Abstract
In calcareous watersheds, groundwater alkalinity results largely from dissolution of carbonate minerals in soils. The alkalinity increases initially approximately in proportion to nitrate (NO3−) concentration and eventually approaches an apparent maximum of approximately 8 mmol L−1 at high NO3− concentrations. This close positive relationship between alkalinity and NO3− concentration appears to be predominantly a result of three processes: (i) mineralization of organic nitrogen fertilizer, (ii) exchange of OH− and H+ during the uptake of NO3− or ammonium by crop plants, and (iii) CO2 released by roots as a result of fertilizer-stimulated plant growth. We suggest that the asymptotic approach to a maximum groundwater alkalinity at NO3− concentrations exceeding 0.25 mmol L−1 may be caused by (i) a maximum possible areal crop production at excessive N fertilization and (ii) an increasing CO2 loss to the atmosphere due to the increasing CO2 production in the soil. Our analysis provides a general understanding and quantitative prediction of steady-state groundwater NO3− concentration, alkalinity, pH, the degree of CO2 supersaturation in the soil, and soil CO2 emissions to the atmosphere. The positive correlation between alkalinity and NO3− concentration observed in groundwaters persists in rivers and lakes. We conclude that an economically efficient agricultural practice that avoids over-fertilization might accelerate the in-soil carbonate weathering rate up to approximately threefold compared to unfertilized soils, but it will not jeopardize the use of aquifers for drinking water.
Similar content being viewed by others
Data availability
The groundwater datasets analyzed during the current study are not publicly available because they belong to the Canton of Zürich and the Swiss Federal Office for the Environment (FOEN), but they are available from the corresponding author on reasonable request.
References
Alberta Manure composting Handbook (2005) https://www1.agric.gov.ab.ca/$department/deptdocs.nsf/all/agdex8875
Abril G, Frankignoulle M (2001) Nitrogen-alkalinity interactions in the highly polluted Scheldt Basin (Belgium). Water Res 35:844–850. https://doi.org/10.1016/S0043-1354(00)00310-9
Abril G, Etcheber H, Borges AV, Frankignoulle M (2000) Excess atmospheric carbon dioxide transported by rivers into the Scheldt estuary. Earth Planet Sci 330:761–768. https://doi.org/10.1016/S1251-8050(00)00231-7
Barnes RT, Raymond PA (2009) The contribution of agricultural and urban activities to inorganic carbon fluxes within temperate watersheds. Chem Geol 266:327–336. https://doi.org/10.1016/j.chemgeo.2009.06.018
Battye W, Aneja VP, Schlesinger WH (2017) Is nitrogen the next carbon? Earth’s Future 5:894–904. https://doi.org/10.1002/2017EF000592
Bauer JE, Cai WJ, Raymond PA, Bianchi TS, Hopkins CS, Regnier AG (2013) The changing carbon cycle of the coastal ocean. Nature 504:61–70. https://doi.org/10.1038/nature12857
Baule B (1917) Mitscherlich’s law of physiological relations (in German). Landwirtschaftl Jahrbücher 51:363–385
Brunet F, Potot C, Probst A, Probst J-L (2011) Stable carbon isotope evidence for nitrogenous fertilizer impact on carbonate weathering in a small agricultural watershed. Rapid Commun Mass Spectrom 25:2682–2690. https://doi.org/10.1002/rcm.5050
Cheng WX, Sims DA, Luo YQ, Coleman JS, Johnson DW (2000) Photosynthesis, respiration, and net primary production of sunflower stands in ambient and elevated atmospheric CO2 concentrations: an invariant NPP:GPP ratio? Global Change Biol 6:931–941. https://doi.org/10.1046/j.1365-2486.2000.00367.x
Dong W, Duan Y, Wang Y, Hu C (2016) Reassessing carbon sequestration in the North China Plain via addition of nitrogen. Sci Tot Environ 563–564:138–144. https://doi.org/10.1016/j.scitotenv.2016.04.115
Duiker SW, Lal R (2000) Carbon budget study using CO2 flux measurements from a no till system in central Ohio. Soil Till Res 54:21–30. https://pdfs.semanticscholar.org/0bb2/49e591468571ea0a6281110ec3b7ca3b41d7.pdf
Eawag (2017) (Swiss Federal Institute of Aquatic Science and Technology): National long-term surveillance of Swiss rivers (NADUF). https://www.eawag.ch/en/department/wut/main-focus/chemistry-of-water-resources/naduf/
Elser JJ, Fagan WF, Denno RF, Dobberfuhl DR, Folarin A, Huberty A, Interlandi S, Kilham SS, McCauley E, Schulz KL, Siemann EH, Sterner RW (2000) Nutritional constraints in terrestrial and freshwater food webs. Nature 408:578–580. https://doi.org/10.1038/35046058
Flisch R, Sinaj S, Charles R, Richner W (2009) Hofdünger. Pages 50–71 in: Grundlagen für die Düngung im Acker- und Futterbau. AGRARForschung, 16(2):1–97. https://www.agrarforschungschweiz.ch/artikel/2009_02_1451.pdf
FOAG (2016) Federal Office for Agriculture. Marktbericht Mineraldünger. https://www.blw.admin.ch/blw/de/home/markt/marktbeobachtung/duenger.html
FOAG (2018) Federal Office for Agriculture. Agrarbericht 2017. https://www.blw.admin.ch/blw/de/home/services/agrarbericht.html, https://www.agrarbericht.ch/de/betrieb/strukturen/landwirtschaftliche-nutzflaeche.
FOEN (2017) National long-term surveillance of Swiss lakes (on request). https://www.bafu.admin.ch/bafu/en/home/state/data/geodata.html
FOMC (2018) Federal Office of Meteorology and Climatology MeteoSwiss. https://www.meteoswiss.admin.ch/home/climate/swiss-climate-in-detail/climate-normals/normal-values-per-measured-parameter.html
FSO (2014) Nitrogen and phosphorus: Nutrients or pollutants? The nitrogen and phosphorus balance of Swiss agriculture. https://www.bfs.admin.ch/bfsstatic/dam/assets/349334/master. Federal statistical office FSO, BFS no. 1165-1400, Neuchatel, August 2014.
Gandois L, Perrin A-S, Probst A (2011) Impact of nitrogenous fertiliser-induced proton release on cultivated soils with contrasting carbonate contents: a column experiment. Geochim Cosmochim Acta 75(5):1185–1198. https://doi.org/10.1016/j.gca.2010.11.025
Guo JH, Liu XJ, Zhang Y, Shen JL, Han WX, Zhang WF, Christie P, Goulding KWT, Vitousek PM, Zhang FS (2010) Significant acidification in major Chinese croplands. Science 327:1008–1010. https://doi.org/10.1126/science.1182570
Graf Pannatier E, Thimonier A, Schmitt M, Walthert L, Waldner P (2011) A decade of monitoring at Swiss Long-Term Forest Ecosystem Research (LWF) sites: can we observe trends in atmospheric acid deposition and in soil solution acidity? Environ Monit Assess 174:3–30. https://doi.org/10.1007/s10661-010-1754-3
GSchG (2017) Swiss law for the protection of the environment, Art. 14 Abs. 4 GSchG. https://www.admin.ch/opc/de/classified-compilation/19910022/201701010000/814.20.pdf
Haber W (1957) Ökologische Untersuchung der Bodenatmung. Flora oder Allgemeine Botanische Zeitung 146:109–157
Hagedorn F, Krause H-M, Studer M, Schellenberger A, Gattinge A (2018) Boden und Umwelt. Organische Bodensubstanz, Treibhausgasemissionen und physikalische Belastung von Schweizer Böden. Thematische Synthese TS2 des Nationalen Forschungsprogramms «Nachhaltige Nutzung der Ressource Boden» (NFP 68). http://www.nfp68.ch/en
Hamilton SK, Kurzman AL, Arango C, Jin L, Robertson GP (2007) Evidence for carbon sequestration by agricultural liming. Global Biogeochem Cycles 21:1–12. https://agupubs.onlinelibrary.wiley.com/doi/full/10.1029/2006GB002738.
Hotchkiss EA, Hall RO Jr, Sponseller RA, Butman D, Klaminder J, Laudon H, Rosvall M, Karlsson J (2015) Sources of and processes controlling CO2 emissions change with the size of streams and rivers. Nature Geosci 8:696–699. https://doi.org/10.1038/NGEO2507
Hürdler J, Prasuhn V, Spiess E (2015) Abschätzung diffuser Stickstoff- und Phosphoreinträge in die Gewässer der Schweiz MODIFFUS 3.0. Report to the hands of the Swiss Federal Office for the Environment, FOEN. Agroscope (in German). http://link.ira.agroscope.ch/de-CH/publication/35052
Jacinthe P-A, Lal R, Kimble JM (2002) Carbon budget and seasonal carbon dioxide emission from a central Ohio Luvisol as influenced by wheat residue amendment. Soil Tillage Res 67:147–157
Jones SK, Rees RM, Skiba UM, Ball BC (2005) Greenhous gas emissions from a managed grassland. Global Planet Change 47:201–211
Kaushal SS, Likens GE, Utz RM, Pace ML, Grese M, Yepsen M (2013) Increased river alkalinization in the Eastern U.S. Environ Sci Technol 47:10302–10311. https://doi.org/10.1021/es401046s
Langmuir D (1997) Aqueous environmental geochemistry. Prentice-Hall, Inc., Upper Saddle River
Li S, Lu XX, Bush RT (2013) CO2 partial pressure and CO2 emission in the Lower Mekong River. J Hydrol 504:40–56. https://doi.org/10.1016/j.jhydrol.2013.09.024
Lorenz K, Lal R (2018) Carbon sequestration in agricultural ecosystems. Springer. https://doi.org/10.1007/978-3-319-92318-5
Müller B (2015) ChemEQL V3.2: A program to calculate chemical speciation equilibria, titrations, dissolution, precipitation, adsorption, kinetics, pX-pY diagrams, solubility diagrams. Eawag: Swiss Federal Institute of Aquatic Science and Technology, Kastanienbaum, Switzerland. https://www.eawag.ch/en/department/surf/projects/chemeql/
Müller B, Meyer JS, Gächter R (2016) Alkalinity regulation in calcium carbonate-buffered lakes. Limnol Oceanogr 61:341–352. https://doi.org/10.1002/lno.10213
NABEL (Nationales Beobachtungsnetz für Luftfremdstoffe (NABEL) (2016) Swiss Federal Office for the Environment (FOEN). https://www.bafu.admin.ch/uz-1624-d.
NAQUA (National groundwater monitoring of Switzerland) (2017) Module ‚TREND’. Swiss Federal Office for the Environment (FOEN), on request. https://www.bafu.admin.ch/bafu/en/home/topics/water/info-specialists/state-of-waterbodies/state-of-groundwater/naqua-national-groundwater-monitoring.html
NOAA (National Oceanic and Atmospheric Administration) (2017) Trends in atmospheric carbon dioxide: Mauna Loa CO2 annual mean data. https://www.esrl.noaa.gov/gmd/ccgg/trends/co2/co2_annmean_mlo.txt
Oh N-H, Raymond PA (2006) Contribution of agricultural liming to riverine bicarbonate export and CO2 sequestration in the Ohio River basin. Glob Biogeochem Cycles 20:GB3012. https://doi.org/10.1029/2005GB002565
Perrin A-S, Probst A, Probst J-L (2008) Impact of nitrogenous fertilizers on carbonate dissolution in small agricultural catchments: implications for weathering CO2 uptake at regional and global scales. Geochim Cosmochim Acta 72:3105–3123. https://doi.org/10.1016/j.gca.2008.04.011
Plummer LN, Busenberg E (1982) The solubilities of calcite, aragonite and vaterite in CO2-H2O solutions between 0 and 90°C, and an evaluation of the aqueous model for the system CaCO3-CO2-H2O. Geochim Cosmochim Acta 46:1011–1040. https://doi.org/10.1016/0016-7037(82)90056-4
Plummer LN, Parkhurst DL, Wigley TML (1979) Critical review of the kinetics of calcite dissolution and precipitation. In: Jenne EA (ed) Chemical modeling in aqueous systems: speciation, sorption, solubility, and kinetics, ACS Symposium Series 93. American Chemical Society, Washington, pp 537–573
Raymond PA, Hamilton SK (2018) Anthropogenic influences on riverine fluxes of dissolved inorganic carbon to the ocean. Limnol Oceanogr Lett 3:143–155. https://doi.org/10.1002/lol2.10069
Raymond PA, Oh N-H, Turner RE, Broussard W (2008) Anthropogenically enhanced fluxes of water and carbon from the Mississippi River. Nature 451:449–452. https://doi.org/10.1038/nature06505
Ren W, Tian H, Tao B, Yang J, Pan S, Cai WJ, Lohrenz SE, He R, Hopkins CS (2015) Large increase in dissolved inorganic carbon flux from the Mississippi River to the Gulf of Mexico due to climatic and anthropogenic changes over the 21st century. J Geophys Res Biogeosci 120:724–736. https://doi.org/10.1002/2014JG002761
Resplandy L, Keeling RF, Rödenbeck C, Stephens BB, Khatiwala S, Rodgers KB, Long MC, Bopp L, Tans PP (2018) Revision of global carbon fluxes based on a reassessment of oceanic and riverine carbon transport. Nat Geosci 11:504–509. https://doi.org/10.1038/s41561-018-0151-3
Schulte-Bisping H, Beese F (2012) Abschlussbericht. UN/ECE Integrated Monitoring-Programm, Fortsetzung des Integrated Monitoring Programms an der Station Neuglobsow. https://www.umweltbundesamt.de/sites/default/files/medien/370/dokumente/bericht_zu_den_monitoringergebnissen_2012_-_abschlussbericht_neuglobsow_2012_-_fkz_3510104004.pdf
Song C, Liu C, Han G, Liu C (2017) Impact of different fertilizers on carbonate weathering in a typical karst area, Southwest China: a field column experiment. Earth Surf Dynam 5:605–616. https://doi.org/10.5194/esurf-5-605-2017
Stets EG, Kelly VJ, Crawford CG (2014) Long-term trends in alkalinity in large rivers of the conterminous US in relation to acidification, agriculture, and hydrologic modification. Sci Tot Environ 488–489:280–289. https://doi.org/10.1016/j.scitotenv.2014.04.054
Stumm W, Morgan JJ (1996) Aquatic chemistry, 3rd edn. Wiley, New York
Tanner RL (1990) Sources of acids, bases, and their precursors in the atmosphere. In: Lindberg SE, Page AL, Norton SA (eds) Acidic precipitation. Advances in environmental science, vol 3. Springer, New York
USDA National Resources Conservation Service (2011) Carbon to nitrogen ratios in cropping systems. https://www.nrcs.usda.gov/Internet/FSE_DOCUMENTS/nrcseprd331820.pdf
Walworth J (2013) Nitrogen in soil and the environment. Cooperate extension publication AZ1591. University of Arizona, Tucson
West TO, McBride AC (2005) The contribution of agricultural lime to carbon dioxide emissions in the United States: Dissolution, transport, and net emissions. Agric Ecosyst Environ 108:145–154. https://doi.org/10.1016/j.agee.2005.01.002
WWEA (Canton Zürich Office of Waste, Water, Energy and Air) (2017) Groundwater quality. https://www.awel.zh.ch/internet/baudirektion/awel/de/wasser/messdaten.html
Zobrist J, Schoenenberger U, Figura S, Hug SJ (2018) Long-term trends in Swiss rivers sampled continuously over 39 years reflect changes in geochemical processes and pollution. Environ Sci Poll Res. https://doi.org/10.1007/s11356-018-1679-x
Acknowledgements
Financial support was provided by Eawag (Switzerland) and Applied Limnology Professionals LLC. Groundwater data from the Canton of Zürich were provided by the Office of Waste, Water, Energy and Air (WWEA) of the Canton of Zürich, Switzerland. Data of the National Groundwater Monitoring program (NAQUA), module ‘TREND’, were provided by the Swiss Federal Office for the Environment (FOEN). The work of two anonymous reviewers is gratefully acknowledged.
Author information
Authors and Affiliations
Contributions
BM, JSM, and RG contributed equally to the manuscript. BM performed ChemEQL speciation calculations.
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Müller, B., Meyer, J.S. & Gächter, R. Nitrogen fertilization of soils fuels carbonate weathering and translocation in calcareous watersheds. Aquat Sci 82, 37 (2020). https://doi.org/10.1007/s00027-020-0712-6
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00027-020-0712-6