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Rapid and Intense Phosphate Desorption Kinetics When Saltwater Intrudes into Carbonate Rock

Abstract

It is important to understand how phosphate sorption dynamics of coastal carbonate aquifers are affected by seawater intrusion, because many coastal aquifers are composed of carbonate rocks and subject to an increase in saltwater intrusion during relative sea-level rise. Twelve carbonate rock and unconsolidated sediment specimens were acquired from a test corehole spanning the full thickness of the Biscayne aquifer in southeastern Florida. All 12 samples exhibit low phosphorus content but variable contents of iron. Column leaching experiments were conducted with two carbonate aquifer samples, alternating between freshwater and saltwater flow. With the first influx of saltwater, phosphate concentration in leachate increased rapidly from a freshwater value of approximately 0.2 μM to peaks of between 0.8 and 1.6 μM. The phosphate concentration began to diminish as saltwater continued to flow, but sustained desorption continued for over 2 h. Overall, seawater drove sorption behavior much more than chemical composition for the aquifer rocks and sediment from the seven rock samples for which we did isotherm sorption experiments. Our results indicate that an immediate and intense pulse of phosphate desorption from carbonate rock and sediment with low phosphorus content occurs in response to an influx of seawater and that the duration of desorption will vary by layer within a single aquifer.

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References

  • Barlow, P.M., and E.G. Reichard. 2010. Saltwater intrusion in coastal regions of North America. Hydrogeology Journal 18: 247–260.

    CAS  Article  Google Scholar 

  • Chambers, R.M., and K.A. Pederson. 2006. Variation in soil phosphorus, sulfur, and iron pools among South Florida wetlands. Hydrobiologia 569: 63–70.

    CAS  Article  Google Scholar 

  • Corbett, D.R., L. Kump, K. Dillon, W. Burnett, and J. Chanton. 2000. Fate of wastewater-borne nutrients under low discharge conditions in the subsurface of the Florida Keys, USA. Marine Chemistry 69: 99–115.

    CAS  Article  Google Scholar 

  • Cotecchia, V., G. Tazioli, and G. Magri. 1974. Isotopic measurements in research on seawater ingression in the carbonate aquifer of the Salentine Peninsula, southern Italy. In Isotope techniques in groundwater hydrology 1974, Vol. I. Proceedings of a symposium.

  • Cunningham, K.J., D. Bukry, T. Sato, J.A. Barron, L.A. Guertin, and R.S. Reese. 2001. Sequence stratigraphy of a South Florida carbonate ramp and bounding siliciclastics (late Miocene–Pliocene). Geology and hydrology of Lee County, Florida: Florida Geological Survey Special Publication 49: 35–66.

    Google Scholar 

  • Cunningham, K.J., M.A. Wacker, E. Robinson, J.F. Dixon, and G.L. Wingard. 2006. A cyclostratigraphic and borehole-geophysical approach to development of a three-dimensional conceptual hydrogeologic model of the karstic Biscayne aquifer, southeastern Florida. In U.S. Geological Survey Scientific Investigations Report 2005–5235, 69 p., plus CD.

  • Cunningham, K.J., M.A. Wacker, E. Robinson, C.J. Gefvert, and S.L. Krupa. 2004. Hydrogeology and ground-water flow at Levee 31N, Miami-Dade County, Florida, July 2003 to May 2004. In U.S. Geological Survey Scientific Investigations Map I-2846, 1 sheet.

  • D’Angelo, E., J. Crutchfield, and M. Vandiviere. 2001. Rapid, sensitive, microscale determination of phosphate in water and soil. Journal of Environmental Quality 30: 2206–2209.

    Article  Google Scholar 

  • Fitterman, D.V. 2014. Mapping saltwater intrusion in the Biscayne aquifer, Miami-Dade County, Florida using transient electromagnetic sounding. Journal of Environmental and Engineering Geophysics 19: 33–43.

    Article  Google Scholar 

  • Flower, H., M. Rains, D. Lewis, J.-Z. Zhang, and R. Price. 2016. Control of phosphorus concentration through adsorption and desorption in shallow groundwater of subtropical carbonate estuary. Estuarine, Coastal and Shelf Science 169: 238–247.

    CAS  Article  Google Scholar 

  • Flower, H., M. Rains, D. Lewis, J.-Z. Zhang, and R. Price. 2017. Saltwater intrusion as potential driver of phosphorus release from limestone bedrock in a coastal aquifer. Estuarine Coastal and Shelf Science 184: 166–176.

  • Froelich, P.N. 1988. Kinetic control of dissolved phosphate in natural rivers and estuaries: a primer on the phosphate buffer mechanism1. Limnology and Oceanography 33: 649–668.

    CAS  Google Scholar 

  • Gaiser, E.E., J.C. Trexler, J.H. Richards, D.L. Childers, D. Lee, A.L. Edwards, L.J. Scinto, K. Jayachandran, G.B. Noe, and R.D. Jones. 2005. Cascading ecological effects of low-level phosphorus enrichment in the Florida Everglades. Journal of Environmental Quality 34: 717–723.

    CAS  Article  Google Scholar 

  • Gao, Y., and A. Mucci. 2003. Individual and competitive adsorption of phosphate and arsenate on goethite in artificial seawater. Chemical Geology 199: 91–109.

    CAS  Article  Google Scholar 

  • Goldberg, S., and G. Sposito. 1985. On the mechanism of specific phosphate adsorption by hydroxylated mineral surfaces: a review. Communications in Soil Science & Plant Analysis 16: 801–821.

    CAS  Article  Google Scholar 

  • Huang, X.-L., and J.-Z. Zhang. 2009. Neutral persulfate digestion at sub-boiling temperature in an oven for total dissolved phosphorus determination in natural waters. Talanta 78: 1129–1135.

    CAS  Article  Google Scholar 

  • Kohout, F., and H. Klein. 1967. Effect of pulse recharge on the zone of diffusion in the Biscayne aquifer. In International Association of Scientific Hydrogeology Symposium, Haifa, Israel, pub, 252–270.

  • Millero, F., F. Huang, X. Zhu, X. Liu, and J.-Z. Zhang. 2001. Adsorption and desorption of phosphate on calcite and aragonite in seawater. Aquatic Geochemistry 7: 33–56.

    CAS  Article  Google Scholar 

  • Moore, W.S. 1999. The subterranean estuary: a reaction zone of ground water and sea water. Marine Chemistry 65: 111–125.

    CAS  Article  Google Scholar 

  • Noe, G.B., D.L. Childers, and R.D. Jones. 2001. Phosphorus biogeochemistry and the impact of phosphorus enrichment: why is the Everglades so unique? Ecosystems 4: 603–624.

    CAS  Article  Google Scholar 

  • NRC. 2010. National Research Council: Progress Toward Restoring the Everglades: The Third Biennial Review. Washington, D.C.: The National Academies Press, 326 p.

  • NRC. 2014. National Research Council: Progress Toward Restoring the Everglades: The Fifth Biennial Review. Washington, DC: The National Academies Press, 302 p.

  • Price, R.M. 2001. Geochemical determinations of groundwater flow in Everglades National Park, Ph.D. Dissertation, University of Miami, 307 p.

  • Price, R.M., and J.S. Herman. 1991. Geochemical investigation of salt-water intrusion into a coastal carbonate aquifer: Mallorca, Spain. Geological Society of America Bulletin 103: 1270–1279.

    CAS  Article  Google Scholar 

  • Price, R.M., M.R. Savabi, J.L. Jolicoeur, and S. Roy. 2010. Adsorption and desorption of phosphate on limestone in experiments simulating seawater intrusion. Applied Geochemistry 25: 1085–1091.

    CAS  Article  Google Scholar 

  • Price, R.M., P.K. Swart, and J.W. Fourqurean. 2006. Coastal groundwater discharge—an additional source of phosphorus for the oligotrophic wetlands of the Everglades. Hydrobiologia 569: 23–36.

    CAS  Article  Google Scholar 

  • Prinos, S.T., M.A. Wacker, K.J. Cunningham, and D.V. Fitterman. 2014. Origins and delineation of saltwater intrusion in the Biscayne aquifer and changes in the distribution of saltwater in Miami-Dade County, Florida. U.S. Geological Survey Scientific Investigations Report 2014–5025, 101 p.

  • Rudnick, R., and S. Gao. 2003. 3.01 Composition of the continental crust. Treatise on geochemistry 3 The Crust: 1–64.

  • Ruttenberg, K.C. 1992. Development of a sequential extraction method for different forms of phosphorus in marine sediments. Limnology and Oceanography 37: 1460–1482.

    CAS  Article  Google Scholar 

  • Slomp, C.P., and P. Van Cappellen. 2004. Nutrient inputs to the coastal ocean through submarine groundwater discharge: controls and potential impact. Journal of Hydrology 295: 64–86.

    CAS  Article  Google Scholar 

  • Spence, V. 2011. Estimating groundwater discharge in the oligohaline ecotone of the Everglades using temperature as a tracer and variable-density groundwater models, Masters Thesis, University of South Florida at Tampa, 36 p.

  • Starr, J., and J.-Y. Parlange. 1979. Dispersion in soil columns: the snow plow effect. Soil Science Society of America Journal 43: 448–450.

    CAS  Article  Google Scholar 

  • Suzumura, M., S. Ueda, and E. Sumi. 2000. Control of phosphate concentration through adsorption and desorption processes in groundwater and seawater mixing at sandy beaches in Tokyo Bay, Japan. Journal of Oceanography 56: 667–673.

    CAS  Article  Google Scholar 

  • USGS. 2003. Lithologic and Geophysical Log for G-3784. U. S. Geological Survey, Center for Water and Restoration Studies, Miami, Florida, 1 sheet Accessed online January 10, 2015 at http://sofia.usgs.gov/exchanget/L31_wells/L-31-N_G-3784_COMBO.pdf.

  • Wang, Q., and Y. Li. 2010. Phosphorus adsorption and desorption behavior on sediments of different origins. Journal of Soils and Sediments 10: 1159–1173.

    CAS  Article  Google Scholar 

  • Yakubu, M., M. Gumel, and A. Abdullahi. 2008. Use of activated carbon from date seeds to treat textile and tannery effluents. African Journal of Science and Technology (AJST) Science and Engineering Series 9: 39–49.

    Google Scholar 

  • Zapata-Rios, X., and R.M. Price. 2012. Estimates of groundwater discharge to a coastal wetland using multiple techniques: Taylor Slough, Everglades National Park, USA. Hydrogeology Journal 20: 1651–1668.

    Article  Google Scholar 

  • Zhang, J.-Z., and X.-L. Huang. 2007. Relative importance of solid-phase phosphorus and iron on the sorption behavior of sediments. Environmental Science & Technology 41: 2789–2795.

    CAS  Article  Google Scholar 

  • Zhang, J.-Z., and X.-L. Huang. 2011. Effect of temperature and salinity on phosphate sorption on marine sediments. Environmental Science & Technology 45: 6831–6837.

    CAS  Article  Google Scholar 

  • Zhang, J.-Z., C. Kelble, and F.J. Millero. 2001. Gas-segmented continuous flow analysis of iron in water with a long liquid waveguide capillary flow cell. Analytica Chimica Acta 438: 49–57.

    CAS  Article  Google Scholar 

  • Zhang, J.-Z., C.J. Fischer, and P.B. Ortner. 2004. Potential availability of sedimentary phosphorus to sediment resuspension in Florida Bay. Global Biogeochemical Cycles 18(4): GB4008. doi:10.1029/2004GB002255.

  • Zhou, M., and Y. Li. 2001. Phosphorus-sorption characteristics of calcareous soils and limestone from the southern Everglades and adjacent farmlands. Soil Science Society of America Journal 65: 1404–1412.

    CAS  Article  Google Scholar 

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Acknowledgements

Thanks to Dr. Kevin Cunningham of US Geological Survey for assisting in the laboratory with lithologic descriptions and selection of intact Tamiami Formation specimens and for providing access to G-3784 test corehole. Dr. René Price, Rafael Travieso, and Edward Linden of Florida International University provided for field and laboratory support, and Charles Fischer of National Oceanic and Atmospheric Administration/Atlantic Oceanographic and Meteorological Laboratory assisted in sample analysis. We also wish to thank the associate editor and anonymous reviewer who provided detailed feedback, vastly improving the manuscript, particularly with regard to stratigraphy. This material is based upon work supported by the National Science Foundation through the Florida Coastal Everglades Long-Term Ecological Research program under Cooperative Agreements #DEB-1237517, #DBI-0620409, and #DEB-9910514. This is contribution number 823 from the Southeast Environmental Research Center in the Institute of Water & Environment at Florida International University.

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Correspondence to Hilary Flower.

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Communicated by Nancy L. Jackson

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Flower, H., Rains, M., Lewis, D. et al. Rapid and Intense Phosphate Desorption Kinetics When Saltwater Intrudes into Carbonate Rock. Estuaries and Coasts 40, 1301–1313 (2017). https://doi.org/10.1007/s12237-017-0228-z

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  • DOI: https://doi.org/10.1007/s12237-017-0228-z

Keywords

  • Florida Everglades
  • Groundwater
  • Submarine groundwater discharge