Evidence of nitrate attenuation in intertidal and subtidal groundwater in a subterranean estuary at a Cape Cod embayment, East Falmouth, Massachusetts, 2015–16

Nitrogen dynamics in intertidal and nearshore subtidal groundwater (subterranean estuary) adjacent to the Seacoast Shores peninsula, Falmouth, Massachusetts, were investigated during 2015–16 by the U.S. Geological Survey. The peninsula is a densely populated residential area with septic systems and cesspools that are substantial sources of nitrogen to groundwater. The study area is in the Eel River, an estuarine saltwater embayment connected to the ocean adjacent to the western shore of the peninsula, that was the subject of an earlier study by Colman and others (2018, https://doi.org/10.3133/sir20185095) on nitrogen transport and transformations in groundwater between onshore and offshore locations. The previous study documented the distribution of nitrate concentrations and nitrate attenuation reactions in fresh groundwater beneath the peninsula and the estuary. The current study extended those observations with more detailed sampling and analysis of shallow groundwater from wells near discharge sites beneath the estuary. The current field investigation included sampling of existing wells and installation and sampling of clusters of wells and temporary sampling points in the subterranean estuary, including (1) shallow transects 0.3 to 1.2 meters (m) deep extending from 1 to 13.5 m offshore and (2) deeper wells (from 1.83 to 4.88 m deep) extending from 4.3 to 14.3 m offshore.

Measurements of hydraulic-head gradients 2–5 m below the sediment/water interface in the intertidal and nearshore subtidal zones indicated that groundwater flow generally was upwards (towards the estuary) under all tide conditions in October 2016. The magnitude of the gradient was greatest during low tide conditions, indicating that groundwater discharge likely decreased during high tides.

Measurements of specific conductance in shallow groundwater in the subterranean estuary in three transects perpendicular to shore were consistent with the existence of saltwater flow cells (infiltration of overlying saline water, mixing with fresh groundwater, and discharge to the overlying saline water) in the intertidal and nearshore subtidal regions. The size of these flow cells was variable in space and time and dependent on the elevation of the tide (spring or neap). At this location in the Eel River subterranean estuary, and offshore to at least 13.5 m, offshore flow of fresh groundwater apparently prevented a deeper saltwater wedge from discharging to the surface.

Nitrate concentrations in shallow groundwater (30 to 122 centimeters [cm] depth) were variable in space and time, ranging from not detectable to 600 micromoles per liter (μmol/L) (8.4 milligrams per liter as N), and were highest in June 2016 at depths from 61 to 122 cm below the sediment/water interface and from 4 to 9 m offshore. Nitrate generally was not detectable in saline shallow groundwater at 30-cm depth or at any depth from 30 to 122 cm from 10 to 13.5 m offshore. Dissolved oxygen concentrations were suboxic (less than 16 μmol/L) in 60 percent of the sampled subterranean groundwater beneath the intertidal and subtidal zones. In the remaining sites, the range of dissolved oxygen concentrations was from 18 to 272 μmol/L and the median concentration was 43 μmol/L.

Evidence for microbial nitrate reduction (denitrification and possibly anammox) was provided by the distribution of the reaction product nitrogen gas (excess N₂, or N_2MIC), as determined from analysis of the dissolved nitrogen gas and argon gas (Ar) concentrations in groundwater samples. Excess nitrogen gas provided evidence for nitrate reduction in shallow groundwater below the subtidal and, to a lesser extent, intertidal zones adjacent to the Seacoast Shores peninsula. These zones, where evidence for nitrate reduction was detected, were in fresh and brackish groundwater near subtidal or intertidal saltwater cells where discharging fresh groundwater mixed with infiltrating saline water. Infiltrating seawater may have supplied organic carbon, one of several potential electron donors that are required for denitrification. Other potential electron donors, such as organic carbon, iron, manganese, hydrogen, methane, ammonium, elemental sulfur, or sulfide phases, may have been supplied by the estuarine sediments. Drainage from surface runoff near the shore also may have supplied organic carbon to fresh groundwater near the intertidal saltwater cell.

The highest amounts of nitrate converted to excess nitrogen gas were estimated to be in the range of 230 to 430 μmol/L in nearly fresh groundwater near the subtidal saltwater cell at depths of 61 to 122 cm below the sediment/water interface and from 10 to 13.5 m offshore. Evidence of denitrification within 10 m of the shore was sparse (generally limited to less than 50 μmol/L of N₂-N) despite the presence of high nitrate concentrations. The spatial distribution of estimated nitrate reduction in the intertidal and nearshore subtidal fresh and brackish groundwater may be related to local variability in the distribution of reactive electron donors in those zones. Variations in the amount of nitrate reduction to nitrogen gas were not clearly related to potential aqueous electron donors such as dissolved organic carbon, nor to potential reaction products such as alkalinity, but may have been controlled by combinations of aqueous and solid-phase reactants. The distribution of relatively shallow fresh groundwater containing nitrate could indicate potential nitrate discharge areas in the lower intertidal zone and uncertain locations farther offshore; however, the data did not extend all the way to the sediment/water interface or to the offshore freshwater limit. This study confirmed substantial loss of nitrate from some of the fresh and brackish groundwater in shallow subestuarine sediments prior to discharge but did not quantify how much nitrate eventually discharged to the estuary.