Abstract
To understand role of biogeochemical reactions in controlling the amount and molecular form of dissolved carbon exported from carbonate terrains, spatiotemporal variations in dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) were observed over one year in the Santa Fe River system, a period of base flow or below. A water mixing model developed using concentrations of Na+, Cl−, and SO −24 identified three major water sources: soil water, groundwater and deep aquifer water. After accounting for mixing of these water sources, additional chemical signatures resulting from biogeochemical processes in the riparian zone were identified. Net mineralization of DOC occurred throughout the Santa Fe River watershed, particularly during the lowest flow conditions and in the upper watershed. However, natural dissolved organic matter was more labile during low flow and in the lower watershed, and predominantly derived from groundwater (rather than soil water) in all samples, likely via releases during carbonate dissolution. Carbonate dissolution commonly occurred in the upper watershed during low flow conditions, while carbonate minerals precipitated during baseflow, as well as in the lower watershed during very low flow conditions. Thus, riparian zone biogeochemical processes were strongly mediated by watershed hydrology, whose spatiotemporal variations resulted in greater inorganic and organic C export production in the lower watershed than the upper watershed, and during higher flow versus lower flow periods. During this lower flow period, the Santa Fe River watershed exported ~1.0 and 10.3 ton km−2 year−1 DOC and DIC, respectively, representing higher C yields than many other types of watersheds.
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References
Aitkenhead JA, McDowell WH (2000) Soil C : N ratio as a predictor of annual riverine DOC flux at local and global scales. Glob Biogeochem Cycles 14(1):127–138
Alberic P, Lepiller M (1998) Oxidation of organic matter in a karstic hydrologic unit supplied through stream sinks (Loiret, France). Water Res 32(7):2051–2064
Aravena R, Wassenaar LI, Spiker EC (2004) Chemical and carbon isotopic composition of dissolved organic carbon in a regional confined methanogenic aquifer. Isot Environ Health Stud 40(2):103–114
Batiot C, Emblanch C, Blavoux B (2003) Total Organic Carbon (TOC) and magnesium (Mg2 +): two complementary tracers of residence time in karstic systems. CR Geosci 335(2):205–214
Benner R, Opsahl S, ChinLeo G, Richey JE, Forsberg BR (1995) Bacterial carbon metabolism in the Amazon River system. Limnol Oceanogr 40(7):1262–1270
Berner RA (1999) A new look at the long-term carbon cycle. GSA Today 9:1–6
Berner RA, Lasaga AC (1989) Modeling the geochemical carbon-cycle. Sci Am 260(3):74–81
Brunet F et al (2009) Terrestrial and fluvial carbon fluxes in a tropical watershed: nyong basin Cameroon. Chem Geol 265(3–4):563–572
Burke EJ, Brown SJ, Christidis N (2006) Modeling the recent evolution of global drought and projections for the twenty-first century with the hadley centre climate model. J Hydrometeorol 7(5):1113–1125
Canfield DE Jr, Hoyer MV (1988) Influence of nutrient enrichment and light availability on the abundance of aquatic macrophytes in Florida streams. Can J Fish Aquat Sci 45(8):1467–1472
CCSP (2008) Reanalysis of historical climate data for key atmospheric features: implications for attribution of causes of observed change. A report by the U.S. Climate Change Science Program and the Subcommittee on Global Change Research, U.S. Environmental Protection Agency. Washington, DC. http://www.climatescience.gov/Library/sap/sap1-3/final-report/#finalreport.
Clark ID, Fritz P (1997) Environmental isotopes in hydrogeology. CRC press
Davis JA (1982) Adsorption of natural dissolved organic-matter at the oxide water interface. Geochim Cosmochim Acta 46(11):2381–2393
Dreybrodt W (1988) Processes in Karst Systems. Springer-Verlag, New York, p 288
Duarte CM et al (2010) Rapid accretion of dissolved organic carbon in the springs of Florida: the most organic-poor natural waters. Biogeosciences 7(12):4051–4057
Falkowski P et al (2000) The global carbon cycle: a test of our knowledge of earth as a system. Science 290(5490):291–296
Findlay SEG, Sinsabaugh RL (2003). Aquatic ecosystems: interactivity of dissolved organic matter Academic press
Ford DC, Williams PW (2007) Karst Hydrogeology and Geomorphology. Wiley, Chichester, p 562
Frimmel FH (1998) Characterization of natural organic matter as major constituents in aquatic systems. J Contam Hydrol 35(1–3):201–216
Frye GC, Thomas MM (1993) Adsorption of Organic-compounds on carbonate minerals. 2. Extraction of carboxylic-acids from recent and ancient carbonates. Chem Geol 109(1–4):215–226
Giesler R et al (2014) Catchment-scale dissolved carbon concentrations and export estimates across six subarctic streams in northern Sweden. Biogeosciences 11(2):525–537
Grubbs J.W (1998) Recharge rates to the upper Floridan aquifer in the Suwannee River Water Management District, Florida. U S geological survey water resources investigations Report 97-4283 30 p
Guo L, Cai Y, Belzile C, Macdonald RW (2012) Sources and export fluxes of inorganic and organic carbon and nutrient species from the seasonally ice-covered Yukon River. Biogeochemistry 107(1–3):187–206
Hancock PJ, Boulton AJ, Humphreys WF (2005) Aquifers and hyporheic zones: towards an ecological understanding of groundwater. Hydrogeol J 13(1):98–111
Heffernan JB et al (2010) Hydrologic and biotic influences on nitrate removal in a subtropical spring-fed river. Limnol Oceanogr 55(1):249–263
Hoch AR, Reddy MM, Aiken GR (2000) Calcite crystal growth inhibition by humic substances with emphasis on hydrophobic acids from the Florida Everglades. Geochim Cosmochim Acta 64(1):61–72
Houghton RA, Woodwell GM (1989) Global climatic-change. Sci Am 260(4):36–44
House WA (1990) The prediction of phosphate coprecipitation with calcite in fresh-waters. Water Res 24(8):1017–1023
Inskeep WP, Bloom PR (1986) Kinetics of calcite precipitation in the presence of water-soluble organic-ligands. Soil Sci Soc Am J 50(5):1167–1172
IPCC (2007) Climate change 2007: the physical basis. Contribution of working group I to the fourth assessment report of the intergovernmental panel on climate change. Cambridge University Press, Cambridge
Jin J (2012) Natural dissolved organic matter dynamics in a karstic surface-groundwater exchange system. Dissertation, University of Florida, Gainesville, FL, 168 pp
Jin J, Zimmerman AR (2010) Abiotic interactions of natural dissolved organic matter and carbonate aquifer rock. Appl Geochem 25(3):472–484
Jin J, Zimmerman AR, Moore PJ, Martin JB (2014) Organic and inorganic carbon dynamics of a karstic aquifer: Santa Fe River sink–rise system, north Florida, USA. J Geophys Res Biogeosci 119(3):340–357
Jones CS, Schilling KE (2012) Carbon export from the Raccoon River, Iowa: patterns, processes, and opportunities. J Environ Qual 42(1):155–163
Katz BG (1992) Hydrochemistry of the upper Floridan aquifer, Florida. US. Geological survey water-resources investigations report 91-4196, 37, p 10
Khadka MB, Martin JB, Jin J (2014) Transport of dissolved carbon and CO2 degassing from a river system in a mixed silicate and carbonate catchment. J Hydrol 513:391–402
Kortelainen NM, Karhu JA (2006) Tracing the decomposition of dissolved organic carbon in artificial groundwater recharge using carbon isotope ratios. Appl Geochem 21(4):547–562
Kurz RC et al (2004) Mapping and monitoring submerged aquatic vegetation in Ichetucknee springs. Suwanee River Water Management District, Live Oak
Laurion I, Vincent WF, Lean DRS (1997) Underwater ultraviolet radiation: development of spectral models for northern high latitude lakes. Photochem Photobiol 65(1):107–114
Lee ES, Krothe NC (2001) A four-component mixing model for water in a karst terrain in south-central Indiana, USA. Using solute concentration and stable isotopes as tracers. Chem Geol 179(1–4):129–143
Lee JU, Lee SW, Kim KW, Yoon CH (2005) The effects of different carbon sources on microbial mediation of arsenic in arsenic-contaminated sediment. Environ Geochem Health 27(2):159–168
Li S-L et al (2010) Geochemistry of dissolved inorganic carbon and carbonate weathering in a small typical karstic catchment of Southwest China: isotopic and chemical constraints. Chem Geol 277(3–4):301–309
Lin YP, Singer PC (2005) Inhibition of calcite crystal growth by polyphosphates. Water Res 39(19):4835–4843
Lindroos AJ, Kitunen V, Derome J, Helmisaari HS (2002) Changes in dissolved organic carbon during artificial recharge of groundwater in a forested esker in Southern Finland. Water Res 36(20):4951–4958
Liu Z, Zhao J (2000) Contribution of carbonate rock weathering to the atmospheric CO2 sink. Environ Geol 39(9):1053–1058
Liu Z, Dreybrodt W, Liu H (2011) Atmospheric CO2 sink: silicate weathering or carbonate weathering? Appl Geochem 26:S292–S294
Lopez R, Del Castillo CE, Miller RL, Salisbury J, Wisser D (2012) Examining organic carbon transport by the Orinoco River using SeaWiFS imagery. J Geophys Res Biogeosci 117(17):9721–9742
Lovley DR, Chapelle FH (1995) Deep subsurface microbial processes. Rev Geophys 33(3):365–381
Lovley DR, Chapelle FH (1996) Hydrogen-based microbial ecosystems in the Earth. Science 272(5263):896–896
Ludwig W, AmiotteSuchet P, Probst JL (1996) River discharges of carbon to the world’s oceans: determining local inputs of alkalinity and of dissolved and particulate organic carbon. Comptes Rendus De L Academie Des Sciences Serie Ii Fascicule a-Sciences De La Terre Et Des Planetes 323(12):1007–1014
Martin JB, Dean RW (2001) Exchange of water between conduits and matrix in the Floridan aquifer. Chemical Geology 179:145–165
Martin JB, Gordon SL (2000) Surface and ground water mixing, flow paths, and temporal variations in chemical compositions and karst springs. In: Sasowsky ID, Wicks CM (eds) Groundwater flow and contaminant transport in carbonate aquifers. A. A Balkema, Amsterdam, pp 65–92
Martin JB, Brown A, Ezell J (2013) Do carbonate karst terrains affect the global carbon cycle? Acta Carsologica 42(2–3):187–196
McCarthy JF et al (1996) Field tracer tests on the mobility of natural organic matter in a sandy aquifer. Water Resour Res 32(5):1223–1238
McKnight DM et al (2001) Spectrofluorometric characterization of dissolved organic matter for indication of precursor organic material and aromaticity. Limnol Oceanogr 46(1):38–48
McMahon PB (2001) Aquifer/aquitard interfaces: mixing zones that enhance biogeochemical reactions. Hydrogeol J 9(1):34–43
Meyer JL, Edwards RT, Risley R (1987) Bacterial-growth on dissolved organic carbon from a blackwater river. Microb Ecol 13(1):13–29
Moore PJ, Martin JB, Screaton EJ (2009) Geochemical and statistical evidence of recharge, mixing, and controls on spring discharge in an eogenetic karst aquifer. J Hydrol 376(3–4):443–455
Moran MA, Sheldon WM, Sheldon JE (1999) Biodegradation of riverine dissolved organic carbon in five estuaries of the southeastern United States. Estuaries 22(1):55–64
Morris DP et al (1995) The attentuation of solar UV radiation in lakes and the role of dissolved organic carbon. Limnol Oceanogr 40(8):1381–1391
Neal C et al (2002) Phosphorus-calcium carbonate saturation relationships in a lowland chalk river impacted by sewage inputs and phosphorus remediation: an assessment of phosphorus self-cleansing mechanisms in natural waters. Sci Total Environ 282:295–310
Nimick DA et al (2003) Diel cycles in dissolved metal concentrations in streams: occurrence and possible causes. Water Resour Res 39(9):1247–1264
Ohno T (2002) Fluorescence inner-filtering correction for determining the humification index of dissolved organic matter. Environ Sci Technol 36(4):742–746
Pabich WJ, Valiela I, Hemond HF (2001) Relationship between DOC concentration and vadose zone thickness and depth below water table in groundwater of Cape Cod USA. Biogeochemistry 55(3):247–268
Pearlstine LG (2009) Potential Ecological consequences of climate change in South Florida and the Everglades: 2008 literature Synthesis South Florida Natural Resources Center, Everglades National Park. Homstead, FL
Petrone KC, Fellman JB, Hood E, Donn MJ, Grierson PF (2011) The origin and function of dissolved organic matter in agro-urban coastal streams. J Geophys Res-Biogeosci 116:13
Petrovic M, Kastelan-Macan M, Horvat AJM (1999) Interactive sorption of metal ions and humic acids onto mineral particles. Water Air Soil Pollut 111(1–4):41–56
Probst JL, Mortatti J, Tardy Y (1994) Carbon river fluxes and weathering CO2 consumption in the Congo and Amazon River basins. Appl Geochem 9(1):1–13
Pronk M, Goldscheider N, Zopfi J (2006) Dynamics and interaction of organic carbon, turbidity and bacteria in a karst aquifer system. Hydrogeol J 14(4):473–484
Quay P (1992) Carbon sink: the role of oceans. Geotimes 37(9):16–18
Randazzo AF, Jones DS (1997). The geology of Florida. University Press of Florida
Rauch T, Drewes L (2004) Assessing the removal potential of soil-aquifer treatment systems for bulk organic matter. Water Sci Technol 50(2):245–253
Saunders TJ, Collins ME, Frazer TK Hurt G.W (2007). The distribution and function of biogeochemical interfaces, gradients, and fluxes in a coastal spring-fed riverine and estuarine system. Ecological society of America annual meeting abstracts
Schulz M, Kohler J (2006) A simple model of phosphorus retention evoked by submerged macrophytes in lowland rivers. Hydrobiologia 563:521–525
Scott TM (1988) The lithostratigraphy of the Hawthorn Group (Miocene) of Florida USA. Florida Dep Nat Resour Bureau Geol Bull 59:XII–148
Screaton E, Martin JB, Ginn B, Smith L (2004) Conduit properties and karstification in the unconfined Floridan Aquifer. Ground Water 42(3):338–346
Selman C, Misra V, Stefanova L, Dinapoli S, Smith TJ III (2013) On the twenty-first-century wet season projections over the Southeastern United States. Reg Environ Change 13:S153–S164
Suchet PA, Probst JL, Ludwig W (2003). Worldwide distribution of continental rock lithology: Implications for the atmospheric/soil CO2 uptake by continental weathering and alkalinity river transport to the oceans. Global Biogeochem Cycles 17(2) 1038
Telmer K, Veizer J (1999) Carbon fluxes, pCO(2) and substrate weathering in a large northern river basin, Canada: carbon isotope perspectives. Chem Geol 159(1–4):61–86
Thomas MM, Clouse JA, Longo JM (1993) Adsorption of organic-compounds on carbonate minerals. 3. influence on dissolution rates. Cheml Geol 109(1–4):227–237
Upchurch SB, Lawrence FW (1984) Impact of ground water chemistry on sinkhole development along a retreating scarp. In: Beck BF (ed) Sinkholes: their geology, engineering, and environmental impact. A.A. Balkema, Rotterdam, pp 189–195
Watson RT, Rodhe H, Oeschger H, Siegenthaler U (1990). Greenhouse gases and aerosols. In: JT Houghton, GJ Jenkins EJJ (Eds), Climate change: the IPCC scientific assessment. Cambridge University Press, Cambridge, pp. 1–40.
Wetzel RG (2001) Limnology: lake and river ecosystems. Academic Press, San Diego
White WB (1988) Geomorphology and hydrology of Karst Terrains. Oxford University Press, New York, p 464
Wilson HF, Saiers JE, Raymond PA, Sobczak WV (2013) Hydrologic drivers and seasonality of dissolved organic carbon concentration, nitrogen content, bioavailability, and export in a forested new england stream. Ecosystems 16(4):604–616
Zachara JM, Cowan CE, Resch CT (1991) Sorption of divalent metals on calcite. Geochim Cosmochim Acta 55(6):1549–1562
Zsolnay A, Baigar E, Jimenez M, Steinweg B, Saccomandi F (1999) Differentiating with fluorescence spectroscopy the sources of dissolved organic matter in soils subjected to drying. Chemosphere 38(1):45–50
Acknowledgments
The authors thank Chad Foster for his help in the field, Jason Curtis for his assistance with the DIC and C isotope measurements, and Kathleen McKee and Megan Wetherington for providing the hydrologic data. This work is supported by NSF Grant EAR-0853956.
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Jin, J., Zimmerman, A.R., Martin, J.B. et al. Spatiotemporal variations in carbon dynamics during a low flow period in a carbonate karst watershed: Santa Fe River, Florida, USA. Biogeochemistry 122, 131–150 (2015). https://doi.org/10.1007/s10533-014-0035-6
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DOI: https://doi.org/10.1007/s10533-014-0035-6