Carbon Dioxide, Alkalinity and ph

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1 Carbon Dioxide, Alkalinity and ph OCN 62 Chemical Oceanography Reading: Libes, Chapter 15, pp (Remainder of chapter: Biogenic production, carbonate saturation and sediment distributions ) 1. CO 2 speciation 2. ph. Alkalinity Outline 4. Calculation of composition of marine CO 2 system 5. Oceanographic applications 6. Global CO 2 1

2 Why is it important to understand the CO 2 system? CO 2 controls the fraction of inbound radiation that remains trapped in the atmosphere (greenhouse effect), which controls planetary climate CO 2 is the raw material used to build organic matter CO 2 controls the ph of the oceans Distribution of CO 2 species affects preservation of CaCO deposited on the sea floor CO 2 Speciation CO 2 (g) has many possible transformations upon dissolution in H 2 O Major dissolved forms: CO 2(aq) (aqueous carbon dioxide a dissolved gas) H 2 CO (carbonic acid trace amount) HCO - (bicarbonate ion) CO (carbonate ion) Species interconvert readily Perturbations to one part of CO 2 system leads to redistribution of species Reactions not always intuitive! 2

3 Equations for CO 2 Speciation The equilibrium of gaseous and aqueous CO 2 : CO 2(g) CO 2(aq) Subsequent hydration and dissociation reactions: CO 2(aq) + H 2 O H 2 CO HCO - + H + Asterisk (*) indicates a stoichiometric constant HCO - CO + H + { H K * = 1 }[ HCO [ CO { H }[ CO K2* = [ HCO 2 Hint: when ph is between 7.5 and 8.5: CO 2(aq) + CO + H 2 O 2HCO - CO 2(aq) Seawater values shown --- freshwater curves are shifted left CO 2(g) CO 2(aq) CO 2(aq) + H 2 O HCO - + H + HCO - CO + H + aob.oxfordjournals.org

4 How to Calculate K 1 * and K 2 * pk = - log K Millero et al. (2006) Mar. Chem. 100, For: S = 0 50, T = 0 50 C At S = 5 and T = 25 C: pk 1 * = pk 2 * = Effects of Pressure pk 1 * pk 2 * 1 atm atm Decreased pressure shifts reactions to left { H K * = 1 }[ HCO [ CO + 2 (K 1 *) d / (K 1 *) 1 (K 2 *) d / (K 2 *) 1 1 = 1 atm As you raise a sample from depth: - Ks decrease - Reactions shift to left -ph increases -CO 2(g) release CO 2(g) CO 2(aq) CO 2(aq) + H 2 O HCO - + H + HCO - CO + H + 4

5 Total CO 2 (ΣCOCO 2 ) Total CO 2 [CO 2(aq) + [H 2 CO + [HCO - + [CO At seawater ph, >99% of CO 2 species are HCO - and CO, so we can simplify: Total CO 2 [HCO - + [CO This is also known as dissolved inorganic carbon (DIC) Equilibrium equations can be combined to allow us to calculate the concentration of any of the CO 2 species CaCO Precipitation/Dissolution A tricky subject when discussing CO 2 (or, more properly, P CO2 ) Ca 2+ + CO 2- CaCO Does this reduce the CO 2 (P CO2 ) level of the seawater? No! Lost CO 2- will be replaced: HCO - CO 2- + H + But this H + release causes: HCO - + H + CO 2 + H 2 O CO 2(g) CO 2(aq) CO 2(aq) + H 2 O HCO - + H + HCO - CO + H + Thus, CaCO precipitation causes a decrease in Total CO 2, but an increase in P CO2 Hint: when ph is between 7.5 and 8.5: CO 2(aq) + CO + H 2 O 2HCO - 5

6 Seawater ph ph = - log {H + } The ph of seawater varies only between about 7.5 and 8.4 (i.e., slightly alkaline) Over geological time, ph is thought to be controlled by water/mineral equilibria Over shorter time scales (10 4 to 10 5 yrs) the CO 2 system (and its shifting equilibria) regulates seawater ph CO 2(aq) + H 2 O HCO - + H + Seawater ph T and P Effects For temperatures T 1 and T 2 : ph T2 = ph T (T 2 T 1 ) Increased T causes ph to increase 1 = 1 atm Increased P causes ph to decrease 6

7 Definitions of Alkalinity GENERAL DEFINITION: The acid-buffering capacity of seawater Total Alkalinity (TA) represents ability of seawater to resist ph change upon addition of acid Remember the concept of a buffer (from basic chemistry): a substance that resists ph change upon addition of acid or base For seawater we focus on its ability to absorb H + Total Alkalinity (TA) TA 2[CO + [HCO - + [H 2 BO - + 2[HBO + [BO - + [OH - + [organic/inorganic H + acceptors - [H + End point of an alkalinity titration (using acid titrant) is when: [H + = 2[CO + [HCO - + [H 2 BO - + 2[HBO + [BO - + [OH - + [H + acceptors TA usually reported in meq/l or meq/kg (an equivalent is a mole of charge) 7

8 Carbonate Alkalinity (CA) CA 2[CO + [HCO - Typically, HCO - and CO are present at ~1000x conc of other proton acceptors Hence: CA nearly equals TA Calculations Any two of the four CO 2 properties (ΣCO 2, P CO2, ph, and carbonate alkalinity) can be used to determine the CO 2 system Traditionally, ph and alkalinity were measured Now we can also use ΣCO 2 and P CO2 to better constrain calculations, improving accuracy 8

9 Example Calculation #1 Use ΣCO 2 and Carbonate Alkalinity data to calculate the concentrations of each inorganic carbon species (CO 2(aq), HCO -, and CO 2- ) (assuming CO 2(aq) is neglibible) two equations & two unknowns: CA 2[CO + [HCO - [HCO - = CA - 2[CO ΣCO 2 [HCO - + [CO = CA - 2[CO + [CO = CA [CO [CO = CA - ΣCO 2 [HCO - = CA 2(CA - ΣCO 2 ) = 2ΣCO 2 -CA Example Calculation # 2 Calculate the concentration (in mm) of each inorganic carbon species (CO 2(aq), HCO -, and CO 2- ) if: ΣCO 2 = 2. mm, ph = 8.0, T = 10 C, P = 1 atm, S = 5 At T = 10ºC, S = 5 : pk 1 * = 6.08 K 1 * = = 8.18 x 10-7 pk 2 * = 9.28 K 2 * = = x ph = 8.0 {H + } = From the definition of stoichiometric equilibrium constants: [CO 2 2 [CO = {H + }[HCO = = [HCO K * 1 K 2 *[HCO = [HCO {H + } 9

10 From the definition of ΣCO 2 : ΣCO 2 = [CO 2 + [HCO - + [CO 2-2. = ( x [HCO - ) + [HCO - + ( x [HCO - ) 2. = x [HCO - [HCO - = 2.16 mm [CO 2 = ( )(2.16) = mm [CO 2- = ( )(2.16) = 0.11 mm What processes affect Alk and ΣCO 2? CO 2 exchange between the atmosphere and surface seawater changes ΣCO 2, but doesn t affect Alk Photosynthesis / respiration also changes ΣCO 2, but doesn t affect Alk (loss of HCO - is balanced by loss of H + ) CaCO dissolution / precipitation changes both ΣCO 2 and Alk 10

11 Calcification Effects on Alk-pH ph-σco 2 Surface-ocean plankton remove CO 2- and Ca 2+ from seawater to form CaCO tests (calcification): CO 2- + Ca 2+ CaCO Calcification alters both Alk and ΣCO 2, but not ph Amount of Alk decrease is 2x the effect on ΣCO 2 because of double negative charge of CO 2- CO 2(aq) + CO + H 2 O 2HCO - Processes Affecting Alkalinity 11

12 Vertical ΣCO 2 and Alkalinity Profiles Figure Current Status of Global CO 2 CO 2 input to atmosphere is primarily through oxidation of fossil organic matter (i.e., oil, coal and natural gas) and cement production We are currently adding considerably to the CO 2 inventory of the atmosphere and the oceans, while stimulating terrestrial biomass production There is ~5x as much CO 2 in the ocean as in the atmosphere 12

13 Fate of Anthropogenic CO 2 Emissions (2010) 9.1±0.5 PgC y ±0.2 PgC y -1 50% + 2.6±1.0 PgC y-1 0.9±0.7 PgC y 26% -1 Calculated as the residual of all other flux components 24% 2.4±0.5 PgC y -1 Average of 5 models Global Carbon Project 2010; Updated from Le Quéré et al. 2009, Nature Geoscience; Canadell et al. 2007, PNAS Ocean CO 2 Increase Tracks Atmosphere Ocean Acidification Pre- industrial (1700s) ph 1

14 In More Detail... Ocean Acidification: Starting with the Science National Research Council Ocean ph Byrne et al. 2010, Geophys. Res. Lett. 7 14

15 Change in seawater ph between 1991 and 2006 Change in seawater ph attributed to natural interdecadal/interannual DIC variability between 1991 and 2006 (due mostly to slowdown in downwelling, with more respiration at given depths) Change in seawater ph attributed to the uptake of anthropogenic carbon between 1991 and 2006 Global Oceanic CO 2 Flux High values at equator (esp. in the Pacific) and along west coasts are from upwelling and subsequent gas evasion to atmosphere Low values where there is high bioproductivity Sabine et al Low values where cooling of ocean increases solubility of gas and causes gas infusion to surface ocean 15

16 El Niño Effects on CO 2 Exchange f = fugacity = partial pressure Intra-annual variability of CO 2 fluxes are primarily affected by: Changes in upwelling rates of CO 2 -enriched waters from the Equatorial Undercurrent Advection of CO 2 -depleted waters from the western equatorial Pacific Both processes are strongly affected by El Niño Ocean Water-column Anthropogenic Carbon (C( ant ) Sabine & Tanhua Ann. Rev. Mar. Sci. 16

17 Homework Due: Thurs, February 16, 2012 Consider a seawater with these characteristics: S = 5 ΣCO 2 = 2.2 mm Carbonate alkalinity = 2.1 meq L -1 T = 25 C 1) What is the pco 2 of this seawater, assuming the Bunsen Coefficient for dissolved carbon dioxide (β CO2 ) is 0 mmol L -1 atm -1? 2) Is this seawater under- or super-saturated with respect to atmospheric CO 2? What is the basis for your answer? Show All Calculations! State All Assumptions! 17

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