1. COMMENCE

2. ANTHROPOCENE COASTAL OCEAN CARBON-CARBONATE SYSTEM Fred T. Mackenzie 1, 2 Andreas Andersson 1, Katie Fagan 1, Dan Hoover 1, Abraham Lerman 2, Stephanie Ringuet 1 1 University of Hawaii; 2 Northwestern University

3. OUTLINE I. Introduction II. Modeling the coastal ocean CO 2 -carbonic acid system, air-sea CO 2 exchange, and effects of rising atmospheric CO 2 and temperature on coastal seawater carbonate saturation states and calcification and carbonate mineral dissolution rates during the Anthropocene III. Coastal ocean air-sea exchange of CO 2 and carbonate saturation state: Lessons on variability from Hawaiian and other coastal ecosystems

4. In contrast to the open ocean, little attention has been given to the role of the shallow coastal ocean in the carbon cycle and its modeling in the context of global change despite the fact that: 8% of the global surface area of the oceans and 2-3% of the volume of the open ocean surface layer reside there 80% of river terrigenous input containing reactive nutrients of N and P and organic carbon is deposited in this region Accounts for 10-30% of global organic primary production Site of 85% of global organic carbon burial Accounts for 26% of global inorganic carbon production, mainly of metastable skeletal aragonite and magnesian calcites Site of 45% of global inorganic carbon burial (reefs account for about 22%); most accumulation of shoal-water CaCO 3 is in the southwest Pacific Ocean Globally still appears to be a source of CO 2 to the atmosphere Heavily impacted by human activities, including doubling of the nutrient N and P and total organic carbon river fluxes since pre-industrial time

6. We have used two models to investigate the Anthropocene history (past few centuries and future) of the global coastal ocean and carbonate ecosystems. These are: TOTEM--Terrestrial Ocean-aTmosphere Ecosystem Model and SOCM--Shallow-Ocean Carbonate. Both models are complex renditions of the carbon (and nitrogen and phosphorus) biogeochemical cycles and their physical, chemical and biological dynamics in the global coastal ocean. Equations for organic productivity, organic respiration, carbonate precipitation and dissolution and temperature and carbonate saturation effect on the rates of carbonate precipitation are part of the SOCM. Depending on the question asked, these two models can be coupled. The major forcings in the models are: INTRODUCTION: MODELING

7. Model forcings based on history from 1700 to early 21st century, BAU to 2100 and linear extrapolation to 2300

8. SOME MODELING RESULTS

11. Coastal ocean surface and pore water carbonate saturation state for different IPCC scenarios of CO 2 and T

12. Changes in calcite saturation state in the North Pacific Central Gyre

13. Major factors involved in air-sea CO 2 exchange in the global coastal ocean

14. Marine carbon chemistry and seawater saturation state of the coastal ocean with respect to various carbonate minerals

15. Carbonate saturation state as a function of latitude (T and DIC); Notice problem with Mg- calcite pKs and the fact that rising CO 2 and temperature may affect high latitude and temperate cold- water carbonate ecosystems to an extent perhaps greater than subtropical/tropical reef ecosystems

16. Calcium carbonate production and dissolution in the coastal ocean using different relationships for the effect of carbonate saturation state and temperature on calcification rate

17. Pore water CaCO 3 saturation state, CaCO 3 dissolution flux and organic matter sedimentation and remineralization fluxes in coastal ocean sediments

18. CONCLUSIONS The global coastal ocean, including most reef ecosystems, probably is still a net source of CO 2 to the atmosphere but soon will become a net sink with rising atmospheric CO 2. Estuaries have a high area specific air-sea CO 2 exchange of -35.8 mol C m -2 y -1 vs +1.17 mol C m -2 y -1 for the distal coastal zone. Both models and observational data show declining carbonate saturation state for the world oceans, including its coastal ocean waters. Modeling shows that saturation state with respect to calcite could decline 45% by the year 2100 and 70% by the year 2300 in coastal ocean waters. Carbonate dissolution and production of alkalinity will not be sufficient enough to buffer the decline in saturation state. The CaCO 3 production rate in coastal seawater could decrease as much as 40 % in the year 2100 and 90% in the year 2300 because of decreasing saturation state and rising temperature.

19. AIR-SEA CO 2 EXCHANGE AND CARBONATE SATURATION STATE RESULTS FROM HAWAIIAN COASTAL ZONE REEF AND NON-REEF ENVIRONMENTS

20. A significant portion of the area of estuaries of 1 x 10 12 m 2 of the world is found in the tropical/subtropical climatic zone. A number of these systems have coralgal reefs associated with them, like Kaneohe Bay, Hawaii. No extended time series studies of the marine carbon system and air-sea exchange of CO 2 have been performed in the coastal zones of tropical/subtropical environments, including reefs. WHY STUDY?

22. METHODS Bimonthly sampling of surface waters at 23 sites for marine carbon parameters since September, 2003. Total alkalinity and dissolved inorganic carbon analysis done using the Hawaii Ocean Time-series program equipment and analytical protocol. PCO 2 calculated using constants from Mehrbach et al. (1973) refit by Dickson and Millero (1987). Additional data for physical properties of the bay (T, S, wind speed and direction, sunlight), river discharge and river and bay nutrient and organic carbon concentrations, dissolved oxygen concentrations, bay productivity, standing crop and phytoplankton community structure, turbidity, etc. were collected through the course of the work.

29. Enchanted Lake Estuarine System--No Coral Reefs

30.  No coral reefs

31. Diel variability of marine carbon system, Mangrove Bay, Bermuda fringing and back-reef Thalassia grass and calcareous green algae biome

32. CONCLUSIONS Majority of estuaries and “ecological” reefs studied to date have been shown to be sources of CO 2 to the atmosphere presently. Estuary and reef ecosystems are extremely dynamic on very short time scales and the direction and magnitude of the air-sea exchange flux and the carbonate saturation state can change rapidly thus: There is a strong need for time series data for the coastal ocean marine carbon system, involving at least two carbon system variables to calculate all carbon system parameters, including carbonate saturation state. Complementary physical and biological data are also needed where possible.

33. FIN

34. Some factors involved in air-sea CO 2 exchange in the global carbonate coastal zone

35. Average PCO 2 s variable and strongly affected by storm runoff from streams: enhanced productivity draws down CO 2 after initial input of high PCO 2 stream waters

36. Storms strongly affect proximal zone PCO 2 s and hence carbonate saturation state due to river runoff flushing out high PCO 2 soil and ground waters

37. Baseline and temporal changes in nutrient and chlorophyll-a concentrations during a storm event: storms bring in nutrient- rich waters with high N/P ratio and promote productivity

38. Productivity, Chl-a and TSS during a storm event: productivity enhanced by input of nutrient-rich river waters after bay waters clear and sun comes out

39. Temporal changes in Chl-a, pigments and pigment ratios during a storm event: the phytoplankton community shifts from one dominated by small diatoms, cyanobacteria and chlorophytes to one dominated by large, chain-forming and pennate diatoms

40. Reminder: organic C and inorganic C coastal zone cycles are coupled

42. Distribution of Modern Warm- and Cool-Water Shelf Carbonates