Environmental Science and Pollution Research

, Volume 25, Issue 17, pp 16788–16809 | Cite as

Long-term trends in Swiss rivers sampled continuously over 39 years reflect changes in geochemical processes and pollution

  • Juerg Zobrist
  • Ursula Schoenenberger
  • Simon Figura
  • Stephan J. Hug
Research Article


Long-term changes of 14 water constituents measured in continuously and water discharge proportionally collected samples of four Swiss rivers over a period of 39 years are analyzed using several statistical techniques. Possible drivers and causes for the identified trends and shifts are explained by consideration of catchment characteristics and anthropogenic activities. Water temperatures increased by 0.8–1.3 °C, whereas water discharges remained largely unchanged. Concentrations of alkalinity, total hardness, Ca, and Mg regulated by dominant carbonate lithologies in catchments increased by up to 10%. We attribute this change to an increase in the partial pressure of CO2 in the subsurface, provoked by increasing temperatures. Re-oligotrophication processes in lakes also influence the behavior of alkalinity and silicic acid. In contrast to concentrations, most loads did not change significantly, due to their large variances. Therefore, no changes in overall weathering rates of carbonate rocks can be detected. The outgassing of CO2 in rivers from the place of carbonate dissolution to measurement stations amounts up to 6% (mean) of CO2 sequestered (mean 1.1 mol m−2 a−1) by the weathering of rock minerals. Changes in alkalinity/Ca/Mg ratios indicate an increase in calcite precipitation over time. Total nitrogen concentrations and loads peaked at the end of the 1980s and then decreased up to 50%, while NO3 concentrations showed almost no changes. This dynamic matches the changes in the agricultural N balance. Concentrations and loads of Na and Cl increased up to 60% due to an increase in the various uses of rock salt.


River Long-term trends Geochemical processes Nitrogen pollution Switzerland 



We gratefully acknowledge the constant effort of numerous collaborators at the “Federal Hydrological Survey” (official name changed many times), at the analytical laboratory and in the data-handling group at Eawag, who have reliably and continuously carried out the long-term river survey NADUF for more than 40 years. We also thank David Livingstone, Rolf Kipfer, and Laura Sigg for their valuable comments and support. The suggestion and comments of two anonymous reviewers are also highly appreciated. Lastly, we are grateful to Jay Matta for improving the English writing.

Supplementary material

11356_2018_1679_MOESM1_ESM.pdf (1.4 mb)
ESM 1 (PDF 1.35 mb)
11356_2018_1679_MOESM2_ESM.pdf (195 kb)
ESM 2 (PDF 194 kb)


  1. Ahel M, Molnar E, Ibric S, Giger W (2000) Estrogenic metabolites of alkylphenol polyethoxylates in secondary sewage effluents and rivers. Water Sci Technol 42:15–22CrossRefGoogle Scholar
  2. Arona R, Tockner K, Venerohr M (2016) Changing river temperatures in northern Germany: trends and drivers of change. Hydrol Process 30:3084–3098CrossRefGoogle Scholar
  3. Barbier C, Quetin P, Anneville O (2017) Evolution pyhisco-chemique des eaux du Léman et données météoroloquiques, Commision internationale pour la protection des eaux du Léman contre la pollution. CIPEL, NyonGoogle Scholar
  4. Berge E, Bartnicki J, Olendrzynski K (1999) Long-term trends in emissions and transboundary transport of acidifying air pollution in Europe. J Environ Manag 57:31–50CrossRefGoogle Scholar
  5. Bundi U, Peter A, Frutiger A, Huette M, Liechti P, Sieber U (2000a) Scientific base and modular concept for comprehensive assessment of streams in Switzerland. Hydrobiologia 422(423):477–487Google Scholar
  6. Bundi U, Peter A, Truffer B, Wagner W, Mauch U, Scheidegger A (2000b) The quality of aquatic ecosystems as an indicator for sustainable water management - country paper of Switzerland. In: Kraals JA (ed) Let the fish speak: the quality of aquatic ecosystems as an indicator for sustainable water management. EurAqua technical review. Institute for Inland Water Management and Waste Water Treatment, Lelystad, pp 205–215Google Scholar
  7. Bürgi HR (2015) 50 Jahre Planktonentwicklung im Vierwaldstättersee von 1960 bis 2010. Aufsichtskommission Vierwaldstättersee (AKW), StansGoogle Scholar
  8. Burt TP, Howden NJK, Worrall F, Whelan MJ (2010) Long-trem monitoring of river water nitrate: how much data do we need? J Environ Monit 12:71–79CrossRefGoogle Scholar
  9. Calmels D, Gaillardet J, Francois L (2014) Sensitivity of carbonate weathering to soil CO2 production by biological activity along a temperate climate transect. Chem Geol 390:74–86CrossRefGoogle Scholar
  10. CIPEL (2017) Rapports sur les études et recherches entreprises dans le bassin lémanique (in french). Interational commitee for the Protection of the Water of Lake Geneva. CIPEL, NyonGoogle Scholar
  11. Cleveland RB, Cleveland WS, McRae JE, Terpenning I (1990) STL: a seasonal-trend decomposition procedure based on Loess. J Off Stat 6:3–73Google Scholar
  12. Drever JI (1997): The geochemistry of natural waters: surface and groundwater environments, 3rd ed. Prentice Hall, Upper Saddle River, NJ 07458, pp. 436Google Scholar
  13. Drever JI, Zobrist J (1992) Chemical weathering of silicate rocks as a function of elevation in the Southern Swiss Alps. Geochim Cosmochim Acta 56:3209–3216CrossRefGoogle Scholar
  14. Esterby SA (1996) Review of methods for the detection and estimation of trends with emphasis on water quality applications. Hydol Process 10:127–149CrossRefGoogle Scholar
  15. Federal Office for the Environment F 2015: NABEL Luftbelastung 2014, Federal Office for the Environment (Foen), Swiss Federal Laboratories for Material Sciences and Technology (Empa)Google Scholar
  16. Figura S, Livingstone DM, Hoehn E, Kipfer R (2011) Regime shift in groundwater temperature trigger by the Artic Ocillation. Geophys Res Lett 38Google Scholar
  17. Friedman JH, Stuetzle W (1981) Projection pursuit regression. J Am Stat Assoc 76:817–823CrossRefGoogle Scholar
  18. Geldern Rv SP, Mader M, Baier A, Barth JAC (2015) Spatial and temporal variations of pCO2, dissolved inorganic carbon and stable isotopes along a temperate karstic watercourse. Hydrol Process 29:3423–3440CrossRefGoogle Scholar
  19. Giger W, Schaffner C, Kohler HPE (2006) Benzotriazole and tolyltriazole as aquatic contaminents. 1. Input and occurrences in rivers and lakes. Environ Sci Technol 40:7186–7192CrossRefGoogle Scholar
  20. Gnägi C, Labhart TP (2017) Geologie der Schweiz. Ott Verlag, BernGoogle Scholar
  21. Godwin KS, Hafner SD, Buff MF (2003) Long-term trends in sodium and chloride in the Mohawk River, New York: the effect of fifty years of road-salt application. Environ Pollut 124:273–281CrossRefGoogle Scholar
  22. Hirsch RM (2014) Large biases in regression-based constituent flux estimates: causes and diagnostic tools. J Am Water Resour Assoc 50:1401–1424CrossRefGoogle Scholar
  23. Hirsch RM, Alley WM, Wilber WG (1988): Concepts for a national water-quality assessment program (NAWQA). U.S. Geological SurveyGoogle Scholar
  24. Hirsch RB, Alexander RB, Smith RA (1991) Selection of methods for the detection and estimation of trends in water quality. Water Resour Res 27:803–813CrossRefGoogle Scholar
  25. Hirsch RB, Hamilton PA, Miller TL (2006) U.S. Geological Survey perspective on water-quality monitoring and assessment. J Environ Monit 8:512–518CrossRefGoogle Scholar
  26. Howden NJK, Burt TP, Worrall F, Whelan MJ, Bieroza M (2010) Nitrate concentrations and fluxes in the River Thames over 140 years (1868–2008): are increases irreversible? Hydrol Process 24:2657–2662CrossRefGoogle Scholar
  27. igbk (2014) Yearly Report Nr. 40, Limnologischer Zustand  des Bodensees (in German). International Commission fort he Protection of Lake Constance. Institut für Seenforschung,- D-88081 Langenargen Google Scholar
  28. Jakob A, Binderheim-Bankay E, Davis JS (2002) National long-term surveillance of Swiss rivers. Verh Internat Verein Limnol 28:1101–1106Google Scholar
  29. Kaushal SS, Groffman PM, Likens GE, Belt KT, Stack WP, Kelly VR, Band LE, Fisher GT (2005) Increased salinization of fresh water in the northeastern United States. Proceed Nat Acad Sci United States 102:13517–13520CrossRefGoogle Scholar
  30. Kaushal SS, Likens GE, Jaworski NA, Pace ML, Sides AM, Seekell D, Belt KT, Secor DH, Wingate RL (2010) Rising stream and river temperatures in the United States. Front Ecol Environ 8:461–466CrossRefGoogle Scholar
  31. Kaushal SS, Likens GE, Utz RM, Pace ML, Grese M, Yepsen M (2013) Increased river alkalinization in the Eastern U.S. Environ Sci Technol 47Google Scholar
  32. Kelly VR, Lovett GM, Weathers KC, Findlay SEG, Strayer DL, Burns DJ, Likens GE (2008) Long-term sodium chloride retention in a rural watershed: legacy effects of road salt on streamwater concentration. Envriron Sci Technol 42:410–415CrossRefGoogle Scholar
  33. Lauerwald R, Hartmann J, Moosdorf N, Kempe S, Raymond PA (2013) What controls the spatial patterns of the riverine carbonate system?—a case study for North America. Chem Geol 337-338:114–127CrossRefGoogle Scholar
  34. Lauerwald R, Laruelle GG, Hartmann J, Ciais P, Regnier PAG (2015) Spatial patterns in CO2 evasion from the global river network. Glob Biogeochem Cycles 29:534–554CrossRefGoogle Scholar
  35. Macpherson GL, Roberts JA, Blair JM, Towsend MA, Fowle DA, Beisner KR (2008) Increasing shallow groundwater CO2 and limestone weathering Konza Prairie, USA. Geochim Cosmochim Acta 82:5581–5599CrossRefGoogle Scholar
  36. Moser A, Wemysss D, Scheidegger R, Fenicia F, Honti M, Stamm C (2017) Modelling biocide and herbicide concentrations in catchments of the Rhine basin. Hydrol Earth Syst Sci Discuss. under reviewGoogle Scholar
  37. Mostert E (2009) International co-operation on Rhine-water quality 1945-2008: an example to follow? Phys Chem Earth 34:142–149CrossRefGoogle Scholar
  38. Mueller B, Gaechter R (2012) Increasing chloride concentrations in Lake Constance: characterization of sources and estimation of loads. Aquat Sci 74:101–112CrossRefGoogle Scholar
  39. Mueller B, Meyer JS, Gaechter R (2015) Alkalinity regulation in calcium carbonate-buffered lakes. Limnol Oceanogr 61:341–352CrossRefGoogle Scholar
  40. North RP, Livingstone DM, Hari RE, Köster O, Niederhauser P, Kipfer R (2013) The physical impact of the late 1980s climate shift on Swiss rivers and lakes. Inland Waters 3:341–350CrossRefGoogle Scholar
  41. Novotny EV, Sander AR, Mohseni O, Stefan HG (2009) Chloride ion transport and mass balance in a metropolitan area using road salt. Water Resour Res 45:W12410CrossRefGoogle Scholar
  42. Orr HG, Simpson GL, Sd C, Watts G, Hughes M, Hannaford J, Dunbar MJ, Laizé CLR, Wilby RL, Battarbee RW, Evans R (2015) Detecting changing river temperatures in England and Wales. Hydrol Process 29:752–766CrossRefGoogle Scholar
  43. Perrin AS, Probst A, Probst JL (2008) Impact of nitrogenous fertilizers on carbonate dissolution in small agricultural catchments: implication for weathering CO2 uptake at regional and global scales. Geochim Cosmochim Acta 72:3105–3123CrossRefGoogle Scholar
  44. Prasuhn V, Sieber U (2005) Changes in diffuse phosphorous and nitrogen inputs into surface waters in the Rhine watershed in Switzerland. Aquat Sci 67:363–371CrossRefGoogle Scholar
  45. Ramakrishna DM, Viraraghavan T (2005) Environmental impact of chemical deicers—a reviw. Water and Soil Pollution 166:49–63CrossRefGoogle Scholar
  46. Raymond PA, Cole JJ (2003) Increase in the export of alkalinity from North America’s largest river. Science 380:88–91CrossRefGoogle Scholar
  47. Raymond PA, Oh N-H, Turner RE, Broussard W (2008) Anthropogenically enhanced fluxes of water and carbon form the Mississippi River. Nature 453:449–452CrossRefGoogle Scholar
  48. Raymond PA, Zappa CJ, Butman D, Bott TL, Potter J, Mulholland P, Laursen AE, McDowell WH, Newbold D (2012) Scaling the gas transfer velocity and hydraulic geometry in streams and small rivers. Limnol Oceanogr: Fluids and Environ 2:41–53CrossRefGoogle Scholar
  49. Reid PC et al. (2015) Global impacts of the 1980s regime shift. Global change biologyGoogle Scholar
  50. Rodionov SN (2004) A sequential algorithm for testing climate regime shifts. Geophys Res Lett 31:L09204CrossRefGoogle Scholar
  51. Rodriguez-Murillo JC, Zobrist J, Fiella M (2015) Temporal trends in organic carbon content in the main Swiss rivers. Sci Total Environ 502:206–217CrossRefGoogle Scholar
  52. Rogara M (2007) Synchronous trends in N-NO3 export from N-saturated river catchments in relation to climate. Biogeochem 86:251–268CrossRefGoogle Scholar
  53. Ruff M, Singer H, Ruppe S, Mazacek J, Dolf R, Leu C (2013) 20 Jahre Rheinüberwachung. Aqua & Gas 5:16–25Google Scholar
  54. Schuerch M, Kozel R, Schotterer U, Tripet JP (2003) Observation of isotopes in the water cycle—the Swiss National Network (NISOT). Environ Geol 45:1–11CrossRefGoogle Scholar
  55. Schwandt D, Deutsch M, Keller M (2010) The beginnings of systematic water quality investigations in the catchments of the rivers Elbe and Rhine—historical situation, protagonists, developments (in German with english summary). Hydrologie und Wassebewirtschaftung 54:116–128Google Scholar
  56. Siegrist HR, Boller M (1999) Auswirkungen des Phosphatverbots in den Waschmitteln auf die Abwasserrreinigung in der Schweiz. Korrespondenz Abwasser 46:57–65Google Scholar
  57. Spiess E (2011) Nitrogen, phosphorous and potassium balances and cycles of Swiss Agriculture from 1975 to 2008. Nutrient Cycle in Agroecosyst 91:351–365CrossRefGoogle Scholar
  58. Stets EG, Kelly VK, Crawford CG (2014) Long-term trends in alkalinity in large rivers of the conterminous US in relation to acidification, agriculture and hydrological modification. Sci Total Environ 488-489:280–289CrossRefGoogle Scholar
  59. Stoll JMA, Giger W (1998) Mass balance for detergent-derived fluorescent whitening agents in surface waters of Switzerland. Water Res 32:2041–2050CrossRefGoogle Scholar
  60. Stumm W, Morgan JJ (1996) Aquatic chemistry. John Wiley & Sons, New York, p 1022Google Scholar
  61. Szramek K, Walter LM (2004) Impact of carbonate precipitation on riverine inorganic carbon mass transport from a mid-continent forested watershed. Aquat Geochem 10:99–137CrossRefGoogle Scholar
  62. Szramek K, Walter LM, Kanduc T, Ogrine N (2011) Dolomite versus calcite weathering in hydrogeochemically diverse watersheds established on bedded carbonates (Sava and Soca Rivers, Slovenia). Aquat Geochem 17:357–396CrossRefGoogle Scholar
  63. Team RDC (2011) R. A language and environment for statistical computing. R Foundation for Statistical Computing, ViennaGoogle Scholar
  64. Webb BW, Nobilis F (2007) Long-term changes in river temperature and the influence of climatic and hydrological factors. Hydrol Sci J 52:74–85CrossRefGoogle Scholar
  65. Wessels M, Mohaupt K, Kummerlin R, Lenhard A (1999) Reconstructing past eutrophication trends from diatoms and biogenic silica in the sediment and the pelagic zone of Lake Constance, Germany. J Palelimnol 21:171–192CrossRefGoogle Scholar
  66. Worrall F, Howden NJK, Burt TP (2012) A 125 year record of fluvial calcium flux from a temperate catchment: interplay of climate, land-use change and atmospheric deposition. J Hydrol 468-469:249–256CrossRefGoogle Scholar
  67. Worrall F, Howden NJK, Burt TP (2013) Assessment of sample frequency bias and precision in fluvial flux calculations—an improved low bias estimation method. J Hydrol 503:101–110CrossRefGoogle Scholar
  68. Worrall F, Howden NJK, Burt TP (2015) Time series analysis of the world’s longest fluvial nitrate record: evidence for changing states of catchment saturation. Hydrol Process 29:434–444CrossRefGoogle Scholar
  69. Zobrist J (2010) Water chemistry of Swiss alpine rivers. In: Bundi U (ed) Alpine waters. Handbook Environmental Chemistry. Springer Verlag, Berlin Heidelberg, pp 95–118Google Scholar
  70. Zobrist J, Reichert P (2006) Bayesian estimation of export coefficients from diffuse and point sources in Swiss watersheds. J Hydrol 329:207–223CrossRefGoogle Scholar
  71. Zobrist J, Sigg L, Schoenenberger U (2004) NADUF - thematische Auswertung der Messresultate 1974 bis 1998. Schriftenreihe der Eawag. Eawag, Duebendorf, p 125Google Scholar
  72. Zobrist J, Schoenenberger U, Alder AC, Kaenel B, Steinmann P, Giger W (2011) 77 Jahre Untersuchungen an der Glatt. Aqu & Gas 315–327Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Eawag, Swiss Federal Institute of Aquatic Science and Technology (Eawag)DübendorfSwitzerland
  2. 2.UsterSwitzerland
  3. 3.ZürichSwitzerland

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