Abstract
Chloride (Cl−) has often been assumed to be relatively unreactive in forest ecosystems, and is frequently used as a conservative tracer to calculate fluxes of water and other ions. Recently, however, several studies have detailed cycling of Cl− in vegetation and soils. In this study Cl− budgets are compiled from 32 catchment studies to determine the extent to which Cl− is conserved in the passage through forest ecosystems. Chloride budgets from these sites vary from net retention (input > output) to net release (output > input). In the overall data set, including those sites with very high inputs of seasalt Cl−, there was a strong correspondence between inputs and outputs. However, sites with low Cl− deposition (<6 kg ha−1 year−1) consistently showed net release of Cl−, suggesting an internal source or a declining internal pool. The results indicate that Cl− may be a conservative ion in sites with high Cl− deposition, but in sites with low deposition Cl− may not be conservative. We discuss the possible causes of the Cl− imbalance and reasons why Cl− may not be conservative in ecosystem functions.
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References
Alewell C, Lischeid G, Hell U, Manderscheid G (2004) High temporal resolution of ion fluxes in semi-natural ecosystems—gain of information or waste of resources? Biogeochemistry 69(1):19–35
Asplund G, Grimvall A (1991) Organohalogens in nature. More widespread than prevoiusly assumed. Environ Sci Technol 25:1347–1350
Asplund G, Borén H, Carlsson U, Grimvall A (1991) Humic substances in the Aquatic and terrestrial Environment. Springer Verlag, Berlin
Asplund G, Christiansen JV, Grimvall A (1993) A chloroperoxidase-like catalyst in soil: Detection and characterization of some properties. Soil Biol Biochem 25(1):41–46
Bailey SW, Buso DC, Likens GE (2003) Implications of sodium mass balance for interpreting the calcium cycle of a forested ecosystem. Ecology 84:471–484
Bastviken D, Sandén P, Svensson T, Ståhlberg C, Magounakis M, Öberg G (2006) Chloride retention and release in a boreal forest soil-effects of soil water residence time and nitrogen and chloride loads. Environ Sci Technol 40:2977–2982
Bastviken D, Thomsen F, Svensson T, Karlsson S, Sandén P, Shaw G, Matucha M, Öberg G (2007) Chloride retention in forest soil by microbial uptake and by natural chlorination of organic matter. Geochim Cosmochim Acta 71(13):3182–3192
Bastviken D, Svensson T, Karlsson S, Sandén P, Öberg G (2009) Temperature sIndicates that chlorination of organic matter in forest soil is primarily biotic environmental. Sci Technol 43(10):3569–3573
Buso DC, Likens GE and Eaton JS (2000) Chemistry of precipitation, streamwater, and lakewater from the Hubbard Brook ecosystem study: a record of sampling protocols and analytical procedures. Gen Tech Rep NE-275:1–52
Campbell K, Wolfsberg A, Fabryka-Martin J, Sweetkind D (2003) Chlorine-36 data at Yucca Mountain: statistical tests of conceptual models for unsaturated-zone flow. J Contam Hydrol 62–63:43–61
Castro MS, Morgan RP (2000) Input–output budgets of major ions for a forested watershed in western Maryland. Water Air Soil Pollut 119(1–4):121–137
Clutterbuck PW, Mukhopadhyay SL, Oxford AE, Raistrick H (1940) Studies in the biochemistry of microorganisms. Biochem J 34:664–677
Dimmer C, Simmonds P, Nickless G, Bassford M (2001) Biogenic fluxes of halomethanes from Irish peatland ecosystems. Atmos Environ 35:321–330
Eriksson E (1955) Air borne salts and the chemical composition of river waters. Tellus 7:243–250
Hedin LO, Armesto JJ, Johnson AH (1995) Patterns of nutrient loss from unpolluted, old-growth temperate forests—evaluation of biogeochemical theory. Ecology 76(2):493–509
Hoekstra EJ, Duyzer JH, Leer EWBD, Brinkman UAT (2001) Chloroform-concentration gradients in soil air and atmospheric air, and emission fluxes from soil. Atmos Environ 35:61–70
Hultberg H, Grennfelt P (1992) Sulfur and seasalt deposition as reflected by throughfall and runoff chemistry in forested catchments. Environ Pollut 75(2):215–222
Johansson E, Ebenå G, Sandén P, Svensson T, Öberg G (2001) Organic and inorganic chlorine in Swedish spruce forest soil: influence of nitrogen. Geoderma 101:1–13
Johansson E, Sandén P, Öberg G (2003) Spatial patterns of organic chlorine and chloride in Swedish forest soil. Chemosphere 52:391–397
Johnson NM, Likens GE, Bormann FH, Fisher DW, Pierce RS (1969) A working model for the variation in stream water chemistry at the Hubbard Brook Experimental Forest, New Hampshire. Water Resour Res 5:1353–1363
Juang F, Johnson N (1967) Cycling of chlorine through a forested watershed in New England. J Geophys Res 72(22):5641–5647
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. Environ Sci Technol 42(2):410–415
Kirchner JW (2003) A double paradox in catchment hydrology and geochemistry. Hydrol Process 17(4):871–874
Kram P, Hruska J, Wenne B, Driscoll C, Johnson C (1997) The biogeochemistry of basic cations in two forest catchments with contrasting lithology in the Czech Republic. Biogeochemistry 37:173–202
Larsson M, Jarvis N (1999) Evaluation of a dual-porosity model to predict field-scale solute transport in a macroporous soil. J Hydrol 215:153–171
Lee R, Shaw G, Wadey P, Wang X (2001) Specific association of 36Cl with low molecular wight humic substances in soil. Chemosphere 43:1063–1070
Likens GE, Bormann FH (1995) Biochemistry of forested ecosystem, Springer-Verlag, New York
Lockwood P, McGarity J, Charley J (1995) Measurement of chemical weathering rates using natural chloride as a tracer. Geoderma 64:215–232
Lovett GM (1994) Atmospheric deposition of nutrients and pollutants in North-America—an ecological perspective. Ecol Appl 4(4):629–650
Lovett GM, Likens GE, Buso DC, Driscoll CT, Bailey SW (2005) The biogeochemistry of chlorine at Hubbard Brook, New Hampshire, USA. Biogeochemistry 72(2):191–232
Matzner E, (ed) (2004) Biogeochemistry of forested catchments in a changing environment: a German case study. Ecological studies 172
Myneni S (2002) Formation of stable chlorinated hydrocarbons in weathering plant material. Science 295:1039–1041
Neal C, Reynolds B, Neal M, Wickham H, Hill L, Williams B (2004) The water quality of streams draining a plantation forest on gley soils: the Nant Tanllwyth, Plynlimon mid-Wales. Hydrol Earth Syst Sci 8(3):485–502
Neal C, Robinson D, Reynolds B, Neal M, Rowland P, Grant S, Norris D, Williams B, Sleep D, Lawlor A (2010) Hydrology and water quality of the headwaters of the River Severn: stream acidity recovery and interactions with plantation forestry under an improving pollution climate. Sci Total Environ 408:5035–5051
Nodvin SC, Driscoll CT, Likens GE (1986) Simple partitioning of anions and dissolved organic-carbon in a forest soil. Soil Sci 142:27–35
Öberg G (2002) The natural chlorine cycle—fitting the scattered pieces. Appl Microbiol Biotechnol 58:565–581
Öberg G, Grön C (1998) Sources of organic halogens in a Danish spruce forest soil. Environ Sci Technol 32:1573–1579
Öberg G, Sandén P (2005) Retention of chloride in soil and cycling of organic matter-bound chlorine. Hydrol Process 19:2123–2136
Öberg G, Holm M, Sandén P, Svensson T, Parikka M (2005) The role of organic-matter-bound chlorine in the chlorine cycle: a case study of the Stubbetorp catchment, Sweden. Biogeochemistry 75:241–269
Ohrui K, Mitchell MJ (1996) Elemental dynamics of a Japanese watershed with sugi (Cryptomeria japonica) and hinoki (Chamaecyparis obtusa) plantations. Can J For Res 26:2160–2169
Ortiz-Bermudez P, Hirth KC, Srebotnik E, Hammel KE (2007) Chlorination of lignin by ubiquitous fungi has a likely role in global organochlorine production. Proc Natl Acad Sci USA 104(10):3895–3900
Peters N (1991) Chloride cycling in two forested lake watersheds in the west-central Adirondack Mountains, New York, USA. Water Air Soil Pollut 59:201–215
Peters NE, Ratcliffe EB (1998) Tracing hydrologic pathways using chloride at the Panola Mountain Research Watershed, Georgia, USA. Water, Air and Soil Pollution 105(1–2):263–275
Peters NE, Ratcliffe EB, Tranter M (1998) Tracing solute mobility at the Panola Mountain Research Water shed, Georgia, USA: variations in NA+, Cl− and H4SiO4 concentrations. In: Kovar K, Tappeiner U, Peters NE, Craig RG (eds) Hydrology, water resources and ecology in headwaters, vol 248. IAHS Publication, pp 483–490
Peters NE, Shanley JB, Aulenbach BT, Webb RM, Campbell DH, Hunt R, Larsen MC, Stallard RF, Troester J, Walker JF (2006) Water and solute mass balance of five small relatively undisturbed watersheds in the US. Sci Total Environ 358:221–243
Probst A, Viville D, Fritz B, Ambroise B, Dambrine E (1992) Hydrochemical budgets of a small forested granitic catchment exposed to acid deposition: the strengbach catchment case study (Vosges massif, France). J Water, Air and Soil Pollution 62(3–4):337–347
Reynolds B, Fowler D, Smith R, Hall J (1997) Atmospheric inputs and catchment solute fluxes for major ions in five Welsh upland catchments. J Hydrol 194:305–329
Rodstedth M, Ståhlberg C, Sandén P, Öberg G (2003) Chloride imbalances in soil lysimeters. Chemosphere 52:381–389
Rustad L, Kahl J, Norton S, Fernandez I (1994) Underestimation of dry deposition by throughfall in mixed northern hardwood forests. J Hydrol 162(3–4):319–336
Schlesinger W (1997) Biogeochemistry. An analysis of global change. Academic Press, San Diego
Svensson T, Sandén P, Bastviken D, Öberg G (2007) Chlorine transport in a small catchment in southeast Sweden during two years. Biogeochemistry 82:181–199
Swank W, Crossley JD (eds) (1988) Ecological Studies 66: forest hydrology and ecology at Coweeta. Springer Verlag, New York
Winterton N (2000) Chlorine: the only green element—towards a wider acceptance of its role in natural cycles. Green Chem 2:173–225
Acknowledgments
We are grateful to the many scientists at the catchment and forest sites whose meticulous collection and publication of data made this study possible. Mary Beth Adams of the USDA Forest Service, Colin Neal of the Center for Ecology and Hydrology in the UK, Sirpa Kleemola at Finnish Environment Institute, Gunilla Pihl-Karlsson at Swedish Environmental Research Institute, Reet Talkop at Estonian Environment Information Centre, Milan Vana at Czech Hydrometeorological Institute generously provided unpublished data, and Steve Norton, Lindsey Rustad, and Jake Peters helped us with discussions and interpretations of their data. We thank Chris Evans and Brian Reynolds for reviews that greatly improved the manuscript. Svensson is grateful for financial support from The Swedish Foundation for International Cooperation in Research and Education (STINT). Lovett was partially supported by the US National Science Foundation through grant DEB-0342198 and DEB-0423259 and the Hubbard Brook LTER program. Long-term data provided by Likens for the Hubbard Brook Experimental forest were supported by the US National Science Foundation, including the LTER and LTREB programs, and The Andrew W. Mellon Foundation.
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Svensson, T., Lovett, G.M. & Likens, G.E. Is chloride a conservative ion in forest ecosystems?. Biogeochemistry 107, 125–134 (2012). https://doi.org/10.1007/s10533-010-9538-y
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DOI: https://doi.org/10.1007/s10533-010-9538-y
Keywords
- Catchment
- Chloride
- Chlorine
- Mass balance
- Soil
- Tracer
- Watershed