Carbonate chemistry in the coastal zone responds more strongly to eutrophication than ocean acidification

The accumulation of anthropogenic CO2 in the ocean has altered carbonate chemistry in surface waters since preindustrial times and is expected to continue to do so in the coming centuries. Changes in carbonate chemistry can modify the rates and fates of marine primary production and calcification. These modifications can in turn lead to feedback on increasing atmospheric CO2. We show, using a numerical model, that in highly productive nearshore coastal marine environments, the effect of eutrophication on carbon cycling can counter the effect of ocean acidification on the carbonate chemistry of surface waters. Also, changes in river nutrient delivery due to management regulation policies can lead to stronger changes in carbonate chemistry than ocean acidification. Whether antagonistic or synergistic, the response of carbonate chemistry to changes of nutrient delivery to the coastal zone (increase or decrease, respectively) is stronger than ocean acidification. The open ocean is a major sink of anthropogenic CO2 (Sabine et al. 2004); however, the accumulation of anthropogenic CO2 has altered carbonate chemistry in surface waters since preindustrial times, and is expected to continue to do so in the coming centuries (Orr et al. 2005). Ocean acidification of surface waters corresponds to the increase of [CO2] and of [H+], the decrease of pH and of [CO 2{ 3 ], and of the saturation state of calcite (Vca) and aragonite (Var), all related to shifts in thermodynamic equilibria in response to the input of anthropogenic CO2 from the atmosphere. Changes of the carbonate chemistry of surface waters related to ocean acidification can alter the rates and fates of primary production and calcification of numerous marine organisms and communities (Kleypas et al. 2006; Doney et al. 2009). Such changes can provide either positive or negative feedback on increasing atmospheric CO2 by modifying the flux of CO2 between the ocean and the atmosphere. The increase of [CO2] can favor the availability of inorganic carbon for primary producers, whereas the decrease of [CO 2{ 3 ], Vca, and Var make the precipitation of CaCO3 thermodynamically less favorable (or impossible spontaneously in CaCO3-undersaturated conditions). An increase in primary production associated with efficient organic carbon export would induce a negative feedback on increasing atmospheric CO2, according to: CO2zH2O?CH2OzO2 ð1Þ

[1]  C. Heip,et al.  Impact of elevated CO2 on shellfish calcification , 2007 .

[2]  A. Borges,et al.  Effect of eutrophication on air–sea CO2 fluxes in the coastal Southern North Sea: a model study of the past 50 years , 2009 .

[3]  F. Mackenzie,et al.  Solution of shallow-water carbonates: An insignificant buffer against rising atmospheric CO2 , 2003 .

[4]  J. Gattuso,et al.  CARBON AND CARBONATE METABOLISM IN COASTAL AQUATIC ECOSYSTEMS , 1998 .

[5]  K. Ruddick,et al.  Modelling diatom and Phaeocystis blooms and nutrient cycles in the Southern Bight of the North Sea: the MIRO model , 2005 .

[6]  Josette Garnier,et al.  Nutrient fluxes and water quality in the drainage network of the Scheldt basin over the last 50 years , 2005, Hydrobiologia.

[7]  Christoph Humborg,et al.  Effect of Danube River dam on Black Sea biogeochemistry and ecosystem structure , 1997, Nature.

[8]  G. Leeuw,et al.  Atmospheric nitrogen inputs into the North Sea: effect on productivity , 2003 .

[9]  Fei-xue Fu,et al.  CO2 control of Trichodesmium N2 fixation, photosynthesis, growth rates, and elemental ratios: Implications for past, present, and future ocean biogeochemistry , 2007 .

[10]  E. Maier‐Reimer,et al.  Anthropogenic ocean acidification over the twenty-first century and its impact on calcifying organisms , 2005, Nature.

[11]  Nicolas Gruber,et al.  The Oceanic Sink for Anthropogenic CO2 , 2004, Science.

[12]  B. Delille,et al.  Response of primary production and calcification to changes of pCO2 during experimental blooms of the coccolithophorid Emiliania huxleyi , 2005 .

[13]  Howard R. Gordon,et al.  Calcium carbonate measurements in the surface global ocean based on Moderate‐Resolution Imaging Spectroradiometer data , 2005 .

[14]  D. Harbour,et al.  Evolution And Structure Of A Shelf Coccolithophore Bloom In The Western English-Channel , 1995 .

[15]  A. Mucci The solubility of calcite and aragonite in seawater at various salinities , 1983 .

[16]  Toby Tyrrell,et al.  Phytoplankton Calcification in a High-CO2 World , 2008, Science.

[17]  J. Garnier,et al.  Testing an integrated river-ocean mathematical tool for linking marine eutrophication to land use: The Phaeocystis-dominated Belgian coastal zone (Southern North Sea) over the past 50 years , 2007 .

[18]  Fei-xue Fu,et al.  Interactive effects of increased pCO2, temperature and irradiance on the marine coccolithophore Emiliania huxleyi (Prymnesiophyceae) , 2008 .

[19]  G. Gong,et al.  Reduction of primary production and changing of nutrient ratio in the East China Sea: Effect of the Three Gorges Dam? , 2006 .

[20]  A. Borges,et al.  Carbon dynamics and CO2 air-sea exchanges in the eutrophied coastal waters of the Southern Bight of the North Sea: a modelling study , 2004 .

[21]  Mark L. Green,et al.  Coastal Acidification by Rivers: A Threat to Shellfish? , 2008 .

[22]  D. Davoult,et al.  Secondary production, calcification and CO2 fluxes in the cirripedes Chthamalus montagui and Elminius modestus , 2008, Oecologia.

[23]  N. Rabalais,et al.  Changes in nutrient structure of river-dominated coastal waters: stoichiometric nutrient balance and its consequences , 1995 .

[24]  X. Ning,et al.  Long term changes in the ecosystem in the northern South China Sea during 1976 2004 , 2008 .

[25]  C. Culberson,et al.  MEASUREMENT OF THE APPARENT DISSOCIATION CONSTANTS OF CARBONIC ACID IN SEAWATER AT ATMOSPHERIC PRESSURE1 , 1973 .

[26]  B. Delille,et al.  Effects of CO 2 on particle size distribution and phytoplankton abundance during a mesocosm bloom experiment (PeECE II) , 2007 .

[27]  J. Lamarque,et al.  Impact of anthropogenic atmospheric nitrogen and sulfur deposition on ocean acidification and the inorganic carbon system , 2007, Proceedings of the National Academy of Sciences.

[28]  N. P. Holliday,et al.  ICES report on ocean climate 2005 , 2006 .

[29]  Other ICES Report on Ocean Climate 2005 , 2006 .

[30]  F. Millero,et al.  A comparison of the equilibrium constants for the dissociation of carbonic acid in seawater media , 1987 .

[31]  David L. Strayer,et al.  Mollusks as ecosystem engineers: the role of shell production in aquatic habitats , 2003 .

[32]  U. Riebesell,et al.  Enhanced biological carbon consumption in a high CO2 ocean , 2006, Nature.

[33]  R. Feely,et al.  Ocean acidification: the other CO2 problem. , 2009, Annual review of marine science.

[34]  J. Gattuso,et al.  Calcium carbonate production of a dense population of the brittle star Ophiothrix fragilis (Echinodermata: Ophiuroidea): role in the carbon cycle of a temperate coastal ecosystem , 1998 .

[35]  Marcello Vichi,et al.  Link or sink: a modelling interpretation of the open Baltic biogeochemistry , 2004 .

[36]  Josette Garnier,et al.  Modeling the response of water quality in the Seine River estuary to human activity in its watershed over the last 50 years , 2001 .

[37]  Denis Allemand,et al.  Impacts of ocean acidification on coral reefs and other marine calcifiers : a guide for future research , 2006 .