, Volume 88, Issue 1, pp 1–13 | Cite as

Influences of calcium availability and tree species on Ca isotope fractionation in soil and vegetation

  • Blair D. Page
  • Thomas D. Bullen
  • Myron J. Mitchell
Original Paper


The calcium (Ca) isotope system is potentially of great use for understanding biogeochemical processes at multiple scales in forest ecosystems, yet remains largely unexplored for this purpose. In order to further our understanding of Ca behavior in forests, we examined two nearly adjacent hardwood-dominated catchments with differing soil Ca concentrations, developed from crystalline bedrock, to determine the variability of 44Ca/40Ca ratios (expressed as δ44Ca) within soil and vegetation pools. For both sugar maple and American beech, the Ca isotope compositions of the measured roots and calculated bulk trees were considerably lighter than those of soil pools at these sites, suggesting that the trees were able to preferentially take up light Ca at the root–soil interface. The Ca isotope compositions of three of four root samples were among the lightest values yet reported for terrestrial materials (δ44Ca ≤−3.95‰). Our results further indicate that Ca isotopes were fractionated along the transpiration streams of both tree species with roots having the least δ44Ca values and leaf litter the greatest. An approximately 2‰ difference in δ44Ca values between roots and leaf litter of both tree species suggests a persistent fractionation mechanism along the transpiration stream, likely related to Ca binding in wood tissue coupled with internal ion exchange. Finally, our data indicate that differing tree species demand for Ca and soil Ca concentrations together may influence Ca isotope distribution within the trees. Inter-catchment differences in Ca isotope distributions in soils and trees were minor, indicating that the results of our study may have broad transferability to studies of forest ecosystems in catchments developed on crystalline substrates elsewhere.


Calcium δ44Ca Fractionation Isotope Soil Vegetation 



This research was supported by the National Science Foundation (Ecosystem Studies) with additional support by the NYSERDA (New York State Energy Research and Development Authority) and the USEPA. Special thanks are given to Patrick McHale, David Lyons, Linda Galloway, Don Bickelhaupt, and Kristin Hawley for help in both the field and laboratory components of this research. Thanks also are given to the staff at the Adirondack Ecological Center for helping to support these efforts at the Huntington Forest. We also thank Steven Perakis, B. Wiegand, and an anonymous reviewer for helpful comments on previous versions of this manuscript.


  1. Bailey SW, Hornbeck JW, Driscoll CT, Gaudette HE (1996) Calcium inputs and transport in a base-poor forest ecosystem as interpreted by Sr isotopes. Water Resour Res 32:707–719CrossRefGoogle Scholar
  2. Bailey SW, Horsley SB, Long RP, Hallett RA (2004) Influence of edaphic factors on sugar maple nutrition and health on the Allegheny Plateau. Soil Sci Soc Am J 68:243–252CrossRefGoogle Scholar
  3. Bailey SW, Horsley SB, Long RP (2005) Thirty years of change in forest soils of the Allegheny Plateau, Pennsylvania. Soil Sci Soc Am J 69:681–690CrossRefGoogle Scholar
  4. Bangerth F (1979) Calcium-related physiological disorders of plants. Annu Rev Phytopathol 17:97–122CrossRefGoogle Scholar
  5. Blum JD, Taliaferro EH, Weisse MT, Holmes RT (2000) Changes in Sr/Ca, Ba/Ca and 87Sr/86Sr ratios between trophic levels in two forest ecosystems in the northeastern U.S.A. Biogeochemistry 49:87–101CrossRefGoogle Scholar
  6. Blum JD, Klaue A, Nezat CA, Driscoll CT, Johnson CE, Siccama TG, Eagar C, Fahey TJ, Likens GE (2002) Mycorrhizal weathering of apatite as an important calcium source in base-poor forest ecosystems. Nature 417:729–731CrossRefGoogle Scholar
  7. Bullen TD, Bailey SW (2005) Identifying calcium sources at an acid deposition-impacted spruce forest: a strontium isotope, alkaline earth element multi-tracer approach. Biogeochemistry 74:63–99CrossRefGoogle Scholar
  8. Bullen TD, Fitzpatrick JA, White AF, Schulz MS, Vivit DV (2004) Calcium stable isotope evidence for three soil calcium pools at a granitoid chrono-sequence. In: Wanty RB, Seal RR II (eds) Water–rock interaction. Proceedings of the eleventh international symposium on water–rock interaction, Saratoga Springs, New York, July 2004, vol 1. Taylor & Francis, London, pp 813–817Google Scholar
  9. Christopher SF, Page BD, Campbell JL, Mitchell MJ (2006) Contrasting stream water NO3 and Ca2+ in two nearly adjacent catchments: the role of soil Ca and forest vegetation. Glob Chang Biol 12:364–381CrossRefGoogle Scholar
  10. Christopher SF, Mitchell MJ, McHale MR, Boyer EW, Burns DA, Kendall C (2007) Factors controlling nitrogen release from two forested catchments with contrasting hydrochemical responses. Hydrol Process 22:46–62CrossRefGoogle Scholar
  11. DePaolo DJ (2004) Calcium isotopic variations produced by biological, kinetic, radiogenic and nucleosynthetic processes. In: Johnson CM, Beard BL, Albarede F (eds) Geochemistry of the non-traditional stable isotopes. Reviews of mineralogy and geochemistry, vol 55. Mineralogical Society of America and Geochemical Society, pp 255–288Google Scholar
  12. Driscoll CT, Newton RM, Gubala CP, Baker JP, Christensen SW (1991) Adirondack Mountains. In: Charles DF (ed) Acidic deposition and aquatic ecosystems: regional case studies. Springer-Verlag, New York, pp 133–202Google Scholar
  13. Driscoll CT, Driscoll KM, Mitchell MJ, Raynal DJ (2003) Effects of acidic deposition on forest and aquatic ecosystems in New York State. Environ Pollut 123:327–336CrossRefGoogle Scholar
  14. Duchesne L, Ouimet R, Camiré C, Houle D (2001) Seasonal nutrient transfers by foliar resorption, leaching, and litter fall in a northern hardwood forest at Lake Clair Watershed, Quebec, Canada. Can J For Res 31:333–344CrossRefGoogle Scholar
  15. Duchesne L, Ouimet R, Moore J-D, Paquin R (2005) Changes in structure and composition of maple-beech stands following sugar maple decline in Québec, Canada. For Ecol Manage 208:223–236CrossRefGoogle Scholar
  16. Fernandez IJ, Rustad LE, Norton SA, Kahl JS, Cosby BJ (2003) Experimental acidification causes soil base-cation depletion at the Bear Brook watershed in Maine. Soil Sci Soc Am J 67:1909–1919CrossRefGoogle Scholar
  17. Fujinuma R, Bockheim J, Balster N (2005) Base-cation cycling by individual tree species in old-growth forests in Upper Michigan, USA. Biogeochemistry 74:357–376CrossRefGoogle Scholar
  18. Gbondo-Tugbawa SS, Driscoll CT, Mitchell MJ, Aber JD, Likens GE (2002) A model to simulate the response of a northern hardwood forest ecosystem to changes in S deposition. Ecol Appl 12:8–23CrossRefGoogle Scholar
  19. Graveland J, Van der Wal R (1996) Decline in snail abundance causes eggshell defects in forest passerines. Oecologia 105:351–360CrossRefGoogle Scholar
  20. Gussone N, Eisenhouer A, Heuser A, Dietzel M, Bock B, Böhm F, Spero HD, Lea DW, Buma J, Nägler TF (2003) Model for kinetic effects on calcium isotope fractionation (δ44Ca) in inorganic aragonite and cultured planktonic foraminifera. Geochim Cosmochim Acta 67:1375–1382CrossRefGoogle Scholar
  21. 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
  22. Hoefs J (2004) Stable isotope geochemistry, 5th edn. Springer-VerlagGoogle Scholar
  23. Jandl R, Alewell C, Prietzel J (2004) Calcium loss in central European forest soils. Soil Sci Soc Am J 68:588–595CrossRefGoogle Scholar
  24. Johnson TM, Herbel MJ, Bullen TD, Zawislanski PT (1999) Selenium isotope ratios as indicators of selenium sources and oxyanion reduction. Geochim Cosmochim Acta 63:2775–2783CrossRefGoogle Scholar
  25. Juice SM, Fahey TJ, Siccama TG, Driscoll CT, Denny EG, Eagar C, Cleavitt NL, Minocha R, Richardson AD (2006) Response of sugar maple to calcium addition to northern hardwood forest. Ecology 87:1267–1280CrossRefGoogle Scholar
  26. Kendall C, Caldwell EA (1998) Fundamentals of isotope geochemistry. In: Kendall C, McDonnell JJ (eds) Isotope tracers in catchment hydrology. Elsevier science, Amsterdam, pp 51–86Google Scholar
  27. Lawrence GB, David MB, Bailey SW, Shortle WC (1997) Assessment of soil calcium in red spruce forests in northeastern United States. Biogeochemistry 38:19–39CrossRefGoogle Scholar
  28. LeMarchand D, Wasserburg GJ, Papanastassiou DA (2004) Rate-controlled calcium isotope fractionation in synthetic calcite. Geochim Cosmochim Acta 68:4665–4678CrossRefGoogle Scholar
  29. Likens GE, Driscoll CT, Buso DC, Siccama TG, Johnson CE, Lovett GM, Fahey TJ, Reiners WA, Ryan DF, Martin CW, Bailey SW (1998) The biogeochemistry of calcium at Hubbard Brook. Biogeochemistry 41:89–173CrossRefGoogle Scholar
  30. Likens GE, Driscoll CT, Buso DC, Mitchell MJ, Lovett GM, Bailey SW, Siccama TG, Reiners WA, Alewell C (2002) The biogeochemistry of sulfur at Hubbard Brook. Biogeochemistry 60:235–316CrossRefGoogle Scholar
  31. McLaughlin SB, Wimmer R (1999) Tansley review no. 104: calcium physiology and terrestrial ecosystem processes. New Phytol 142:373–417CrossRefGoogle Scholar
  32. Mitchell MJ, Burke MK, Shepard JP (1992) Seasonal and spatial patterns of S, Ca, and N dynamics of a northern hardwood forest ecosystem. Biogeochemistry 17:165–189CrossRefGoogle Scholar
  33. Moore AK (1995) The mineralogy and chemistry on an Adirondack spodosol. M.S. Thesis, State University of New York College of Environmental Science and Forestry, Syracuse, NY, p 139Google Scholar
  34. Page BD, Mitchell MJ (2008a) Influences of a calcium gradient on soil inorganic nitrogen in the Adirondack Mountains, New York. Ecol Appl (in press)Google Scholar
  35. Page BD, Mitchell MJ (2008b) The influence of American basswood (Tilia americana) and soil chemistry on soil nitrate concentrations in a northern-hardwood forest. Can J For Res (in press)Google Scholar
  36. Park J-H, Mitchell MJ, McHale PJ, Christopher SF, Meyers TP (2003) Impacts of changing climate and atmospheric deposition on N and S drainage losses from a forested watershed of the Adirondack Mountains, New York State. Glob Chang Biol 9:1602–1619CrossRefGoogle Scholar
  37. Perakis SS, Maguire DA, Bullen TD, Cromack K, Waring RH, Boyle JR (2006) Coupled nitrogen and calcium cycles in forests of the Oregon coast range. Ecosystems 9:63–74CrossRefGoogle Scholar
  38. SAS Institute Inc (1999) SAS procedures guide, version 8. SAS Institute Inc., Cary, NC, 1729 ppGoogle Scholar
  39. Schmitt A-D, Stille P (2005) The source of calcium in wet atmospheric deposits: Ca-Sr isotope evidence. Geochim Cosmochim Acta 69:3463–3468CrossRefGoogle Scholar
  40. Shepard JP, Mitchell MJ, Scott TJ, Zhang YM, Raynal DJ (1989) Measurements of wet and dry deposition in a northern hardwood forest. Water Air Soil Pollut 48:225–238CrossRefGoogle Scholar
  41. Skulan J, DePaolo DJ, Owens TL (1997) Biological control of calcium isotopic abundances in the global calcium cycle. Geochim Cosmochim Acta 61:2205–2210CrossRefGoogle Scholar
  42. Skulan J, Bullen TD, Anbar A, Puzas JE, Shackelford L, LeBlanc A, Smith SM (2007) Natural calcium isotopic composition of urine as a marker of bone mineral balance. Clin Chem 53:1155–1158CrossRefGoogle Scholar
  43. Sullivan TJ, Fernandez IJ, Herlihy AT, Driscoll CT, McDonnell TC, Nowicki NA, Snyder KU, Sutherland JW (2006) Acid-base characteristics of soils in the Adirondack Mountains, New York. Soil Sci Soc Am J 70:141–152CrossRefGoogle Scholar
  44. Ter-Mikaelian MT, Korzukhin MD (1997) Biomass equations for sixty-five North American tree species. For Ecol Manage 97:1–24CrossRefGoogle Scholar
  45. Tipper E, Galy A, Bickle MJ (2006) Rivering evidence for a fractionated reservoir of Ca and Mg on the continents: implications for the oceanic Ca cycle. Earth Planet Sci Lett 247:267–279CrossRefGoogle Scholar
  46. Tomlinson GH (2003) Acidic deposition, nutrient leaching and forest growth. Biogeochemistry 65:51–81CrossRefGoogle Scholar
  47. Ulrich B, Matzner E (1986) Anthropogenic and natural acidification in terrestrial ecosystems. Experientia 42:344–350CrossRefGoogle Scholar
  48. Wallander H, Hagerberg D, Åberg G (2006) Uptake of 87Sr from microcline and biotite by ectomycorrhizal fungi in a Norway spruce forest. Soil Biol Biochem 38:2487–2490CrossRefGoogle Scholar
  49. Watmough SA, Dillon PJ (2003) Base cation and nitrogen budgets for seven forested catchments in central Ontario, 1983–1999. For Ecol Manage 177:155–177CrossRefGoogle Scholar
  50. Watmough SA, Aherne J, Alewell C, Arp P, Bailey S, Clair T, Dillon P, Duchesne L, Eimers C, Fernandez I, Foster N, Larssen T, Miller E, Mitchell M, Page S (2005) Sulphate, nitrogen and base cation budgets at 21 forested catchments in Canada, the United States, and Europe. Environ Monit Assess 109:1–36CrossRefGoogle Scholar
  51. White PJ (1998) Calcium channels in the plasma membrane of root cells. Ann Bot 81:173–183CrossRefGoogle Scholar
  52. Whittaker RH, Bormann FH, Likens GE, Siccama TG (1974) The Hubbard Brook ecosystem study: forest biomass and production. Ecol Monogr 44:233–254CrossRefGoogle Scholar
  53. Wiegand BA, Chadwick OA, Vitousek PM, Wooden JL (2005) Ca cycling and isotopic fluxes in forested ecosystems in Hawaii. Geophys Res Lett 32, L11404. doi: 10.1029/2005GL022746
  54. Yanai RD, Blum JD, Hamburg SP, Arthur MA, Nezat CA, Siccama TG (2005) New insights into calcium depletion in northeastern forests. J For 103:14–20Google Scholar

Copyright information

© Springer Science+Business Media B.V. 2008

Authors and Affiliations

  • Blair D. Page
    • 1
  • Thomas D. Bullen
    • 2
  • Myron J. Mitchell
    • 1
  1. 1.SUNY College of Environmental Science and ForestrySyracuseUSA
  2. 2.U.S. Geological SurveyMenlo ParkUSA

Personalised recommendations