The role of external ammonium inputs in freshwater acidification

Abstract

Gaseous ammonia released into the atmosphere from animal manure, fertilizer and industrial processes, neutralizes acid oxidation products of sulphur and nitrogen oxides in precipitation. This results in a substantial increase in pH of precipitation. Once deposited in soil or water, the ammonium compounds may be oxidized to nitric acid. This means that hydrogen ions neutralized in the atmosphere are now released. This paper concerns bulk precipitation sampled at some selected northern Italian and Dutch sites, representing areas with different regional industrial and agricultural impact. In addition the role of external loads of ammonium in freshwater acidification is discussed considering an ammonium sulphate polluted subalpine lake in northern Italy and the results of experimentla studies on susceptible soft water systems in The Netherlands. In these cases the acidifying effect of biochemical ammonium conversions, particularly ammonium oxidation, was evident, reaching pH values below 4. Regarding the deleterious chemical and ecological effects, a reduction in the emission of gaseous ammonia is programmed for The Netherlands. In the Alpine region atmospheric ammonia and ammonium also constitute a threat for sensitive ecosystems.

Zusammenfassung

Gasförmiges Ammoniak, das durch tierische Abgänge, Düngemittel und industrielle Prozesse in die Atmosphäre gelangt, neutralisiert saure Oxidationsprodukte von Schwefel-und Stickoxiden im Niederschlag. Dies führt zu einer erheblichen Erhöhung des pH-Wertes in den Niederschlägen. Sobald Ammoniumverbindungen in Boden oder Wasser gelangen, können sie zu Salpetersäure umgewandelt werden, wobei Wasserstoffionen freiwerden.

Die Chemie der Niederschläge in einigen ausgewählten und unterschiedlich belasteten norditalienischen und holländischen Regionen wird behandelt. In den Niederlanden wie auch in der subalpinen Region Italiens einschließlich der Poebene ist die atmosphärische Belastung durch Ammoniumionen hoch.

Die Bedeutung der externen Ammoniumbelastung für die Azidifizierung von Süßwasser wird anhand eines durch Ammoniumsulphat hoch belasteten subalpinen Sees in Norditalien sowie experimentelle Studien an gefährdeten Süßwassersystemen mit geringer Pufferkapazität in de Niederlanden diskutiert. In diesen Fällen ist die durch biochemische Umwandlung des Ammoniumions, besonders durch Oxidation, verursachte Azidifizierung erheblich, mit pH-Werten ≤4.

Die Wichtigkeit des Ammoniaks und Ammoniumions als Azidifizierung verursachende Verbindungen wurde in den Niederlanden erkannt, und eine Verringerung der Emissionen ist geplant. Es wird ausdrücklich darauf hingewiesen, daß diese atmosphärischen Schadstoffe auch für die Alpenregion eine Bedrohung darstellen.

Résumé

L'ammonium gazeux cédé a l'atmosphère par l'engrais animal, par les fertilisants et par les procédés industriels neutralise les produits acides de l'oxydation du soufre et les oxydes de l'azote dans les précipitations. Cela provoque une augmentation remarquable de la valeur pH des précipitations. Une fois déposés sur le terrain ou dans les eaux les composés de l'ammonium peuvent être transformés en acide nitrique, et les ions d'hydrogène, neutralisés dans l'atmosphère, sont liberés.

Cet article considère la chimie des précipitations sèches et humides cumulées («bulk») dans une série de localités, en Italie du Nord et en Hollande, qui représentent des aires avec un impact industriel et agricole différent selon les régions choisies. Soît en Hollande soît dans le régions subalpines de l'Italie et dans la vallée du Po la déposition atmosphérique d'ammonium est élevée. On discute le rôle des charges externes d'ammonium dans l'acidification des eaux douces en considerant le cas d'un lac subalpin de l'Italie du Nord pollué par le sulfate d'ammonium et les recherches experimentales sur des systèmes d'eaux très douces particulièrement sensibles, en Hollande. Dans tous ces cas l'effet de l'acidification due aux transformations biochimiques de l'ammonium, et en particulier à l'oxydation de l'ammonium, e été mis bien en évidence par l'abaissement du pH jusqu'à des valeurs inférieures à 4.

L'importance de l'ammoniaque et de l'ammonium dans les procès d'acidification a été reconnue en Hollande, où un programme de réduction des émissions a déjà été mis à point. On souligne que ces polluants atmosphériques constituent une menace aussi pour les Alpines.

This is a preview of subscription content, log in to check access.

References

  1. 1

    Oden, S.: The acidity problem—an outline of concepts. Water, Air Soil Poll.6, 137–166 (1976).

    Article  CAS  Google Scholar 

  2. 2

    Henriksen, A.: Acidification of freshwater—a large scale titration. Proc. “Int. Conf. Ecol. Imp. Acid. Precip.”, Norway 1980, SNSF project, 68–74 (1980).

  3. 3

    Schnoor, J. L., and Stumm, W.: The role of chemical weathering in the neutralization of acidic deposition. Schweiz. Z. Hydrol.48, 171–195 (1986).

    CAS  Google Scholar 

  4. 4

    Ruess, J. O.: Chemical/biological relationships relevant to ecological effects of acid rainfall, 46p. E. P. A.-600/3-75-032 (1975).

  5. 5

    Ulrich, B.: Soil acidity and its relation to acid deposition. In: Ulrich, B. and Pankrath, J. (eds.): Effects of accumulation of air pollutants in forest ecosystems, pp. 127–146. Reidel Publ. 1983.

  6. 6

    Breemen, N. van, Driscoll, C. T., and Mulder, J.: Acidic deposition and internal proton sources in acidification of soils and waters. Nature307, 599–604 (1984).

    Article  Google Scholar 

  7. 7

    Kelly, C. A., Rudd, J. W. M., Cook, R. B., and Schindler, D. W.: The potential importance of bacterial processes in regulating rate of lake acidification. Limnol. Oceanogr.27, 868–882 (1982).

    CAS  Google Scholar 

  8. 8

    Schnoor, J. L., and Stumm, W.: Acidification of aquatic and terrestrial ecosystems. In: Stumm, W. (ed.): Chemical processes in lakes, pp. 311–337. Wiley & Sons, New York (1985).

    Google Scholar 

  9. 9

    Breemen, N. van, Burrough, P. A., Velthorst, E. J., Dobben, H. F. van, Wit, T. de, Ridder, T. B. de, and Reynders, H. F.: Soil acidification from atmospheric ammonium sulphate in canopy troughfall. Nature299, 548–550 (1982).

    Article  Google Scholar 

  10. 10

    Anonymous: Acid rain, a review of the phenomenon in the EEC, and Europe, 159p. Environmental Resources Ltd., Graham and Trotman. London 1983.

  11. 11

    Galloway, J. N., and Dillon, P. J.: Effects of acid deposition: the importance of nitrogen. In: “Ecological effects of acid deposition.” Nat. Swedish Env. Prot. Board. Report PM 1636, pp. 145–160 (1983).

  12. 12

    Nihlgård, B.: The ammonium hypothesis: an additional explanation to the forest die-back in Europe. Ambio14, 2–8 (1985).

    Google Scholar 

  13. 13

    Roelofs, J. G. M.: The effect of airborne sulphur and nitrogen deposition on aquatic and terrestrial heathland vegetation. Experientia42, 372–377 (1986).

    Article  CAS  Google Scholar 

  14. 14

    Asman, W. A. H., and Janssen, A. J.: A long-range transport model for ammonia and ammonium for Europe and some model experiments. Report R-86-6. Institute for Meteorology and Oceanography. State University Utrecht, The Netherlands 1986.

    Google Scholar 

  15. 15

    Schuurkes, J. A. A. R.: Atmospheric ammonium sulphate deposition and its role in the acidification and nitrogen enrichment of poorly buffered aquatic systems. Experientia42, 351–357 (1986).

    Article  CAS  Google Scholar 

  16. 16

    Gruppo di Studio delle caratteristiche chimiche delle precipitazoni dell'Italia Settentrionale. Rapporto finale (anni 1983–1984). Ingegneria Ambientale (in press).

  17. 17

    Monti, R.: La graduale estinzione della vita nel Lago d'Orta. Rend. R. Ist. Lomb. Sci. Lett.63, 3–22 (1930),

    Google Scholar 

  18. 18

    Baldi, E.: Il Lago d'Orta, suo declino biologico e condizioni attuali. Mem. Ist. Ital. Idrobiol.5, 145–188 (1949).

    Google Scholar 

  19. 19

    Vollenweider, R. A.: Studi sulla situazione attuale del regime chimico e biologico del Lago d'Orta. Mem. Ist. Ital. Idrobiol.16, 21–125 (1963).

    Google Scholar 

  20. 20

    Mosello, R., Bonacina, C., Carollo, A., Libera, V., and Tartari, G. A.: Acidification due to in-lake ammonia oxidation: an attempt to quantify the proton production in a highly polluted subalpine Italian lake (Lake Orta). Mem. Ist. Ital. Idrobiol.44, (in press).

  21. 21

    Schuurkes, J. A. A. R., Heck, I. C. C., Hesen, P. L. G. M., Leuven, R. S. E. W., and Roelofs, J. G. M.: Effects of sulphuric acid and acidifying ammonium deposition on water quality and vegetation of simulated soft water ecosystems. Water, Air Soil Poll.31, 267–272 (1986).

    Article  CAS  Google Scholar 

  22. 22

    Schuurkes, J. A. A. R.: Exposure of small-scale aquatic systems to various deposition levels of ammonium, sulphate and acid rain. In: H. Barth (ed.): Proc. “COST Workshop on reversibility of acidification”. Grimstad, Norway, June 1986, pp. 45–57. Commission of the European Communities, Brussels 1986.

    Google Scholar 

  23. 23

    Schuurkes, J. A. A. R., Jansen, J., and Maessen, M.: Water acidification by addition of ammonium sulphate in sediment-water columns and in natural waters. Arch. Hydrobiol. (in press).

  24. 24

    Mosello, R., Pugnetti, A., and Tartari, G. A.: Chemistry of atmospheric deposition and lake acidification in Northern Italy, with emphasis on the role of ammonia. In: H. Barth (ed.): Proc. “COST workshop on reversibility of acidification”. Grimstad, Norway, June 1986, pp. 99–115. Commission of the European Communities, Brussels 1986.

    Google Scholar 

  25. 25

    Barbieri, A., and Righetti, G.: Le precipitazioni acide e i loro problemi nel Canton Ticino e in Svizzera. Atti Giornate di Studio SEP Pollution, 275–282 (1984).

  26. 26

    Leuven, R. S. E. W., Kersten, H. L. M., Schuurkes, J. A. A. R., Roelofs, J. G. M., and Arts, G. H. P.: Evidence for recent acidification of lentic soft waters in The Netherlands. Water, Air Soil Poll.30, 387–392 (1986).

    Article  CAS  Google Scholar 

  27. 27

    Buysman, E., Maas, J. F. M., and Asman, W. H. M.: Ammonia emission in Europe, 28p. Report R-85-2. Institute for Meteorology and Oceanography. State University Utrecht, The Netherlands 1985.

    Google Scholar 

  28. 28

    Goldman, J. C., and Brewer, P. G.: Effect of nitrogen source and growth rate on microflora-mediated changes in alkalinity. Limnol. Oceanogr.25, 352–357 (1980).

    CAS  Article  Google Scholar 

  29. 29

    Raven, J. A., Regulation of pH and generation of osmolarity in vascular plants: a cost-benefit analysis in relation of efficiency of use of energy, nitrogen and water. Tansley Review no. 2. New Phytol.101, 25–77 (1985).

    Article  CAS  Google Scholar 

  30. 30

    Goering, J. J.: The role of nitrogen in eutrophic processes. In: R. Mitchell (ed.): Water Pollution Biology1, 46–68 (1972).

  31. 31

    Schindler, D. W., Turner, M. A., and Hesslein, R. H.: Acidification and alkalinization of lakes by experimental addition of nitrogen compounds. Biogeochemistry1, 117–133 (1985).

    Article  CAS  Google Scholar 

  32. 32

    Leuven, R. S. E. W., and Schuurkes, J. A. A. R.: Effecten van zure neerslag op zwak gebufferde en voedselarme wateren, 131p. Dutch Ministry of Housing, Physical Planning and Environment. Publication series “Lucht”47, in Dutch (1985).

  33. 33

    Anonymous: Acidification in The Netherlands—effects and policies, 9p. Conference Munich 1984, Dutch Ministry of Housing, Physical Planning and Environment, The Hague 1985.

  34. 34

    Anonymous: The role of ammonia in acidification in The Netherlands, 8p. Dutch Ministry of Housing, Physical Planning and Environment, The Hague 1986.

  35. 35

    National Institute of Human Health and Environment. The Netherlands. Kwaliteitsonderzoek in de rijskwateren, Reports 1981, 1982, 1983, 1984, 1985, in Dutch.

  36. 36

    Buysman, E.: Historical trend in the ammonia emission in Europe, 50p. Report R-86-9. Institute for Meteorology and Oceanography. State University Utrecht, The Netherlands 1986.

    Google Scholar 

Download references

Author information

Affiliations

Authors

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Schuurkes, J.A.A.R., Mosello, R. The role of external ammonium inputs in freshwater acidification. Schweiz. Z. Hydrol 50, 71–86 (1988). https://doi.org/10.1007/BF02538372

Download citation

Keywords

  • Ammonium Sulphate
  • Ammonium Oxidation
  • Gaseous Ammonia
  • Ammonium Compound
  • Soft Water