CARBCALC 5e, E. Boyle, MIT (Jan. 2005).

This spreadsheet is designed to calculate carbon system parameters given T, S, P, TotCO2, and Alkalini It is based on the Dickson and Millero (1987) recommended constants.

It uses the cubic [H+] simplification of the carbon system, which only applies in the range of natural seaw (so it cannot be used to calculate at low and high pH values such as found in a titration). It uses the formula for the exact solution of the cubic equation to find the pH

This speadsheet is released for your convenience without any guarantees of accuracy. It is intended as a tool to get carbon system estimates, but it is not intended to be a slick professional-l nor is it intended to be an example of good spreadsheet programming. Many of the formulas were inh Apple II spreadsheet - so don't expect it to take advantage of modern spreadsheet features. It was devised using a Macintosh, and I don't know if everything will display properly on a PC. I have tried to get these calculations right, but I am not a professional carbonate chemist nor programm If you find a mistake, let me know and in time I will fix the problem in future versions. I am not willing to engage in extended discussions on how to use it or debates on the calculation schem - if it isn't obvious how to use it, then don't!

Don't modify any of the cells other than the boldface blue input cells. If you do, I cannot guarantee that th to function properly.

You are free to redistribute this speadsheet without charge. The copyright notice below is intended to discourage attempts to sell this spreadsheet or modifications 2005 Ed Boyle, MIT

Instructions: (a) Enter values for T, S, P, Total CO2, and Alkalinity in cells B6,C6,E6,G6, and H6. Then recalcula (b) The main CO2 system parameters are shown in cells B11-G11. Other properties (e.g. carbon i

en T, S, P, TotCO2, and Alkalinity inputs (boldface blue cells).

plies in the range of natural seawater pH. ound in a titration).

antees of accuracy. ended to be a slick professional-looking piece of software, g. Many of the formulas were inherited from an old n spreadsheet features. splay properly on a PC. carbonate chemist nor programmer, so bugs can always creep in. uture versions. debates on the calculation scheme.

ou do, I cannot guarantee that the spreadsheet will continue

his spreadsheet or modifications of it.

,E6,G6, and H6. Then recalculate (or set to auto-calculate). Other properties (e.g. carbon isotope values) are estimated elsewhere.

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Equations assume H+, OH-, and other weak acids are negligible compared to CO3=, HCO3-, and B(OH)4(mathematically, this spreadsheet only gives an answer when Alk>0 and Alk/CO2<2.2) Sal, ppt T, deg C T, deg K D, m P, bar (approx) CO2, mol/kg Alk, eq/kg -------- --------------- -------- -------- ---------------------34.700 27.000 300.15 0 1.0 1930 2290 ------------------ ----> pK(T,P=1,S=0) Don't delete --> this section! Don't delete --> this section! Don't delete --> this section!

pH
------

pCO2 CO2(aq) HCO3- CO3=

---------36 ----------

Omega
-----6.467 calcite 4.287 aragonite

8.114

317

8.6 ### ####

0.4% #### 13.8%
1.18 -6.97 -5.82 -1.05 -7.70 -8.75 -8.15 -9.31

frac. of tot CO2:

1a 1b 1c 2 3 4 5 6

epsilon CO2(gas) rel. to CO2 (aq) epsilon CO2 (gas) rel. to HCO3epsilon CO2 (gas) rel. to CO3= epsilon CO2(gas) rel. to CO2 (aq) epsilon CO2 (gas) rel to HCO3epsilon CO2 (aq) rel. to HCO3epsilon CO2 (gas) rel. to CO3= epsilon CO2 (gas) rel. to CaCO3 Using 1a-c and 6 above: epsilon CO2(aq) rel to HCO3epsilon CO3 rel to HCO3epsilon CaCO3 rel to HCO3-

source: Zhang, Quay, Wilbur GCA 59:107 source: Zhang, Quay, Wilbur GCA 59:107 source: Zhang, Quay, Wilbur GCA 59:107 source: Vogel et al. 1970 (Z. phys. 230: 225) as computed by Mook et al. 1974 source: Mook et al. 1974 (EPSL 22:169-176) source: Mook et al. 1974 (EPSL 22:169-176), by combining 2 and 3 source: Lesniak and Sakai 1989 (EPSL 95:297-301) source: Emrich et al. 1970 (EPSL 8:363-371) (but note they excluded their 20C meas Pre-anth d13C of atm: -6.4 (280 ppmV) 1990 d13C of atm: -7.8 (350 ppmV) Glacial max d13C of atm: -6.9 to -7.1 (200 ppmV)

-8.15 -1.16 2.34

eq. d13C (rel. to tot CO2) gas CO2(aq)HCO3- CO3= CaCO3 (calcite) -6.78 -7.95 0.20 -0.96 2.53 If d13C tot CO2 = 0.4 , then: eq. d13C (absolute) -6.38 -7.55 0.60 -0.56 2.93

Don't delete -->

ref: Basicly uses UNESCO (1987) recommendations this section! K1' and K2' [(T,1,S) ]from Dickson and Millero, 1987 Deep-Sea Res. 34:1733-1743 using Hansson, Mehrbach, Harned and Owen pooled equations converted to hydrogen ion concentration Don't scaledelete for 0<S<40 --> Kb: Ref: Millero, 1979 using Hansson constant for borate this section! Ksp: Mucci (1983) equations for solubility; with correction for typo in Unesco/Millero/Dickson Y and Millero (1979) expression for pressure dependence cubic -5.29253E-22 #DIV/0! Don't delete -->

setup Geochim. Cosmochim. Acta 43:651-666 ion solutions: X3 7.68286E-09 8.11447685 0.002188393 0.000266983 0.001654428 8.58954E-06 0.000317415

-3.14318E-45 #DIV/0!

this section!

[H+] pH Carb Alk CO3= HCO3H2CO3 pCO2

Don't delete --> #DIV/0! this section! #DIV/0! #DIV/0! Don't delete --> #DIV/0! this section! #DIV/0! #DIV/0! Don't delete --> #DIV/0! --------------------------

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101.6 B(OH)4305.9 B(OH)3 407.5 sumB omega calcite 6.466663682 omega aragonite 4.287182828

CO2-Alk-pCO2 table offset= 25 317.42 1800 1825 1850 1875 1900 1925 1950 1975 2000 2025

CO2

offset= 10 Alkalinity 2190 2200 249 241 280 270 315 303 355 342 402 386 457 438 522 499 599 572 692 659 805 764

2210 233 261 293 329 371 421 478 546 627 725

2220 225 252 282 317 357 404 458 522 598 689

2230 217 243 272 306 344 388 440 500 571 656

2240 210 235 263 295 331 373 422 479 546 626

-> 2250 2260 204 197 227 220 254 246 285 275 319 308 359 346 405 390 459 441 522 500 597 571

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......... pK(T,P=1,S=0)pK(T,P=1,S) 6.340 5.8302 10.310 8.907 9.220 8.594 8.491 6.376 8.317 6.197 13.929 13.109

......... K9 0.0007 0.0028 0.0029 0.0018 0.0018 ? ?

......... .......... V9 pK(T,P,S) 22.053 5.83 16.443 8.91 27.031 8.59 34.439 6.38 31.639 6.20 ? 13.10902 ? 1.57

..lin...

...log.10

.........

...................

1.48E-06 -5.830 1.24E-09 -8.907 2.55E-09 -8.593 4.22E-07 -6.375 6.36E-07 -6.197 7.78E-14 -13.109 0.027061 -1.568

K_1 K_2 K_B Ks_calc Ks_arag K_w a_0 Setup solution to cubic equation: B/CO2

puted by Mook et al. 1974

mbining 2 and 3

te they excluded their 20C measurement)

Don't delete -->

this section! Don't delete --> this section! Don't delete --> this section! Don't delete --> this section! Don't delete --> this section! Don't delete --> ------------------------- --------------------------------- ---------

sumB/CO2 0.2111 ##### -4.8E-24 A0 -1.59E-15 A1 2.785E-07 A2 1.1865285 A3

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.........

.........

......... e: 2.71828

solution to cubic equation: Alk/CO2

sumB/CO2

Alk/CO2 1.18653 #DIV/0! #DIV/0! #DIV/0! #DIV/0! #DIV/0! Q -6.6E-15 #DIV/0!

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avgs and typ values

CO2 Global Ocean Avg. (@S=34.7) Warm surface waters (Pre-Anth) Cold surface waters

Alk 2260 1920 2140 2375 2290 2310

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Revision 5b assumes that Adkins has correctly identified the following errors: 1. Temperature dependance of epsilon HCO3-gas is 0.141 in Zhang et al. (1995) but Ed has 0.1141 in spreadsheet 2. In the equation for pK1_TP1S the linear salinity dependance should be 0.0068 not 0.00668 3. P dependence (column Q) of K_1 and K_2 need to have negative sign and factor of ln(10) added ----------------------------------------------------------------

June 20, 1999: change to create CarbCalc.5c X-Sender: tmarchitto@mail.whoi.edu Mime-Version: 1.0 To: eaboyle@MIT.EDU From: tmarchitto@whoi.edu (Tom Marchitto) Subject: CaCO3 solubility calculation Date: Sat, 19 Jun 1999 16:26:49 -0400 Hi Ed, While converting your carbonate spreadsheet to Matlab, I think I found a` small error in the Ksp(calcite) calculation (at least in the version of the spreadsheet I have). Depending on how it's corrected, it changes [CO3]sat'n(calcite) by up to a few umol/kg. The error arises from a typo in UNESCO (1987). They give Mucci's (1983) equation as: log(Kspar/Kspcal)=0.0385+63.974/T but Mucci gives it as: log(Kspar/Kspcal)=-0.0385+63.974/T In your spreadsheet, you effectively corrected this error by subtracting a fudge factor of 0.1 from pKsp_cal_(t,p1,s), to force a value of 6.35 at 25C and S=35, which was given by UNESCO as "preferred". The correct equation (with the "-") gives a value of 6.37, same as what Mucci got, and within error of the preferred 6.35 +/-0.02. With no fudge factor, [CO3]sat'n changes by a few umol/kg. If a new fudge factor of -0.02 is used, there is less than 1 umol/kg change. The old fudge factors for both calcite (-0.1) and aragonite (-0.01) were justified because the calcite pKsp value was so far off (by 0.1). But with the correct Mucci equation, I'd argue that fudge factors are not required (both pKsp values at 25C and S=35 are only off by 0.02, within error of the preferred). Let me know what you think when you get a chance. Tom ---------Jan. 21, 2000 -------------------------------------------------------

change to CarbCalc.5d XL Mar 9, 1999: Yair says: While looking into the problem I noticed that your file need a minor correction for R. It should be 83.143 rather than 82.05 when using pressure in bars Jan. 21, 2000: verfied that 1 bar = 0.9869 atm this would correspond to R=83.139 for bar units (not exactly what Yair proposes, but very close) But rather than changing R, I chose to convert pressure to atm. instead. ---------------------------21-Jun-00 change to CarbCalc.5e XL added in Revelle Factor calculation -------------------------------------

d has 0.1141 in spreadsheet

ln(10) added ----------

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