Seasonality of Nitrogen Sources, Cycling, and Loading in a New England River Discerned from Nitrate Isotope Ratios
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Biogeosciences, 18, 3421–3444, 2021 https://doi.org/10.5194/bg-18-3421-2021 © Author(s) 2021. This work is distributed under the Creative Commons Attribution 4.0 License. Seasonality of nitrogen sources, cycling, and loading in a New England river discerned from nitrate isotope ratios Veronica R. Rollinson1, Julie Granger1, Sydney C. Clark2, Mackenzie L. Blanusa1, Claudia P. Koerting1, Jamie M. P. Vaudrey1, Lija A. Treibergs1,4, Holly C. Westbrook1,3, Catherine M. Matassa1, Meredith G. Hastings2, and Craig R. Tobias1 1Department of Marine Sciences, University of Connecticut, Groton, 06340, USA 2Department of Earth, Environmental and Planetary Sciences, Brown University, Providence, 02912, USA 3School or the Earth, Ocean and Environment, University of South Carolina, Columbia, 29208, USA 4Adirondack Watershed Institute, Paul Smith’s College, Paul Smiths, 12970, USA Correspondence: Veronica R. Rollinson ([email protected]) Received: 17 October 2020 – Discussion started: 4 November 2020 Revised: 10 February 2021 – Accepted: 11 February 2021 – Published: 10 June 2021 Abstract. Coastal waters globally are increasingly impacted and forested catchments to the more urbanized watershed due to the anthropogenic loading of nitrogen (N) from the downriver. The evolution of 18O = 16O isotope ratios along- watershed. To assess dominant sources contributing to the river conformed to the notion of nutrient spiraling, reflect- − eutrophication of the Little Narragansett Bay estuary in ing the input of NO3 from the catchment and from in-river New England, we carried out an annual study of N loading nitrification and its coincident removal by biological con- from the Pawcatuck River. We conducted weekly monitor- sumption. These findings stress the importance of consider- − 15 14 ing of nutrients and nitrate (NO3 ) isotope ratios ( N = N, ing seasonality of riverine N sources and loading to mitigate 18O = 16O, and 17O = 16O) at the mouth of the river and from eutrophication in receiving estuaries. Our study further ad- the larger of two wastewater treatment facilities (WWTFs) vances a conceptual framework that reconciles with the cur- along the estuary, as well as seasonal along-river surveys. rent theory of riverine nutrient cycling, from which to ro- − Our observations reveal a direct relationship between N load- bustly interpret NO3 isotope ratios to constrain cycling and ing and the magnitude of river discharge and a consequent source partitioning in river systems. seasonality to N loading into the estuary – rendering loading from the WWTFs and from an industrial site more impor- tant at lower river flows during warmer months, compris- ing ∼ 23 % and ∼ 18 % of N loading, respectively. River- 1 Introduction ine nutrients derived predominantly from deeper groundwa- ter and the industrial point source upriver in summer and Human activities have resulted in a substantial increase in from shallower groundwater and surface flow during colder the delivery of nutrients from terrestrial to aquatic and ma- − rine systems (Gruber and Galloway, 2008). In marine sys- months – wherein NO3 associated with deeper groundwa- ter had higher 15N = 14N ratios than shallower groundwater. tems, increased loading of reactive nitrogen (N) has re- − 18 16 sulted in coastal eutrophication, engendering the loss of Corresponding NO3 O = O ratios were lower during the warm season, due to increased biological cycling in-river. valuable nearshore habitat such as seagrass beds and oys- − ter reefs, depletion of dissolved oxygen (creating so-called Uncycled atmospheric NO3 , detected from its unique mass- − 17 16 18 16 “dead zones”), and increased frequency and severity of al- independent NO3 O = O vs. O = O fractionation, ac- − gal blooms – including toxic brown and red tides causing counted for < 3 % of riverine NO3 , even at elevated dis- − 15 14 fish kills (Heisler et al., 2008). In densely populated areas charge. Along-river, NO3 N = N ratios showed a corre- spondence to regional land use, increasing from agricultural like the northeast United States, excess anthropogenic ni- trogen loads originate from wastewater treatment facilities Published by Copernicus Publications on behalf of the European Geosciences Union. 3422 V. R. Rollinson et al.: Seasonality of nitrogen sources, cycling, and loading (WWTFs), septic systems, industrial discharge, fertilizer ap- tation: plied to turf and agricultural lands, and atmospheric sources isotope ratio of sample from industry and fossil fuel use (Valiela et al., 1997; Mc- δ .‰/ D − 1 × 1000: (1) isotope ratio of reference Clelland et al., 2003; Latimer and Charpentier, 2010). The 15 18 pervasive degradation of coastal marine ecosystems is alarm- The reference for δ N is N2 in air and for δ O is Vienna ing and of significant concern to coastal communities world- Standard Mean Ocean Water (VSMOW). The N and O iso- − wide. tope ratios of NO3 provide constraints on N sources and The transfer of nutrients from land to the coast is facil- cycling in part because respective N sources cover discrete itated by rivers, which constitute an effective pipeline that ranges of δ15N and δ18O values (Kendall et al., 2007). Re- collects nutrients from the watershed, ultimately discharging active N species from atmospheric deposition, biological N2 these to the coast. The mitigation of estuarine eutrophica- fixation, and industrial N2 fixation share overlapping ranges tion thus relies on identifying primary sources of nutrients of δ15N values (≤ 0 ‰), which differ appreciably from those to riverine systems. Nutrients are fundamentally delivered to of livestock and human waste (8 ‰–25 ‰; Kendall, 1998; rivers from non-point sources: from waters entering the river Böhlke, 2003; Xue et al., 2009). In contrast, the δ18O sig- − via surface runoff, sub-surface groundwater in the unsatu- natures of atmospheric NO3 (60 ‰–80 ‰) are distinct from − ∼ − rated zone, and groundwater within the water table. Nutrients those of industrial NO3 ( 25 ‰) and from NO3 produced also enter rivers from point sources, including WWTFs as by nitrification, which aligns closely with that of ambient well as industrial discharge, which can dominate N loading water (Boshers et al., 2019, and references therein). Atmo- − in urbanized watersheds (Howarth et al., 1996). The nutri- spheric NO3 is further distinguished by a mass-independent ent loads contained in surface and deeper groundwater enter- δ17O vs. δ18O fractionation that is not manifest in industrial ing rivers differ markedly depending on land use. In temper- and biological NO− (Savarino and Thiemens, 1999). 3 − ate pristine systems, soil and groundwater concentrations are The isotope ratios of NO3 also provide constraints on N generally low, with reactive N originating from atmospheric cycling because N and O isotopologues are differentially sen- deposition, biological N2 fixation in soils, and N in rocks sitive to respective biological N transformations (reviewed and minerals (Hendry et al., 1984; Holloway et al., 1998; by Casciotti, 2016), implicating different mass balance con- Morford et al., 2016). Higher concentrations of reactive N siderations within the N cycle that permit differentiation of are found in waters draining agricultural and urbanized areas N sources from cycling. Briefly, in riverine systems where − 15 (Dubrovsky et al., 2010; Baron et al., 2013). NO is the dominant N pool, δ NNO integrates across val- 3 3 − The N loaded to the watershed is partially attenuated ues of reactive N delivered from the watershed, minus NO3 through biological cycling in soils and aquifers. Specifically, removed by benthic denitrification (if associated with N iso- 15 organic N is degraded to reduced N species that are oxidized topic fractionation; Sebilo et al., 2003). Values of δ NNO − 3 (nitrified) to nitrate (NO3 ) in oxygenated zones of ground- are additionally sensitive to isotopic fractionation due to in- water. NO− is otherwise removed from anoxic groundwater ternal cycling in-river – assimilation and remineralization to 3 − by denitrification, reduced to inert N2. Reactive N is further NO3 via nitrification – in systems where riverine N is other- cycled and attenuated in-river. The hyporheic zone, where wise partitioned comparably between oxidized and reduced − groundwater interchanges with stream and river water, cre- pools (i.e., NO3 vs. ammonium and particulate N; Sebilo et 18 ates a complex environment that can stimulate nitrification al., 2006). Riverine δ ONO , in turn, integrates across values − 3 and denitrification, as oxic and anoxic pockets exist in close of exogenous NO3 delivered to the river from the watershed proximity (Sebilo et al., 2003; Harvey et al., 2013). Reactive and from atmospheric deposition, those of NO− produced − 3 nitrogen can be further attenuated by benthic denitrification in-river by nitrification, minus the NO3 lost concurrently within the river channel (Sebilo et al., 2003; Kennedy et al., to denitrification and assimilation (see Sigman and Fripiat, − 2008; Mulholland et al., 2008). 2019). Interpreted in tandem, NO3 N and O isotopologue Identifying sources of N to rivers can be difficult due to ratios thus offer complementary constraints to identify im- the expanse and heterogeneity of the watershed, the long in- portant source terms and characterize cycling. tegration time of deeper groundwater, and the degree of bi- Here we present a study of annual N loading from the Paw- ological N cycling in groundwater and in-river. While mea- catuck River to the Little Narragansett Bay in southern