Articles | Volume 18, issue 11
https://doi.org/10.5194/bg-18-3421-2021
© Author(s) 2021. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/bg-18-3421-2021
© Author(s) 2021. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
10 Jun 2021
Research article |
| 10 Jun 2021
| 10 Jun 2021
Seasonality of nitrogen sources, cycling, and loading in a New England river discerned from nitrate isotope ratios
Veronica R. Rollinson
CORRESPONDING AUTHOR
Department of Marine Sciences, University of Connecticut, Groton,
06340, USA
Julie Granger
Department of Marine Sciences, University of Connecticut, Groton,
06340, USA
Sydney C. Clark
Department of Earth, Environmental and Planetary Sciences, Brown
University, Providence, 02912, USA
Mackenzie L. Blanusa
Department of Marine Sciences, University of Connecticut, Groton,
06340, USA
Claudia P. Koerting
Department of Marine Sciences, University of Connecticut, Groton,
06340, USA
Jamie M. P. Vaudrey
Department of Marine Sciences, University of Connecticut, Groton,
06340, USA
Lija A. Treibergs
Department of Marine Sciences, University of Connecticut, Groton,
06340, USA
Adirondack Watershed Institute, Paul Smith's College, Paul Smiths,
12970, USA
Holly C. Westbrook
Department of Marine Sciences, University of Connecticut, Groton,
06340, USA
School or the Earth, Ocean and Environment, University of South
Carolina, Columbia, 29208, USA
Catherine M. Matassa
Department of Marine Sciences, University of Connecticut, Groton,
06340, USA
Meredith G. Hastings
Department of Earth, Environmental and Planetary Sciences, Brown
University, Providence, 02912, USA
Craig R. Tobias
Department of Marine Sciences, University of Connecticut, Groton,
06340, USA
Related authors
Josie L. Mottram, Anne M. Gothmann, Maria G. Prokopenko, Austin Cordova, Veronica Rollinson, Katie Dobkowski, and Julie Granger
Biogeosciences, 21, 1071–1091, https://doi.org/10.5194/bg-21-1071-2024, https://doi.org/10.5194/bg-21-1071-2024, 2024
Short summary
Short summary
Knowledge of ancient ocean N cycling can help illuminate past climate change. Using field and lab studies, this work ground-truths a promising proxy for marine N cycling, the N isotope composition of cold-water coral (CWC) skeletons. Our results estimate N turnover in CWC tissue; quantify the isotope effects between CWC tissue, diet, and skeleton; and suggest that CWCs possibly feed mainly on metazoan zooplankton, suggesting that the marine N proxy may be sensitive to the food web structure.
Wendell W. Walters, Masayuki Takeuchi, Danielle E. Blum, Gamze Eris, David Tanner, Weiqi Xu, Jean Rivera-Rios, Fobang Liu, Tianchang Xu, Greg Huey, Justin B. Min, Rodney Weber, Nga L. Ng, and Meredith G. Hastings
Atmos. Chem. Phys., 25, 10707–10730, https://doi.org/10.5194/acp-25-10707-2025, https://doi.org/10.5194/acp-25-10707-2025, 2025
Short summary
Short summary
We studied how chemicals released from plants and pollution interact in the atmosphere, affecting air quality and climate. By combining laboratory experiments and chemistry models, we tracked unique chemical fingerprints to understand how nitrogen compounds transform to form particles in the air. Our findings help explain the role of these reactions in pollution and provide tools to improve predictions for cleaner air and better climate policies.
Wendell W. Walters, Masayuki Takeuchi, Nga L. Ng, and Meredith G. Hastings
Geosci. Model Dev., 17, 4673–4687, https://doi.org/10.5194/gmd-17-4673-2024, https://doi.org/10.5194/gmd-17-4673-2024, 2024
Short summary
Short summary
The study introduces a novel chemical mechanism for explicitly tracking oxygen isotope transfer in oxidized reactive nitrogen and odd oxygen using the Regional Atmospheric Chemistry Mechanism, version 2. This model enhances our ability to simulate and compare oxygen isotope compositions of reactive nitrogen, revealing insights into oxidation chemistry. The approach shows promise for improving atmospheric chemistry models and tropospheric oxidation capacity predictions.
Josie L. Mottram, Anne M. Gothmann, Maria G. Prokopenko, Austin Cordova, Veronica Rollinson, Katie Dobkowski, and Julie Granger
Biogeosciences, 21, 1071–1091, https://doi.org/10.5194/bg-21-1071-2024, https://doi.org/10.5194/bg-21-1071-2024, 2024
Short summary
Short summary
Knowledge of ancient ocean N cycling can help illuminate past climate change. Using field and lab studies, this work ground-truths a promising proxy for marine N cycling, the N isotope composition of cold-water coral (CWC) skeletons. Our results estimate N turnover in CWC tissue; quantify the isotope effects between CWC tissue, diet, and skeleton; and suggest that CWCs possibly feed mainly on metazoan zooplankton, suggesting that the marine N proxy may be sensitive to the food web structure.
Jessica M. Burger, Emily Joyce, Meredith G. Hastings, Kurt A. M. Spence, and Katye E. Altieri
Atmos. Chem. Phys., 23, 5605–5622, https://doi.org/10.5194/acp-23-5605-2023, https://doi.org/10.5194/acp-23-5605-2023, 2023
Short summary
Short summary
A seasonal analysis of the nitrogen isotopes of atmospheric nitrate over the remote Southern Ocean reveals that similar natural NOx sources dominate in spring and summer, while winter is representative of background-level conditions. The oxygen isotopes suggest that similar oxidation pathways involving more ozone occur in spring and winter, while the hydroxyl radical is the main oxidant in summer. This work helps to constrain NOx cycling and oxidant budgets in a data-sparse remote marine region.
Claire Bekker, Wendell W. Walters, Lee T. Murray, and Meredith G. Hastings
Atmos. Chem. Phys., 23, 4185–4201, https://doi.org/10.5194/acp-23-4185-2023, https://doi.org/10.5194/acp-23-4185-2023, 2023
Short summary
Short summary
Nitrate is a critical component of the atmosphere that degrades air quality and ecosystem health. We have investigated the nitrogen isotope compositions of nitrate from deposition samples collected across the northeastern United States. Spatiotemporal variability in the nitrogen isotope compositions was found to track with nitrate formation chemistry. Our results highlight that nitrogen isotope compositions may be a robust tool for improving model representation of nitrate chemistry.
Heejeong Kim, Wendell W. Walters, Claire Bekker, Lee T. Murray, and Meredith G. Hastings
Atmos. Chem. Phys., 23, 4203–4219, https://doi.org/10.5194/acp-23-4203-2023, https://doi.org/10.5194/acp-23-4203-2023, 2023
Short summary
Short summary
Atmospheric nitrate has an important impact on human and ecosystem health. We evaluated atmospheric nitrate formation pathways in the northeastern US utilizing oxygen isotope compositions, which indicated a significant difference between the phases of nitrate (i.e., gas vs. particle). Comparing the observations with model simulations indicated that N2O5 hydrolysis chemistry was overpredicted. Our study has important implications for improving atmospheric chemistry model representation.
Wendell W. Walters, Madeline Karod, Emma Willcocks, Bok H. Baek, Danielle E. Blum, and Meredith G. Hastings
Atmos. Chem. Phys., 22, 13431–13448, https://doi.org/10.5194/acp-22-13431-2022, https://doi.org/10.5194/acp-22-13431-2022, 2022
Short summary
Short summary
Atmospheric ammonia and its products are a significant source of urban haze and nitrogen deposition. We have investigated the seasonal source contributions to a mid-sized city in the northeastern US megalopolis utilizing geospatial statistical analysis and novel isotopic constraints, which indicate that vehicle emissions were significant components of the urban-reduced nitrogen budget. Reducing vehicle ammonia emissions should be considered to improve ecosystems and human health.
Jessica M. Burger, Julie Granger, Emily Joyce, Meredith G. Hastings, Kurt A. M. Spence, and Katye E. Altieri
Atmos. Chem. Phys., 22, 1081–1096, https://doi.org/10.5194/acp-22-1081-2022, https://doi.org/10.5194/acp-22-1081-2022, 2022
Short summary
Short summary
The nitrogen (N) isotopic composition of atmospheric nitrate in the Southern Ocean (SO) marine boundary layer (MBL) reveals the importance of oceanic alkyl nitrate emissions as a source of reactive N to the atmosphere. The oxygen isotopic composition suggests peroxy radicals contribute up to 63 % to NO oxidation and that nitrate forms via the OH pathway. This work improves our understanding of reactive N sources and cycling in a remote marine region, a proxy for the pre-industrial atmosphere.
Jiajue Chai, Jack E. Dibb, Bruce E. Anderson, Claire Bekker, Danielle E. Blum, Eric Heim, Carolyn E. Jordan, Emily E. Joyce, Jackson H. Kaspari, Hannah Munro, Wendell W. Walters, and Meredith G. Hastings
Atmos. Chem. Phys., 21, 13077–13098, https://doi.org/10.5194/acp-21-13077-2021, https://doi.org/10.5194/acp-21-13077-2021, 2021
Short summary
Short summary
Nitrous acid (HONO) derived from wildfire emissions plays a key role in controlling atmospheric oxidation chemistry. However, the HONO budget remains poorly constrained. By combining the field-observed concentrations and novel isotopic composition (N and O) of HONO and nitrogen oxides (NOx), we quantitatively constrained the relative contribution of each pathway to secondary HONO production and the relative importance of major atmospheric oxidants (ozone versus peroxy) in aged wildfire smoke.
Guitao Shi, Hongmei Ma, Zhengyi Hu, Zhenlou Chen, Chunlei An, Su Jiang, Yuansheng Li, Tianming Ma, Jinhai Yu, Danhe Wang, Siyu Lu, Bo Sun, and Meredith G. Hastings
The Cryosphere, 15, 1087–1095, https://doi.org/10.5194/tc-15-1087-2021, https://doi.org/10.5194/tc-15-1087-2021, 2021
Short summary
Short summary
It is important to understand atmospheric chemistry over Antarctica under a changing climate. Thus snow collected on a traverse from the coast to Dome A was used to investigate variations in snow chemistry. The non-sea-salt fractions of K+, Mg2+, and Ca2+ are associated with terrestrial inputs, and nssCl− is from HCl. In general, proportions of non-sea-salt fractions of ions to the totals are higher in the interior areas than on the coast, and the proportions are higher in summer than in winter.
Wendell W. Walters, Linlin Song, Jiajue Chai, Yunting Fang, Nadia Colombi, and Meredith G. Hastings
Atmos. Chem. Phys., 20, 11551–11567, https://doi.org/10.5194/acp-20-11551-2020, https://doi.org/10.5194/acp-20-11551-2020, 2020
Short summary
Short summary
This article details new field observations of the nitrogen stable isotopic composition of ammonia emitted from vehicles conducted in the US and China. Vehicle emissions of ammonia may be a significant source to urban regions with important human health and environmental implications. Our measurements have indicated a consistent isotopic signature from vehicle ammonia emissions. The nitrogen isotopic composition of ammonia may be a useful tool for tracking vehicle emissions.
Cited articles
4500-NH3 NITROGEN (AMMONIA), Standard Methods For the
Examination of Water and Wastewater,
https://doi.org/10.2105/SMWW.2882.087, 2018.
4500-NO3− NITROGEN (NITRATE), Standard Methods For the
Examination of Water and Wastewater,
https://doi.org/10.2105/SMWW.2882.089, 2018.
4500-P PHOSPHORUS, Standard Methods For the Examination of Water and
Wastewater, https://doi.org/10.2105/SMWW.2882.093, 2018.
Amundson, R., Austin, A. T., Schuur, E. A. G., Yoo, K., Matzek, V., Kendall,
C., Uebersax, A., Brenner, D., and Baisden, W. T.: Global patterns of the
isotopic composition of soil and plant nitrogen, Global Biogeochem. Cy.,
17, https://doi.org/10.1029/2002GB001903, 2003.
Andersson, K. K. and Hooper, A. B.: O2 and H2O are each the source of one O
in NO2 produced from NH3 by Nitrosomonas: 15N-NMR evidence, FEBS Lett.,
164, 236–240, 1983.
Arar, E. and Collins, G.: In vitro determination of Chlorophyll a and
pheophytin in marine freshwater and algae by fluoresecence, National
Exposure Research Laboratory, Cincinnatri, USA, 22 pp., 1997.
Barnes, R. T. and Raymond, P.: The contribution of agricultural and urban
activities to inorganic carbon fluxes within temperate watersheds, Chem.
Geol., 266, 318–327, 2009.
Barnes, R. T., Raymond, P. A., and Casciotti, K. L.: Dual isotope analyses
indicate efficient processing of atmospheric nitrate by forested watersheds
in the northeastern U.S, Biogeochemistry, 90, 15–27, 2008.
Baron, J. S., Hall, E. K., Nolan, B. T., Finlay, J. C., Bernhardt, E. S.,
Harrison, J. A., Chan, F., and Boyer, E. W.: The interactive effects of
excess reactive nitrogen and climate change on aquatic ecosystems and water
resources of the United States, Biogeochemistry, 114, 71–92, 2013.
Beale, B. M. L.: Some uses of computers in operational research,
Industrielle Organisation, 31, 27–28, 1962.
Berezina, N. and Golubkov, S.: Effect of drifting macroalgae Cladophora
glomerata on benthic community dynamics in the easternmost Baltic Sea, J.
Mar. Syst., 74, S80–S85, https://doi.org/10.1016/j.jmarsys.2008.03.027, 2008.
Böhlke, J. K.: Sources, transport, and reaction of nitrate in ground
water, Residence times and nitrate transport in ground water discharging
to streams in the Chesapeake Bay Watershed, US Geological Survey
Water-Resources Investigations Report 03-4035, US Geological Survey, New Cumberland, Pennsylvania, USA, 215 pp.,
2003.
Böhlke, J. K., Smith, R. L., and Miller, D. N.: Ammonium transport and
reaction in contaminated groundwater: Application of isotope tracers and
isotope fractionation studies, Water Resour. Res., 42, W05411, https://doi.org/10.1029/2005WR004349, 2006.
Böhlke, J. K., Hatzinger, P. B., Sturchio, N. C., Gu, B., Abbene, I., and
Mroczkowski, S. J.: Atacama Perchlorate as an Agricultural Contaminant in
Groundwater: Isotopic and Chronologic Evidence from Long Island, New York,
Environ. Sci. Technol., 43, 5619–5625, 2009.
Boshers, D. S., Granger, J., Tobias, C. R., Böhlke, J. K., and
Smith, R. L.: Constraining the Oxygen Isotopic Composition of Nitrate
Produced by Nitrification, Environ. Sci. Technol., 53, 1206–1216, 2019.
Braman, R. S. and Hendrix, S. A.: Nanogram nitrite and nitrate determination
in environmental and biological materials by vanadium (III) reduction with
chemiluminescence detection, Anal. Chem., 61, 2715–2718, 1989.
Brandes, J. A. and Devol, A. H.: Isotopic fractionation of oxygen and
nitrogen in coastal marine sediments, Geochim. Cosmochim. Ac., 61,
1793–1801, https://doi.org/10.1016/S0016-7037(97)00041-0, 1997.
Brookshire, E. N. J., Valett, H. M., Thomas, S. A., and Webster, J. R.:
Coupled cycling of dissolved organic nitrogen and carbon in a forest stream,
Ecology, 86, 2487–2496, 2005.
Buchwald, C. and Casciotti, K. L.: Oxygen isotopic fractionation and
exchange during bacterial nitrite oxidation, Limnol. Oceanogr., 55,
1064–1074, 2010.
Casciotti, K., Trull, T. W., Glover, D. M., and Davies, D.: Constraints
on nitrogen cycling in the subtropical North Pacific Station ALOHA from
isotopic measurements of nitrate and particulate nitrogen, Deep Sea Res.,
55, 1661, https://doi.org/10.1016/j.dsr2.2008.04.017, 2008.
Casciotti, K. L.: Nitrogen and Oxygen Isotopic Studies of the Marine
Nitrogen Cycle, Annu. Rev. Mar. Sci., 8, 379–407, 2016.
Casciotti, K. L., Sigman, D. M., Hastings, M. G., Böhlke, J. K., and
Hilkert, A.: Measurement of the oxygen isotopic composition of nitrate in
seawater and freshwater using the denitrifier method, Anal. Chem., 74, 4905,
https://doi.org/10.1021/ac020113w, 2002.
D'Avanzo, C. and Kremer, J. N.: Diel oxygen dynamics and anoxic events in an
eutrophic estuary of Waquoit Bay, Massachusetts, Estuaries, 17, 131–139,
1994.
Deutsch, B., Liskow, I., Kahle, P., and Voss, M.: Variations in the δ15N and δ18O values of nitrate in drainage water of two fertilized
fields in Mecklenburg-Vorpommern (Germany), Aquat. Sci., 67, 156–165, 2005.
Dickerman, D. C. and Bell, R. W.: Hydrogeology, Water Quality, and
Ground-water-development Alternatives in the Lower Wood River Ground-water
Reservoir, Rhode Island, US Department of the Interior, US Geological
Survey, Providence, Rhode Island, USA, 92 pp., 1993.
Dickerman, D., Bell, R., Mulvey, K., Peterman, E., and Russell, J.:
Geohydrologic data for the upper Wood River ground-water reservoir, Rhode
Island, Rhode Island Water Resources Board Water Information Series Report,
Providence, RI, USA, 274 pp.,
1989.
Dillingham, T. P.: The Pawcatuck River Estuary and Little Narragansett Bay:
An Interstate Management Plan: Adopted July 14, 1992, Rhode Island Coastal Resources Management Council
Connecticut Department of Environmental Protection
Stonington, Connecticut and Westerly Rhode Island, 1993.
Divers, M., Elliott, E., and Bain, D.: Quantification of Nitrate Sources to
an Urban Stream Using Dual Nitrate Isotopes, Environ. Sci. Technol., 48, 10580-7, https://doi.org/10.1021/es404880j, 2014.
Dodds, W. K. and Gudder, D. A.: The Ecology Of Cladophora, J. Phycol., 28,
415–427, 1992.
Dubrovsky, N. M., Burow, K. R., Clark, G. M., Gronberg, J. M., Hamilton, P. A.,
Hitt, K. J., Mueller, D. K., Munn, M. D., Nolan, B. T., Puckett, L. J., Rupert,
M. G., Short, T. M., Spahr, N. E., Sprague, L. A., and Wilber, W. G.: The quality
of our Nation's waters – Nutrients in the Nation's streams and groundwater,
1992–2004, US Geological Survey Circular 1350, available at: http://water.usgs.gov/nawqa/nutrients/pubs/circ1350 (last access: 9 March 2020), 2010.
Elwood, J. W. and Turner, R. R.: Streams: Water Chemistry and Ecology, in:
Analysis of Biogeochemical Cycling Processes in Walker Branch Watershed, edited by:
Johnson, D. W. and Van Hook, R. I., Springer, New York, USA,
301–350, 1989.
Ensign, S. H. and Doyle, M. W.: Nutrient spiraling in streams and river
networks, J. Geophys. Res., 111, G04009, https://doi.org/10.1029/2005JG000114, 2006.
Fang, Y., Koba, K., Makabe, A., Zhu, F., Fan, S., and Yoh, M.: Low
δ18O Values of Nitrate Produced from Nitrification in Temperate Forest
Soils, Environ. Sci. Technol., 46, 8723–8730, 2012.
Froelich, P. N.: Kinetic control of dissolved phosphate in natural rivers
and estuaries: A primer on the phosphate buffer mechanism, Limnol.
Oceanogr., 33, 649–668, 1988.
Fulweiler, R. W. and Nixon, S. W.: Export of Nitrogen, Phosphorus, and
Suspended Solids from a Southern New England Watershed to Little
Narragansett Bay, Biogeochemistry, 76, 567–593, 2005.
Garside, C.: A chemiluminescent technique for the determination of nanomolar
concentrations of nitrate and nitrite in seawater, Mar. Chem., 11, 159–167,
1982.
Granger, J. and Wankel, S. D.: Isotopic overprinting of nitrification on
denitrification as a ubiquitous and unifying feature of environmental
nitrogen cycling, P. Natl. Acad. Sci. USA, 113, 6391–6400,
https://doi.org/10.1073/pnas.1601383113, 2016.
Granger, J., Sigman, D. M., Needoba, J. A., and Harrison, P. J.: Coupled
nitrogen and oxygen isotope fractionation of nitrate during assimilation by
cultures of marine phytoplankton, Limnol. Oceanogr., 49, 1763–1773, 2004.
Granger, J., Prokopenko, M. G., Sigman, D. M., Mordy, C. W., Morse, Z. M.,
Morales, L. V., Sambrotto, R. N., and Plessen, B.: Coupled
nitrification-denitrification in sediment of the eastern Bering Sea shelf
leads to 15N enrichment of fixed N in shelf waters, J. Geophys. Res., 116, C11006, https://doi.org/10.1029/2010JC006751,
2011.
Granger, J., Prokopenko, M. G., Mordy, C. W., and Sigman, D. M.: The
proportion of remineralized nitrate on the ice-covered eastern Bering Sea
shelf evidenced from the oxygen isotope ratio of nitrate, Global Biogeochem.
Cy., 27, 962–971, 2013.
Grasshoff, K., Kremling, K., and Ehrhardt, M.: Methods of Seawater Analysis,
Third Edition, Wiley, New York, USA, https://doi.org/10.1002/9783527613984, 1999.
Green, C. T., Fisher, L. H., and Bekins, B. A.: Nitrogen Fluxes through
Unsaturated Zones in Five Agricultural Settings across the United States, J.
Environ. Qual., 37, 1073–1085, 2008.
Gruber, N. and Galloway, J. N.: An Earth-system perspective of the global
nitrogen cycle, Nature, 451, 293–296,
https://doi.org/10.1038/nature06592, 2008.
Harvey, J. W., Böhlke, J. K., Voytek, M. A., Scott, D., and Tobias, C.
R.: Hyporheic zone denitrification: Controls on effective reaction depth and
contribution to whole-stream mass balance, Water Resour. Res., 49,
6298–6316, 2013.
Hauxwell, J., Cebrian, J., and Valiela, I.: Eelgrass Zostera marina loss in
temperate estuaries: Relationship to land-derived nitrogen loads and effect
of light limitation imposed by algae, Mar. Ecol. Prog. Ser., 247, 59–73, 2003.
Hedin, L. O., von Fischer, J. C., Ostrom, N. E., Kennedy, B. P., Brown, M. G., and Robertson, G. P.: Thermodynamic constraints on nitrogentransformations and other biogeochemicalprocesses at soil–stream interfaces, Ecology, 79, 684–703, 1998.
Heisler, J. P., Glibert, P., Burkholder, J., Anderson, D., Cochlan, W.,
Dennison, W., Dortch, Q., Gobler, C., Heil, C., Humphries, E., Lewitus, A.,
Magnien, R., Marshall, H., Sellner, K., Stockwell, D. A., Stoecker, D., and
Suddleson, M.: Eutrophication and Harmful Algal Blooms: A Scientific
Consensus, Harmful Algae, 8, 3–13, 2008.
Hendry, M. J., McCready, R. G. L., and Gould, W. D.: Distribution, source and
evolution of nitrate in a glacial till of southern Alberta, Canada, J.
Hydrol., 70, 177–198, https://doi.org/10.1016/0022-1694(84)90121-5, 1984.
Hinkle, S. R., Böhlke, J. K., and Fisher, L. H.: Mass balance and isotope
effects during nitrogen transport through septic tank systems with
packed-bed (sand) filters, Sci. Total Environ., 407, 324–332,
https://doi.org/10.1016/j.scitotenv.2008.08.036, 2008.
Hollocher, T. C.: Source of the oxygen atoms of nitrate in the oxidation of
nitrite by Nitrobacter agilis and evidence against a P-O-N anhydride
mechanism in oxidative phosphorylation, Arch. Biochem. Biophys., 233,
721–727, https://doi.org/10.1016/0003-9861(84)90499-5, 1984.
Holloway, J., Dahlgren, R., Hansen, B., and Casey, W.: Contribution of
bedrock nitrogen to high nitrate concentrations in stream water, Nature,
395, 785–788, 1998.
Houlton, B. Z. and Bai, E.: Imprint of denitrifying bacteria on the global
terrestrial biosphere, P. Natl. Acad. Sci. USA, 106, 21713, https://doi.org/10.1073/pnas.0912111106, 2009.
Houlton, B. Z., Sigman, D. M., and Hedin, L. O.: Isotopic evidence for large
gaseous nitrogen losses from tropical rainforests, P. Natl. Acad. Sci.
USA, 103, 8745–8750, https://doi.org/10.1073/pnas.0510185103,
2006.
Howarth, R. W., Jensen, H. S., Marina, R., and Postma, H.: Transport to and
processing of P in near-shore and oceanic waters, in: Phosphorus in the
global environment, John Wiley & Sons Ltd, Chichester, UK, 323–346, 1995.
Howarth, R. W., Billen, G., Swaney, D., Townsend, A., Jaworski, N., Lajtha,
K., Downing, J. A., Elmgren, R., Caraco, N., Jordan, T., Berendse, F.,
Freney, J., Kudeyarov, V., Murdoch, P., and Zhao-Liang, Z.: Regional nitrogen
budgets and riverine N and P fluxes for the drainages to the North Atlantic
Ocean: Natural and human influences, Biogeochemistry, 35, 75–139, 1996.
Johannsen, A., Dähnke, K., and Emeis, K.: Isotopic composition of nitrate
in five German rivers discharging into the North Sea, Org. Geochem., 39,
1678–1689, 2008.
Kaiser, J., Hastings, M. G., Houlton, B. Z., Röckmann, T., and Sigman, D.
M.: Triple Oxygen Isotope Analysis of Nitrate Using the Denitrifier Method
and Thermal Decomposition of N2O, Anal. Chem., 79, 599–607, 2007.
Kasper, J. W., Denver, J. M., and York, J. K.: Suburban Groundwater Quality
as Influenced by Turfgrass and Septic Sources, Delmarva Peninsula, USA, J.
Environ. Qual., 44, 642–654, 2015.
Katz, B., Hornsby, H., Bohlke, J., and Mokray, M.: Sources and Chronology of
Nitrate Contamination in Spring Waters, Suwannee River Basin, Florida,
Water-Resources Investigations Report 99-4252, US Geological Survey,
Tallahassee, USA, 59 pp.,
https://doi.org/10.3133/wri994252, 1999.
Keeling, C. D.: The concentration and isotopic abundances of atmospheric
carbon dioxide in rural areas, Geochim. Cosmochim. Ac., 13, 322–334,
https://doi.org/10.1016/0016-7037(58)90033-4, 1958.
Keeling, C. D.: The concentration and isotopic abundances of carbon dioxide
in rural and marine air, Geochim. Cosmochim. Ac., 24, 277–298,
https://doi.org/10.1016/0016-7037(61)90023-0, 1961.
Kellman, L. and Hillaire-Marcel, C.: Nitrate cycling in streams: using
natural abundances of NO3–δ15N to measure in-situ denitrification,
Biogeochemistry, 43, 273–292, 1998.
Kendall, C.: Tracing Nitrogen Sources and Cycling in Catchments, chap. 16, in: Isotope Tracers in Catchment Hydrology, edited by:
Kendall, C. and McDonnel, J. J.,
Elsevier Science B.V.,
Amsterdam, the Netherlands,
519–576, 1998.
Kendall, C., Elliott, E., and Wankel, S.: Tracing Anthropogenic Inputs of
Nitrogen to Ecosystems, in: Stable isotopes in ecology and environmental
science, edited by: Michener, R. and Lajtha, K., Blackwell, Oxford, UK, 375–449,
2007.
Kennedy, C., Genereux, D., Corbett, D., and Mitasova, H.:
Relationships among groundwater age, denitrification, and the coupled
groundwater and nitrogen fluxes through a streambed, Water Resour.
Res., 45, W09402, https://doi.org/10.1029/2008WR007400, 2009.
Knapp, A. N., Sigman, D. M., and Lipschultz, F.: N isotopic composition of
dissolved organic nitrogen and nitrate at the Bermuda Atlantic Time-series
Study site, Global Biogeochem. Cy., 19, GB1018, https://doi.org/10.1029/2004GB002320, 2005.
Kreitler, C. W., Ragone, S. E., and Katz, B. G.: N15/N14 Ratios of
Ground-Water Nitrate, Long Island, New Yorka, Groundwater, 16, 404–409,
1978.
Kroopnick, P. and Craig, H.: Atmospheric oxygen: isotopic composition and
solubility fractionation, Science, 175, 54–55,
https://doi.org/10.1126/science.175.4017.54, 1972.
Krumholz, J. S.: Spatial and temporal patterns in nutrient standing stock
and mass-balance in response to load reduction in a temperate estuary,
PhD thesis, University of Rhode Island, Kingston, RI, USA, 401 pp., 2012.
Latimer, J. and Charpentier, M.: Nitrogen inputs to seventy-four southern
New England estuaries: Application of a watershed nitrogen loading model,
Estuar. Coast. Shelf Sci., 89, 125–136, 2010.
Lehmann, M. F., Sigman, D. M., McCorkle, D. C., Brunelle, B. G., Hoffmann,
S., Kienast, M., Cane, G., and Clement, J.: Origin of the deep Bering Sea
nitrate deficit: Constraints from the nitrogen and oxygen isotopic
composition of water column nitrate and benthic nitrate fluxes, Global
Biogeochem. Cy., 19, GB4005, https://doi.org/10.1029/2005GB002508, 2005.
Lin, J., Böhlke, J. K., Huang, S., Gonzalez-Meler, M., and Sturchio, N.
C.: Seasonality of nitrate sources and isotopic composition in the Upper
Illinois River, J. Hydrology, 568, 849–861, 2019.
Mayer, B., Boyer, E. W., Goodale, C., Jaworski, N. A., van Breemen, N.,
Howarth, R. W., Seitzinger, S., Billen, G., Lajtha, K., Nadelhoffer, K., Van
Dam, D., Hetling, L. J., Nosal, M., and Paustian, K.: Sources of nitrate in
rivers draining sixteen watersheds in the northeastern US: Isotopic
constraints, Biogeochemistry, 57, 171–197, 2002.
McClelland, J. W., Valiela, I., and Michener, R. H.: Nitrogen-stable isotope
signatures in estuarine food webs: A record of increasing urbanization in
coastal watersheds, Limnol. Oceanogr., 42, 930–937, 1997.
McMahon, P. B. and Böhlke, J. K.: Regional patterns in the isotopic
composition of natural and anthropogenic nitrate in groundwater, High
Plains, USA, Environ. Sci. Technol., 40, 2965–2970,
https://doi.org/10.1021/es052229q, 2006.
Mengis, M., Walther, U., Bernasconi, S. M., and Wehrli, B.: Limitations of
Using δ18O for the Source Identification of Nitrate in Agricultural
Soils, Environ. Sci. Technol., 35, 1840–1844, 2001.
Michener, R. and Lajtha, K.: Stable Isotopes in Ecology and Environmental Science, Second Edition, Blackwell Publishing LTd, 2007.
Moran, S. B., Stachelhaus, S. L., Kelly, R. P., and Brush, M. J.: Submarine
Groundwater Discharge as a Source of Dissolved Inorganic Nitrogen and
Phosphorus to Coastal Ponds of Southern Rhode Island, Estuar. Coast.,
37, 104–118, 2014.
Morford, S. L., Houlton, B. Z., and Dahlgren, R. A.: Geochemical and tectonic
uplift controls on rock nitrogen inputs across terrestrial ecosystems,
Global Biogeochem. Cy., 30, 333–349, 2016.
Mueller, D. K., Hamilton, P. A., Helsel, D. R., Hitt, K. J., and Ruddy, B. C.: Nutrients in ground water and surface water of the United
States: An analysis of data through 1992, US Department of the Interior, US
Geological Survey, Denver, Colorado, USA, 81 pp., https://doi.org/10.3133/wri954031, 1995.
Mulholland, M. R. and Lomas, M. W.: Chap. 7, Nitrogen Uptake and Assimilation, in: Nitrogen in the Marine Environment, 2nd Edn., edited by: Capone, D. G., Bronk, D. A., Mulholland, M. R., and Carpenter, E. J., Academic Press, San Diego, 303–384, 2008.
Mulholland, P. J. and Hill, W. R.: Seasonal patterns in streamwater nutrient
and dissolved organic carbon concentrations: Separating catchment flow path
and in-stream effects, Water Resour. Res., 33, 1297–1306, 1997.
Mulholland, P. J., Wilson, G. V., and Jardine, P. M.: Hydrogeochemical
Response of a Forested Watershed to Storms: Effects of Preferential Flow
Along Shallow and Deep Pathways, Water Resour. Res., 26, 3021–3036, 1990.
Murphy, J. and Riley, J. P.: A modified single solution method for the determinatino of
phosphate in natural waters, Anal. Chim. Acta, 27, 31, https://doi.org/10.1016/S0003-2670(00)88444-5, 1962.
Narragansett Bay Estuary Program: State of Narragansett Bay and Its
Watershed, Narragansett Bay Estuary Program, Technical Report for Narragansett Bay Estuary Program
Providence, RI, USA,
166 pp., 2017.
National Atmospheric Deposition Program, NTN Data Retrieval, available at:
http://nadp.slh.wisc.edu/data/NTN/ (last access: November 2019), 2019.
National Water Quality Monitoring Council: Water Quality Portal, available at: https://www.waterqualitydata.us/ (last access: November 2019), 2020.
Needoba, J., Waser, D., Harrison, P., and Calvert, S.: Nitrogen Isotope
Fractionation in 12 Species of Marine Phytoplankton During Growth on
Nitrate, Mar. Ecol. Progr. Ser., 255, 81–91,
2003.
Nixon, S. W., Granger, S. L., and Nowicki, B. L.: An assessment of the annual mass balance of carbon, nitrogen, and phosphorus in Narragansett Bay, Biogeochemistry, 31, 15–61, 1995.
Nixon, S. W., Buckley, B. A., Granger, S. L., Harris, L. A., Oczkowski, A.
J., Fulweiler, R. W., and Cole, L. W.: Nitrogen and Phosphorus Inputs to
Narragansett Bay: Past, Present, and Future, in: Science for
Ecosystem-based Management, edited by:
Desbonnet, A. and Costa-Pierce, B. A., Springer, New York, USA,
2008.
NOAA National Centers for Environmental information: Climate at a Glance:
County Time Series, available at: https://www.ncdc.noaa.gov/cag/ (last access: 15 November 2019), 2019.
Pabich, W., Valiela, I., and Hemond, H.: Relationship between DOC
concentration and vadose zone thickness and depth below water table in
groundwater of Cape Cod, USA, Biogeochemistry, 55, 247–268, 2001.
Quilbé, R., Rousseau, A., Duchemin, M., Poulin, A., Gangbazo, G., and
Villeneuve, J.: Selecting a Calculation Method to Estimate Sediment and
Nutrient Loads in Streams: Application to the Beaurivage River (Québec,
Canada), J. Hydrology, 326, 295, https://doi.org/10.1016/j.jhydrol.2005.11.008, 2006.
Rollinson, V. R., Granger, J., Clark, S. C., Blanusa, M. L., Koerting, C. P., Vaudrey, J. M. P., Treibergs, L. A., Westbrook, H. C., Matassa, C. M., Hastings, M. K., Tobias, C. R.: Seasonal nitrogen concentrations and nitrate isotopes of a New England River from 2018 to 2019, PANGAEA [Dataset], https://doi.org/10.1594/PANGAEA.931561, 2021.
Savarino, J. and Thiemens, M.: Analytical procedure to determine both
δ18O and δ17O of H2O2 in natural water and first
measurements, Atmos. Environ., 33, 3683–3690, 1999.
Sebestyen, S. D., Ross, D. S., Shanley, J. B., Elliott, E. M., Kendall, C.,
Campbell, J. L., Dail, D. B., Fernandez, I. J., Goodale, C. L., Lawrence, G.
B., Lovett, G. M., McHale, P. J., Mitchell, M. J., Nelson, S. J., Shattuck,
M. D., Wickman, T. R., Barnes, R. T., Bostic, J. T., Buda, A. R., Burns, D.
A., Eshleman, K. N., Finlay, J. C., Nelson, D. M., Ohte, N., Pardo, L. H.,
Rose, L. A., Sabo, R. D., Schiff, S. L., Spoelstra, J., and Williard, K. W.
J.: Unprocessed Atmospheric Nitrate in Waters of the Northern Forest Region
in the US and Canada, Environ. Sci. Technol., 53, 3620–3633, 2019.
Sebilo, M., Billen, G., Grably, M., and Mariotti, A.: Isotopic composition of
nitrate-nitrogen as a marker of riparian and benthic denitrification at the
scale of the whole Seine River system, Biogeochemistry, 63, 35–51, 2003.
Sebilo, M., Billen, G., Mayer, B., Billiou, D., Grably, M., Garnier, J., and
Mariotti, A.: Assessing Nitrification and Denitrification in the Seine River
and Estuary Using Chemical and Isotopic Techniques, Ecosystems, 9, 564–577,
2006.
Seitzinger, S. and Sanders, R.: Contribution of Dissolved Organic Nitrogen
From Rivers to Estuarine Eutrophication, Mar. Ecol. Progr. Ser., 159, 1–12, 1997.
Sigman, D. and Fripiat, F.: Nitrogen isotopes in the ocean, in:
Encyclopedia of Ocean Sciences, edited by: Kirk, J., Cochran Henry Bokuniewicz Patricia Yager
Cambridge, MA, USA, Elsevier, 263–278, https://doi.org/10.1016/B978-0-12-409548-9.11605-7, 2019.
Sigman, D., Casciotti, K., Andreani, M., Barford, C., Hastings, M., and
Bohlke, J.: A Bacterial Method for the Nitrogen Isotopic Analysis of Nitrate
in Seawater and Freshwater, Anal. Chem., 73, 4145–4153, 2001.
Sigman, D., Karsh, K., and Casciotti, K. L.: Nitrogen Isotopes in the Ocean,
in: Encyclopedia of ocean sciences, edited by: Steele, J. H., Encyclopedia of Ocean Sciences, 2nd Edn.,
Amsterdam, the Netherlands, Academic Press, 40–54, 2009.
Snider, D. M., Spoelstra, J., Schiff, S. L., and Venkiteswaran, J. J.: Stable
Oxygen Isotope Ratios of Nitrate Produced from Nitrification: 18O-Labeled
Water Incubations of Agricultural and Temperate Forest Soils, Environ. Sci.
Technol., 44, 5358–5364, 2010.
Solórzano, L. and Sharp, J. H.: Determination of total dissolved
phosphorus and particulate phosphorus in natural waters, Limnol. Oceanogr.,
25, 754–758, 1980.
Stevenson, F. J.: Humus Chemistry: Genesis, Composition, Reactions, 2nd edition,
John Wiley and Sons, New York, USA, 1994.
Strickland, J. D. and Parsons, T. R.: A Practical Handbook of Seawater
Analysis, 2nd edition, Fisheries Research Board of Canada, Ottawa, Canada,
1972.
Thiemens, M. H.: Mass-Independent Isotope Effects in Planetary Atmospheres
and the Early Solar System, Science, 283, 341–345,
https://doi.org/10.1126/science.283.5400.341, 1999.
Tiner, R., Berquist, H., Halavik, T., and MacLachlan, A.: Eelgrass Survey for
Eastern Long Island Sound, Connecticut and New York, US Fish and Wildlife
Service, National Wetlands Inventory Program, Hadley, USA, 22 pp., 2003.
Townsend, M., Young, D., and Macko, S.: Kansas case study applications of
nitrogen-15 natural abundance method for identification of nitrate sources,
Journal of Hazardous Substance Research, 4, 22 pp., 2003.
US Census Bureau: 2017 TIGER/Line Shapefiles (Area_Water), 2019 TIGER/Line Shapefiles (machinereadable data files)/prepared by the U.S. Census Bureau, 2019,
2017.
US Environmental Protection Agency: Method 365.3: Phosphorous, All Forms
(Colorimetric, Ascorbic Acid, Two Reagent), Environmental Monitoring
Systems Laboratory Office of Research and Development, Environmental Monitoring Systems Laboratory Office Of Research and Development U.S. Environmental Protection Agency Cincinnati, Ohio 45268, 18 pp., 1978.
US Environmental Protection Agency: Method 350.1: Determination of Ammonia
Nitrogen by semi-automated Colorimetry, Environmental Monitoring Systems
Laboratory Office of Research and Development, Environmental Monitoring Systems Laboratory Office Of Research and Development U.S. Environmental Protection Agency Cincinnati, Ohio 45268, 15 pp., 1993a.
US Environmental Protection Agency: Method 353.2: Revision 2.0:
Determination of Nitrate-Nitrite Nitrogen by Automated Colorimetry,
Environmental Monitoring Systems Laboratory Office of Research and
Development, Environmental Monitoring Systems Laboratory Office Of Research and Development U.S. Environmental Protection Agency Cincinnati, Ohio 45268, 15 pp., 1993b.
US Environmental Protection Agency: Fact Sheet Spring 2005: South County
RI Watersheds, SDMS Doc ID 579486, Flyer created by: United States Enivronmental Protection Agency New England, 2005.
US Environmental Protection Agency: Authorization to Discharge under the
Rhode Island Pollutant Discharge Elimination System, Permit No. RI0000191, Kenyon Industries, Richmond, USA, 2010.
US Geological Survey: National Atlas of the United States for Streams and
Waterbodies of the United States, available at: http://nationalatlas.gov (last acces: September 2020),
2005.
US Geological Survey: 20140331, NLCD 2011 Land Cover, U.S. Geological Survey, Sioux Falls, SD, U.S. Geological Survey,
2011.
URIEDC_RIGIS: Watershed Boundary Dataset HUC 12, Credit:
USDA-NRCS, USEPA, RI-DEM, 2019.
Valiela, I., McClelland, J., Hauxwell, J., Behr, P. J., Hersh, D., and
Foreman, K.: Macroalgal blooms in shallow estuaries: controls and
ecophysiological and ecosystem consequences, Limnol. Oceanogr., 42,
1105–1118, 1997.
Vaudrey, J., Yarish, C., Kim, J., Pickerell, C., Brousseau, L., Eddings, J.,
and Sautkulis, M.: Long Island Sound Nitrogen Loading Model, 2016.
Vaudrey, J., Brousseau, L., Yarish, C., and Kyun Kim, J.: Modeling nitrogen
loads to address point and non-point source nutrient pollution, in: 24th
Biennial CEFT Conference, Rhode Island, USA, November 5–9, 2017,
Providence, RI, 41 pp., 2017.
Veale, N., Visser, A., Esser, B., Singleton, M., and Moran, J.: Nitrogen
Cycle Dynamics Revealed Through δ18O–NO3-Analysis in California
Groundwater, Geosciences, 9, 95, https://doi.org/10.3390/geosciences9020095, 2019.
Wood-Pawcatuck Watershed Association: Wood-Pawcatuck Watershed Baseline
Assessment, Wood-Pawcatuck Watershed Flood Resiliency Management Plan, Fuss
and O'Neill, Manchester, USA, 2016.
Wood-Pawcatuck Watershed Association: Wood-Pawcatuck Water Quality
Monitoring Data: available at: https://wpwa.org/water-quality/ (last access: November 2019), 2020.
Xue, D., Botte, J., De Baets, B., Accoe, F., Nestler, A., Taylor, P., Van
Cleemput, O., Berglund, M., and Boeckx, P.: Present limitations and future
prospects of stable isotope methods for nitrate source identification in
surface- and groundwater, Water Res., 43, 1159–1170,
https://doi.org/10.1016/j.watres.2008.12.048, 2009.
Zhang, L., Altabet, M. A., Wu, T., and Hadas, O.: Sensitive measurement of
NH4 +15N/14N (δ15NH4 + ) at natural abundance levels in fresh and
saltwaters, Anal. Chem., 79, 5297–5303, 2007.
Short summary
We measured nutrients and the naturally occurring nitrogen (N) and oxygen (O) stable isotope ratios of nitrate discharged from a New England river over an annual cycle, to monitor N loading and identify dominant sources from the watershed. We uncovered a seasonality to loading and sources of N from the watershed. Seasonality in the nitrate isotope ratios also informed on N cycling, conforming to theoretical expectations of riverine nutrient cycling.
We measured nutrients and the naturally occurring nitrogen (N) and oxygen (O) stable isotope...
Altmetrics
Final-revised paper
Preprint