaturated (vadose) zone is already thin, thus creating concerns for groundwater inundation of subsurface infrastructure, such as basements, septic systems, and subway systems. This increase in the water table also will likely alter the distribution of groundwater discharge to surface-water bodies thus increasing groundwater flow to streams that would have otherwise discharged directly to coastal waters. Throughout the NACP aquifer system, this redistribution of groundwater discharge results in an additional 2 percent of base flow in streams. Although the increases in groundwater discharge to streams (and corresponding decreases in discharge to coastal waters) calculated for the entire NACP aquifer system and its geographic areas represent only a small increase compared with current [2013] conditions, this redistribution of groundwater discharge from the coast to streams locally can alter the delivery of freshwater input to coastal receiving waters and have ecohydrological implications on the sensitive ecosystems which rely on a balance of groundwater discharge and surface-water flow.

Delaware, Maryland, New Jersey, New York, North Ca↗