Geochemical conditions and nitrogen transport in nearshore groundwater and the subterranean estuary at a Cape Cod embayment, East Falmouth, Massachusetts, 2013–14

Abstract

Nitrogen transport and transformation were studied during 2013 to 2014 by the U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency, in a subterranean estuary beneath onshore locations on the Seacoast Shores peninsula, a residential area in Falmouth, Massachusetts, served by septic systems and cesspools, and adjacent offshore locations in the Eel River, a saltwater embayment connected to the ocean. The field investigation included installation and sampling of clusters of wells and temporary sampling points near a transect extending from about 35 meters (m) onshore to 18 m offshore. The fresh groundwater at the study site formed a lens about 11 m thick at the shoreline that was underlain by saline groundwater. Groundwater flow in the water-table aquifer was oriented northwestward toward the embayment. Nitrate concentrations in the fresh groundwater at a site about 35 m onshore increased in the downward direction from less than 500 micromoles per liter near the water table to about 1,700 micromoles per liter just above the freshwater/saltwater transition zone. Dissolved oxygen was largely absent in the onshore fresh groundwater. Distributions of salinity, dissolved oxygen, and nitrate at the shoreline and offshore generally were similar to those onshore; at some locations, however, shallow saline water was present above the freshwater, and there were scattered occurrences of elevated dissolved oxygen concentrations. Geochemical indicators of nitrate reduction, including concentrations of the reaction product nitrogen gas, stable isotope ratios of nitrate and nitrogen gas, and changes in alkalinity, provided evidence for nitrate reduction in two zones separated vertically by a zone 7–8 m thick with no evidence of nitrate reduction. The shallow nitrate-reduction zone was near the water table in fresh groundwater onshore, where nitrate reduction may be related to particular recharge conditions at nearby sources. The shallow nitrate-reduction zone also may be related to an interval of fine-grained sediments at about the same altitude (−1 to −6 m relative to the National Geodetic Vertical Datum of 1929), where flow is slower and reactive electron donors such as solid organic carbon, iron, or sulfide phases may be present to drive the reduction. The deep nitrate-reduction zone was near the freshwater/saltwater transition zone, where nitrate reduction may be related to mixing of freshwater containing nitrate and saltwater containing dissolved organic carbon and ammonium, or to fine-grained sediments near the transition zone. The maximum amount of nitrate converted to nitrogen gas was estimated to be less than or equal to 300 micromoles per liter in both nitrate-reduction zones. The presence of nitrate and low dissolved oxygen concentrations in the 7–8-meter-thick zone between the shallow and deep nitrate-reduction zones are conditions that could permit nitrate reduction. The absence of evidence of nitrate reduction in the high-nitrate zone may have resulted from the lack of reactive electron donors in that depth interval. The high-nitrate zone dissipated somewhat in the offshore direction, but the current study did not extend far enough to encompass the fresh groundwater discharge area or determine how much of the nitrate was removed prior to discharge. A shallow intertidal saltwater cell was formed during a spring tide by saltwater infiltration during tidal run-up on the beach. Nitrate reduction might have occurred if nitrate-containing fresh groundwater discharging to the estuary mixed with the saltwater containing dissolved organic carbon in this zone, but samples collected from the intertidal saltwater cell during this study were not analyzed for indicators of nitrate reduction. Elevated dissolved oxygen concentrations in fresh groundwater 9 m offshore may indicate that groundwater flow was partly oblique to the sampling transect or that groundwater from a regional flow system was converging under the river near the study area. Flow directions also may have been affected by aquifer heterogeneity such as the shallow fine-grained sediments onshore and at the bottom of the Eel River. Improved understanding of the fate of nitrate in this type of complex setting might be gained by including additional characterization of aquifer heterogeneity and groundwater flow and extending investigations of nitrate reduction to the shallow sediments in the intertidal saltwater cell and adjacent subtidal zone and to locations farther offshore beneath the estuary.