1. Lecture 10: Ocean Carbonate Chemistry: Ocean Distributions Controls on Distributions What is the distribution of CO 2 added to the ocean? See Section 4.4 Emerson and Hedges

2. Sarmiento and Gruber (2002) Sinks for Anthropogenic Carbon Physics Today August 2002 30-36

3. CO 2 CO 2 → H 2 CO 3 → HCO 3 - → CO 3 2- + H 2 O = CH 2 O + O 2 B orgC + Ca 2+ = CaCO 3 B CaCO3 Atm Ocn Biological Pump Controls: pH of ocean Sediment diagenesis CO 2 Gas Exchange Upwelling/ Mixing River Flux CO 2 + rocks = HCO 3 - + clays

4. Influences on pCO 2 K o : Solubility of CO 2 K 1, K 2 : Dissociation constants Function of Temperature, Salinity Depends on biology and gas exchange Depends on biology only

5. Influence of Nitrogen Uptake/Remineralization on Alkalinity NO 3 - assimilation by phytoplankton 106 CO 2 + 138 H 2 O + 16 NO 3 - → (CH 2 O) 106 (NH 3 ) 16 + 16 OH - + 138 O 2 NH 3 assimilation by phytoplankton 106 CO 2 + 106 H 2 O + 16 NH 4 + → (CH 2 O) 106 (NH 3 ) 16 + 16 H + + 106 O 2 NO 3 - uptake is balanced by OH - production Alk ↑ NH 4 + uptake leads to H + generation Alk ↓ Alk = HCO 3 - + 2 CO 3 2- + OH - - H + See Brewer and Goldman (1976) L&O Goldman and Brewer (1980) L&O Experimental Culture

6. Air-Sea CO 2 Disequilibrium

7. Emerson and Hedges Plate 8

8. Effect of El Nino on ∆pCO 2 fields High resolution pCO 2 measurements in the Pacific since Eq. Pac-92 Eq Pac-92 process study Cosca et al. in press El Nino Index P CO2sw Always greater than atmospheric

9. Expression of Air -Sea CO 2 Flux k-transfer velocity From Sc # & wind speed From CMDL CCGG network S – Solubility From SST & Salinity From measurements and proxies F = k s (pCO 2w - pCO 2a ) = K ∆ pCO 2 pCO 2a pCO 2w  Magnitude  Mechanism  Apply over larger space time domain

10. Global Map of Piston Velocity (k in m yr -1 ) times CO 2 solubility (mol m -3 ) = K from satellite observations (Nightingale and Liss, 2004 from Boutin).

11. Overall trends known: * Outgassing at low latitudes (e.g. equatorial) * Influx at high latitudes (e.g. circumpolar) * Spring blooms draw down pCO 2 (N. Atl) * El Niños decrease efflux ∆pCO 2 fields

12. Monthly changes in pCO 2w ∆pCO 2 fields:Takahashi climatology JGOFS Gas Exchange Highlight #4 -

13. Fluxes: JGOFS- Global monthly fluxes Combining pCO 2 fields with k: F = k s (pCO 2w - pCO 2a )  On first order flux and ∆pCO 2 maps do not look that different

14. Do different parameterizations between gas exchange and wind matter? Global uptakes Liss and Merlivat-83: 1 Pg C yr -1 Wanninkhof-92: 1.85 Pg C yr -1 Wanninkhof&McGillis-98: 2.33 Pg C yr -1 Zemmelink-03: 2.45 Pg C yr -1 Yes! CO 2 Fluxes: Status Global average k (=21.4 cm/hr): 2.3 Pg C yr -1 We might not know exact parameterization with forcing but forcing is clearly important Compare with net flux of 1.3 PgCy -1 (1.9 - 0.6) in Sarmiento and Gruber (2002), Figure 1

15. What happens to the CO 2 that dissolves in water? CO 2 is taken up by ocean biology to produce a flux of organic mater to the deep sea (B orgC ) CO 2 + H 2 O = CH 2 O + O 2 Some carbon is taken up to make a particulate flux of CaCO 3 (B CaCO3 ) Ca 2+ + 2HCO 3 - = CaCO 3 (s) + CO 2 + H 2 O The biologically driven flux is called the “Biological Pump”. The sediment record of B orgC and B CaCO3 are used to unravel paleoproductivity. The flux of B orgC to sediments drives an extensive set of oxidation-reduction reactions that are part of sediment diagenesis. Carbonate chemistry controls the pH of seawater which is a master Variable for many geochemical processes.

16. Ocean Distributions – versus depth, versus ocean Atlantic Pacific Points: 1. Uniform surface concentrations 2. Surface depletion - Deep enrichment 3. DIC < Alk  DIC >  Alk See Key et al (2004) GBC Q?

17. The main features are: 1. uniform surface values 2. increase with depth 3. Deep ocean values increase from the Atlantic to the Pacific 4. DIC < Alk  DIC >  Alk 5. Profile of pH is similar in shape to O 2. 6. Profile of P CO2 (not shown) mirrors O 2. Ocean Distributions of, DIC, Alk, O 2 and PO 4 versus Depth and Ocean

18. Inter-Ocean Comparison

19. Carbonate ion (CO 3 2- ) and pH decrease from Atlantic to Pacific x 10 -3 mol kg -1 x 10 -6 mol kg -1 AlkDICCO 3 2- pH Surface Water2.3001.9502428.30 North Atlantic2.3502.1901098.03 Deep Water Antarctic2.3902.280 847.89 Deep Water North Pacific2.4202.370 577.71 Deep water Deep Atlantic to Deep Pacific D Alk = 0.070 D DIC = 0.180 So D Alk/ D DIC = 0.40 CO 3 2- decreases from surface to deep Atlantic to deep Pacific. These CO 3 2- are from CO2Sys. Can Approximate as CO 3 2- ≈ Alk - DIC Q? CO 2 Sys

20. Controls on Ocean Distributions A) Photosynthesis/Respiration Organic matter (approximated as CH 2 O for this example) is produced and consumed as follows: CH 2 O + O 2  CO 2 + H 2 O Then: CO 2 + H 2 O  H 2 CO 3 * H 2 CO 3 *  H + + HCO 3 - HCO 3 -  H + + CO 3 2- As CO 2 is produced during respiration we should observe: pH  DIC  Alk  P CO2  The trends will be the opposite for photosynthesis. B) CaCO 3 dissolution/precipitation CaCO 3 (s)  Ca 2+ + CO 3 2- Also written as: CaCO 3 (s) + CO 2 + H 2 O  Ca 2+ + 2 HCO 3 - As CaCO 3 (s) dissolves, CO 3 2- is added to solution. We should observe: pH  DIC  Alk  P CO2 

21. Photosynthesis/respiration (shown as apparent oxygen utilization or AOU = O 2,sat – O 2,obs ) and CaCO 3 dissolution/precipitation vectors (from Park, 1969) CH 2 O + O 2 → CO 2 + H 2 O as O 2 ↓ AOU ↑ CO 2 ↑

22. Composition of Sinking Particles and Predicted Changes

23. Ocean Alkalinity versus Total CO2 in the Ocean (Broecker and Peng, 1982)

24. Emerson and Hedges Color Plate  DIC/  Alk ≈ 1.5/1 Work Backwards  Alk /  DIC ≈ 0.66 = 2/3 = 2 mol Org C / 1 mol CaCO 3

25. From Klaas and Archer (2002) GBC Data from annual sediment traps deployments 5 g POC g m -2 y -1 / 12 g mol -1 = 0.4 mol C m -2 y -1 40 g CaCO 3 g m -2 y -1 / 105 g mol -1 = 0.38 mol C m -2 y -1 What is composition of sinking particles? Org C / CaCO 3 ~ 1

26. PIC/POC in sediment trap samples

27. POC and CaCO 3 Export Fluxes This StudyPrevious Studies POC (Gt a −1 ) Global export9.6 ± 3.611.1–12.9 [Laws et al., 2000] b b 9.2 [Aumont et al., 2003] c c 8.6 [Heinze et al., 2003] c c 8.7–10.0 [Gnanadesikan et al., 2004] c c 9.6 [Schlitzer, 2004] d d 5.8–6.6 [Moore et al., 2004] c c CaCO 3 (GtC a −1 ) Global export0.52 ± 0.150.9–1.1 [Lee, 2001] b b 1.8 [Heinze et al., 1999] c c 1.64 [Heinze et al., 2003] c c 0.68–0.78 [Gnanadesikan et al., 2004] c c 0.38 [Moore et al., 2004] c c 0.84 [Jin et al., 2006] c c 0.5–4.7 [Berelson et al., 2007] b b Based on Global Model results of Sarmiento et al (2992) GBC; Dunne et al (2007) GBC

28. Revelle Factor The Revelle buffer factor defines how much CO 2 can be absorbed by homogeneous reaction with seawater.  = dP CO2 /P CO2 / dDIC/ DIC B = C T / P CO2 (∂P CO2 /∂C T ) alk = C T (∂P CO2 /∂H) alk P CO2 (∂C T /∂H) alk After substitution B ≈ C T / (H 2 CO 3 + CO 3 2- ) For typical seawater with pH = 8, Alk = 10 -2.7 and C T = 10 -2.7 H 2 CO 3 = 10 -4.7 and CO 3 2- = 10 -3.8 ; then B = 11.2 Field data from GEOSECS Sundquist et al., Science (1979) dPCO2/PCO2 = B dDIC/DIC A value of 10 tells you that a change of 10% in atm CO 2 is required to produce a 1% change in total CO 2 content of seawater, By this mechanism the oceans can absorb about half of the increase in atmospheric CO 2 B↑ as T↓

30. CO 2 CO 2 → H 2 CO 3 → HCO 3 - → CO 3 2- Atm Ocn 350ppm + 10% = 385ppm 11.3  M +1.2 (10.6%) 12.5 1640.5  M +27.7 (1.7%) 1668.2 183.7 -11.1 (-6.0%) 174.2 Revelle Factor Numerical Example (using CO 2 Sys) CO 2 + CO 3 2- = HCO 3 - 1837 +17.9 (+0.97%) 1854.9 DIC The total increase in DIC of +17.9  M is mostly due to a big change in HCO 3 - (+27.7  M) countering a decrease in CO 3 2- (-11.1  M). Most of the CO 2 added to the ocean reacts with CO 3 2- to make HCO 3 -. The final increase in H 2 CO 3 is a small (+1.2  M) portion of the total.