, Volume 116, Issue 1–3, pp 303–334 | Cite as

Trends in cation, nitrogen, sulfate and hydrogen ion concentrations in precipitation in the United States and Europe from 1978 to 2010: a new look at an old problem

  • Kate Lajtha
  • Julia Jones


Industrial emissions of SO2 and NOx, resulting in the formation and deposition of sulfuric and nitric acids, affect the health of both terrestrial and aquatic ecosystems. Since the mid-late 20th century, legislation to control acid rain precursors in both Europe and the US has led to significant declines in both SO4–S and H+ in precipitation and streams. However, several authors noted that declines in streamwater SO4–S did not result in stoichiometric reductions in stream H+, and suggested that observed reductions in base cation inputs in precipitation could lessen the effect of air pollution control on improving stream pH. We examined long-term precipitation chemistry (1978–2010) from nearly 30 sites in the US and Europe that are variably affected by acid deposition and that have a variety of industrial and land-use histories to (1) quantify trends in SO4–S, H+, NH4–N, Ca, and NO3–N, (2) assess stoichiometry between H+ and SO4–S before and after 1990, and (3) examine regional synchrony of trends. We expected that although the overall efforts of developed countries to reduce air pollution and acid rain by the mid-late 20th century would tend to synchronize precipitation chemistry among regions, geographically varied patterns of fossil fuel use and pollution control measures would produce important asynchronies among European countries and the United States. We also expected that control of particulate versus gaseous emission, along with trends in NH3 emissions, would be the two most significant factors affecting the stoichiometry between SO4–S and H+. Relationships among H+, SO4–S, NH4–N, and cations differed markedly between the US and Europe. Controlling for SO4–S levels, H+ in precipitation was significantly lower in Europe than in the US, because (1) alkaline dust loading from the Sahara/Sahel was greater in Europe than the US, and (2) emission of NH3, which neutralizes acidity upon conversion to NH4 +, is generally significantly higher in Europe than in the US. Trends in SO4–S and H+ in precipitation were close to stoichometric in the US throughout the period of record, but not in Europe, especially eastern Europe. Ca in precipitation declined significantly before, but not after 1990 in most of the US, but Ca declined in eastern Europe even after 1990. SO4–S in precipitation was only weakly related to fossil fuel consumption. The stoichiometry of SO4–S and H+ may be explained in part by emission controls, which varied over time and among regions. Control of particulate emissions reduces alkaline particles that neutralize acid precursors as well as S-containing particulates, reducing SO4–S and Ca more steeply than H+, consistent with trends in the northeastern US and Europe before 1990. In contrast, control of gaseous SO2 emissions results in a stoichiometric relationship between SO4–S and H+, consistent with trends in the US and many western European countries, especially after 1991. However, in many European countries, declining NH3 emissions contributed to the lack of stoichiometry between SO4–S and H+.Recent reductions in NOx emissions have also contributed to declines in H+ in precipitation. Future changes in precipitation acidity are likely to depend on multiple factors including trends in NOx and NH3 emission controls, naturally occurring dust, and fossil fuel use, with significant implications for the health of both terrestrial and aquatic ecosystems.


Acid deposition Ammonium Base cations Clean air act EMEP LTER NADP Nitrate Sulfate 



This study was supported in part by NSF Grants 0823380, 0333257, and 0817064, as well as NSF LTER and US Forest Service support to sites with long-term precipitation chemistry records (Andrews, Coweeta, Fernow, Hubbard Brook, Kane, and Marcell Experimental Forests, Kellogg Biological Station). We also acknowledge funding to the National Atmospheric Deposition Program, as well as support for the EMEP (European precipitation monitoring program). C.T. Driscoll generously provided invaluable advice for the analysis and interpretation of the data.


  1. Aber JD (1982) Potential effects of acid precipitation on soil nitrogen and productivity of forest ecosystems. Water Air Soil Pollut 18:405–412CrossRefGoogle Scholar
  2. Aber JD, McDowell NG, Nadelhoffer KJ, Magill A, Berntson G, Kamakea M, McNully S, Currie W, Rustad L, Fernandez I (1998) Nitrogen saturation in temperate forest ecosystems. Bioscience 48:921–934CrossRefGoogle Scholar
  3. Baker LA, Herlihy AT, Kaufmann PR (1991) Acidic lakes and streams in the United States: the role of acidic deposition. Science 252:1151–1154CrossRefGoogle Scholar
  4. Battye R, Battye W, Overcash C, Fudge S (1994) Development and selection of ammonia emission factors. EPA/600/R-94/190. Final report prepared for United States Environmental Protection Agency, Office of Research and Development. USEPA Contract No. 68-D3-0034, Work Assignment 0–3Google Scholar
  5. Bowman WD, Cleveland CC, Halada L, Hresko J, Baron JS (2008) Negative impact of nitrogen deposition on soil buffering capacity. Nat Geosci 1:767–770CrossRefGoogle Scholar
  6. Brown TC, Froemke P (2012) Improved measures of atmospheric deposition have a negligible effect on multivariate measures of risk of water-quality impairment: response from Brown and Froemke. Bioscience 62:621–622Google Scholar
  7. Burton AW, Aherne J (2012) Changes in the chemistry of small Irish lakes. Ambio 41:170–179CrossRefGoogle Scholar
  8. Clarisse L, Clerbaux C, Dentener F, Hurtmans D, Coheur P-F (2009) Global ammonia distribution derived from infrared satellite observations. Nature Geosci 2:479–483CrossRefGoogle Scholar
  9. Draaijers GJP, Leeuwen EP, Jong PGH, Erisman JW (1997) Base-cation deposition in Europe—Part II. Acid neutralization capacity and contribution to forest nutrition. Atmos Environ 31:4159–4168CrossRefGoogle Scholar
  10. Driscoll CT, Likens GE, Hedin LO, Eaton JS, Bormann FH (1989) Changes in the chemistry of surface waters. Environ Sci Technol 23:137–143CrossRefGoogle Scholar
  11. Earthtrends (2003) Earthtrends: environmental information. Accessed March 2012
  12. Elliott EM, Kendall C, Boyer EW, Burns DA, Lear GG, Golden HE, Harlin K, Bytnerowicz A, Butler TJ, Glatz R (2009) Dual nitrate isotopes in dry deposition: utility for partitioning NOx source contributions to landscape nitrogen deposition. J Geophys Res Biogeosci 114:G04020Google Scholar
  13. Emmett B (2007) Nitrogen Saturation of Terrestrial Ecosystems: some recent findings and their implications for our conceptual framework. Water Air Soil Pollut Focus 7:99–109CrossRefGoogle Scholar
  14. EPA (2001). National pollutant discharge elimination system permit regulation and effluent limitations: guidelines and standards for concentrated animal feeding operations; proposed rule (January 2001)Google Scholar
  15. EPA (2012). Nitrogen Oxides (NOx) Control Regulations. Accessed 14 May 2013
  16. Erisman JW, Draaijers GPJ (1995) Atmospheric deposition in relation to acidification and eutrophication. Studies in Environmental Science, vol 63. Elsevier, Amsterdam, p 9Google Scholar
  17. Erisman JW, Grennfelt P, Sutton M (2003) The European perspective on nitrogen emission and deposition. Environ Int 29:311–325CrossRefGoogle Scholar
  18. Federer CA, Hornbeck JW, Tritton LM, Martin CW, Pierce RS, Smith CT (1989) Long term depletion of calcium and other nutrients in eastern US forests. Environ Manage 13:593–601CrossRefGoogle Scholar
  19. Fraser MP, Cass GR (1998) Detection of excess ammonia emissions from in-use vehicles and the implications for fine particle control. Environ Sci Technol 32:1053–1057CrossRefGoogle Scholar
  20. Gbondo-Tugbawa SS, Driscoll CT (2003) Factors controlling long-term changes in soil pools of exchangeable basic cations and stream acid neutralizing capacity in a northern hardwood forest ecosystem. Biogeochemistry 63:161–185CrossRefGoogle Scholar
  21. Ginoux P, Prospero JM, Torres O, Chin M (2004) Long-term simulation of global dust distribution with the GOCART model: correlation with North Atlantic Oscillation. Environ Model & Softw 19:113–128Google Scholar
  22. Greaver TL, Sullivan TJ, Herrick JD, Barber MC, Baron JS, Cosby BJ, Deerhake ME, Dennis RL, Dubois J-JB, Goodale CL, Herlihy AT, Lawrence GB, Liu L, Lynch JA, Novak KJ (2012) Ecological effects of nitrogen and sulfur air pollution in the US: what do we know? Front Ecol Environ 10:365–372CrossRefGoogle Scholar
  23. Grini A, Myhre G, Zender CS, Isaksen ISA (2005) Model simulations of dust sources and transport in the global atmosphere: effects of soil erodibility and wind speed variability. J Geophys Res 110:D02205Google Scholar
  24. Hedin LO, Granat L, Likens GE, Buishand TA, Galloway JN, Butler TJ, Rodhe H (1994) Steep declines in atmospheric base cations in regions of Europe and North America. Nature 367:351–354CrossRefGoogle Scholar
  25. Horváth L, Sutton MA (1998) Long term record of ammonia and ammonium concentrations at K-Puszta, Hungary. Atmos Environ 32:339–344CrossRefGoogle Scholar
  26. Horváth L, Fagerli H, Sutton MA (2009) Long-term record (1981-2005) of ammonia and ammonium concentrations at K-Puszta Hungary and the effect of sulphur dioxide emission change on measured and modelled concentrations. In: Sutton MA, Reis S, Baker SMH (eds) Atmospheric ammonia: detecting emission changes and environmental impacts. Springer, Berlin, pp 181–185CrossRefGoogle Scholar
  27. Joslin JD, Kelly JM, Van Miegroet H (1992) Soil chemistry and nutrition of North American spruce-fir stands: evidence for recent change. J Environ Qual 21:12–30CrossRefGoogle Scholar
  28. Juice SM, Fahey TJ, Siccama TG, Driscoll CT, Denny EG, Eager C, Cleavitt NL, Minocha R, Richardson AD (2006) Response of sugar maple to calcium addition to northern hardwood forest. Ecology 87:1267–1280CrossRefGoogle Scholar
  29. Lehmann CB, Bowersox V, Larson R, Larson S (2007) Monitoring Long-term Trends in Sulfate and Ammonium in US Precipitation: results from the National Atmospheric Deposition Program/National Trends Network. Water Air Soil Pollut Focus 7:59–66CrossRefGoogle Scholar
  30. Likens GE, Bormann FH, Pierce RS, Eaton JS, Munn RE (1984) Long-term trends in precipitation chemistry at Hubbard Brook, New Hampshire. Atmos Environ 18:2641–2647CrossRefGoogle Scholar
  31. Likens GE, Driscoll CT, Buso DC (1996) Long-term effects of acid rain: response and recovery of a forest ecosystem. Science 272:244–246CrossRefGoogle Scholar
  32. Lövblad G, Tarrason L, Tørseth K, Dutchak S (2004) EMEP Assessment. Part I, European perspective, Norwegian Meteorological Institute, OsloGoogle Scholar
  33. Lovett GM, Lindberg SE (1993) Atmospheric deposition and canopy interactions of nitrogen in forests. Can J For Res 23:1603–1616CrossRefGoogle Scholar
  34. Loye-Pilot MD, Martin JM, Morelli K (1986) Saharan dust: influence on the rain acidity and significance for atmospheric input to Mediterranean. Nature 321:427–428CrossRefGoogle Scholar
  35. Martinez-Garcia A, Rosell-Mele A, Jaccard SL, Geibert W, Sigman DM, Haug GH (2011) Southern Ocean dust-climate coupling over the past four million years. Nature 476:312–315CrossRefGoogle Scholar
  36. Medhi N (2009) Regulatory matters: which factors matter in regulating the environment? APPAM 2009 Conference PaperGoogle Scholar
  37. Merkel M (2002) Raising a stink: air emissions from factory farms. Report of environmental integrity project. Accessed 14 May 2013
  38. Metcalfe SE, Atkins DHF, Derwent RG (1989) Acid deposition modelling and the interpretation of the United Kingdom secondary precipitation network data. Atmos Environ (1967) 23:2033–2052CrossRefGoogle Scholar
  39. Mosquera J, Monteny GJ, Erisman JW (2005) Overview and assessment of techniques to measure ammonia emissions from animal houses: the case of the Netherlands. Environ Pollut 135:381–388CrossRefGoogle Scholar
  40. Mulitza S, Heslop D, Pittauerova D, Fischer HW, Meyer I, Stuut JB, Zabel M, Mollenhauer G, Collins JA, Kuhnert H, Schulz M (2010) Increase in African dust flux at the onset of commercial agriculture in the Sahel region. Nature 466:226–228CrossRefGoogle Scholar
  41. Neff JC, Ballantyne AP, Farmer GL, Mahowald NM, Conroy JL, Landry CC, Overpeck JT, Painter TH, Lawrence CR, Reynolds RL (2008) Increasing eolian dust deposition in the western United States linked to human activity. Nature Geosci 1:189–195CrossRefGoogle Scholar
  42. Norton SA, Vesely J (2003) Acidification and acid rain. Treatise Geochem 9:367–406CrossRefGoogle Scholar
  43. Oulehle F, McDowell WH, Aitkenhead-Peterson JA, Krám P, Hruška J, Navrátil T, Buzek F, Fottová D (2008) Long-term trends in stream nitrate concentrations and losses across watersheds undergoing recovery from acidification in the Czech Republic. Ecosystems 11:410–425CrossRefGoogle Scholar
  44. Pannatier EG, Luster J, Zimmermann S, Blaser P (2005) Acidification of Soil solution in a chestnut forest stand in southern Switzerland: are there signs of recovery? Environ Sci Technol 39:7761–7767CrossRefGoogle Scholar
  45. Piccolo MC, Perillo GME, Varela P (1988) Alkaline precipitation in Bahia Blanca, Argentina. Environ Sci Technol 22:216–219CrossRefGoogle Scholar
  46. Prospero JM, Lamb PJ (2003) African droughts and dust transport to the Caribbean: climate change implications. Science 302:1024–1027CrossRefGoogle Scholar
  47. Rusek J (1993) Air-pollution-mediated changes in alpine ecosystems and ecotones. Ecol Appl 3:409–416CrossRefGoogle Scholar
  48. Schindler DW (1988) Effects of acid rain on freshwater ecosystems. Science 239:149–157CrossRefGoogle Scholar
  49. Schlesinger WH, Hartley AE (1992) A global budget for atmospheric NH3. Biogeochemistry 15:191–211CrossRefGoogle Scholar
  50. Schulze E-D (1989) Air pollution and forest decline in a spruce (Picea abies) forest. Science 244:776–783CrossRefGoogle Scholar
  51. Skjøth CA, Geels C (2013) The effect of climate and climate change on ammonia emissions in Europe. Atmos Chem Phys 13:117–128Google Scholar
  52. Smith SJ, van Aardenne J, Klimont Z, Andres RJ, Volke A, Delgado Arias S (2011) Anthropogenic sulfur dioxide emissions: 1850–2005. Atmos Chem Phys 11(1101–1116):2011Google Scholar
  53. Stoddard JL, Jeffries DS, Lukewille A, Clair TA, Dillon PJ, Driscoll CT, Forsius M, Johannessen M, Kahl JS, Kellogg JH, Kemp A, Mannio J, Monteith DT, Murdoch PS, Patrick S, Rebsdorf A, Skjelkvale BL, Stainton MP, Traaen T, van Dam H, Webster KE, Wieting J, Wilander A (1999) Regional trends in aquatic recovery from acidification in North America and Europe. Nature 401:575–578CrossRefGoogle Scholar
  54. Sullivan TJ, Charles DF, Smol JP, Cumming BF, Selle AR, Thomas DR, Bernert JA, Dixit SS (1990) Quantification of changes in lakewater chemistry in response to acidic deposition. Nature 345:54–58CrossRefGoogle Scholar
  55. Sullivan TJ, Cosby BJ, Jackson WA, Snyder KU, Herlihy AT (2011) Acidification and prognosis for future recovery of acid-sensitive streams in the Southern Blue Ridge Province. Water Air Soil Pollut 219:11–26CrossRefGoogle Scholar
  56. Taylor MR, Rubin ES, Hounshell DA (2005) Control of SO2 emissions from power plants: a case of induced technological innovation in the US. Technol Forecast Soc Change 72:697–718CrossRefGoogle Scholar
  57. Vicars WC, Sickman JO (2011) Mineral dust transport to the Sierra Nevada, California: loading rates and potential source areas. J Geophys Res 116:G01018Google Scholar
  58. Warby RA, Johnson CE, Driscoll CT (2009) Continuing acidification of organic soils across the northeastern USA: 1984–2001. Soil Sci Soc Am J 73:274–284CrossRefGoogle Scholar
  59. Yu H, Remer LA, Chin M, Bian H, Tan Q, Yuan T, Zhang Y (2012) Aerosols from overseas rival domestic emissions over North America. Science 337:566–569CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2013

Authors and Affiliations

  1. 1.Department of Crop and Soil SciencesOregon State UniversityCorvallisUSA
  2. 2.College of Earth, Ocean, and Atmospheric Sciences, Oregon State UniversityCorvallisUSA

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