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

This spreadsheet is designed to calculate carbon system parameters given T, S, P, TotCO2, a

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
(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 accur
It is intended as a tool to get carbon system estimates, but it is not intended to be a slick
nor is it intended to be an example of good spreadsheet programming. Many of the formu
Apple II spreadsheet - so don't expect it to take advantage of modern spreadsheet featur
It was devised using a Macintosh, and I don't know if everything will display properly on a P
I have tried to get these calculations right, but I am not a professional carbonate chemist n
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 calcu
- 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 guar
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
©2005 Ed Boyle, MIT

Instructions:
(a) Enter values for T, S, P, Total CO2, and Alkalinity in cells B6,C6,E6,G6, and H6.
(b) The main CO2 system parameters are shown in cells B11-G11. Other propertie
ven T, S, P, TotCO2, and Alkalinity inputs (boldface blue cells).

pplies in the range of natural seawater pH.

ound in a titration).

uarantees of accuracy.
tended to be a slick professional-looking piece of software,
ng. 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.
future versions.
debates on the calculation scheme.

you do, I cannot guarantee that the spreadsheet will continue

this spreadsheet or modifications of it.

C6,E6,G6, and H6. Then recalculate (or set to auto-calculate).

11. Other properties (e.g. carbon isotope values) are estimated elsewhere.
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 ( CO2, µmol/kg Alk, µeq/kg ---------
-------- -------- -------- -------- -------- ------------ -----------
34.700 27.000 300.15 0 1.0 1930 2290 Don't delete -->
this section!

pH pCO2O2(aq) CO3- CO3= Omega Don't delete -->

------ ----- ------ ------ ----- ------ this section!
8.114 317 8.6 ### ### 6.467 calcite
36 4.287 aragonite Don't delete -->
frac. of tot CO2: 0.4% ### 13.8% this section!

1a epsilon CO2(gas) rel. to CO2 (aq) 1.18 source: Zhang, Quay, Wilbur GCA 59:107
1b epsilon CO2 (gas) rel. to HCO3- -6.97 source: Zhang, Quay, Wilbur GCA 59:107
1c epsilon CO2 (gas) rel. to CO3= -5.82 source: Zhang, Quay, Wilbur GCA 59:107
2 epsilon CO2(gas) rel. to CO2 (aq) -1.05 source: Vogel et al. 1970 (Z. phys. 230: 225) as computed by Mook et
3 epsilon CO2 (gas) rel to HCO3- -7.70 source: Mook et al. 1974 (EPSL 22:169-176)
4 epsilon CO2 (aq) rel. to HCO3- -8.75 source: Mook et al. 1974 (EPSL 22:169-176), by combining 2 and 3
5 epsilon CO2 (gas) rel. to CO3= -8.15 source: Lesniak and Sakai 1989 (EPSL 95:297-301)
6 epsilon CO2 (gas) rel. to CaCO3 -9.31 source: Emrich et al. 1970 (EPSL 8:363-371) (but note they excluded

Using 1a-c and 6 above: Pre-anth d13C of atm: -6.4 (280 ppmV)
epsilon CO2(aq) rel to HCO3- -8.15 1990 d13C of atm: -7.8 (350 ppmV)
epsilon CO3 rel to HCO3- -1.16 Glacial max d13C of atm: -6.9 to -7.1 (200 ppmV)
epsilon CaCO3 rel to HCO3- 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

ref: Basicly uses UNESCO (1987) recommendations

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
Kb: Ref: Millero, 1979 using Hansson constant for borate
Ksp: Mucci (1983) equations for solubility; with c Y
and Millero (1979) expression for pressure depen cubic -5.292534E-22 #DIV/0!
setup -3.14318E-45 #DIV/0!
Geochim. Cosmochim. Acta 43:651-666 ion solutions:
X3
7.6828641E-09 [H+] #DIV/0!
8.1144768504 pH #DIV/0!
0.0021883933 Carb Alk #DIV/0!
0.0002669829 CO3= #DIV/0!
0.0016544276 HCO3- #DIV/0!

Page
 8.5895364E-06 H2CO3 #DIV/0!
0.0003174155 pCO2 #DIV/0! ---------
101.6 B(OH)4-
305.9 B(OH)3
407.5 sumB
omega calcite 6.4666636817
omega aragonit 4.2871828278

CO2-Alk-pCO2 table offset 10

Alkalinity
offset= 317.415 2190 2200 2210 2220 2230 2240
25 CO2 1800 249 241 233 225 217 210
1825 280 270 261 252 243 235
1850 315 303 293 282 272 263
1875 355 342 329 317 306 295
1900 402 386 371 357 344 331
1925 457 438 421 404 388 373
1950 522 499 478 458 440 422
1975 599 572 546 522 500 479
2000 692 659 627 598 571 546
2025 805 764 725 689 656 626

Page
CO3-, and B(OH)4-

--------- ----> ......... ......... ......... .......... ..lin... ...log.10

pK(T,P=1,S=0) pK(T,P=1,S) K9 V9 pK(T,P,S)
Don't delete --> 6.340 5.8302 0.0007 22.053 5.83 1.48E-06 -5.830 K_1
this section! 10.310 8.907 0.0028 16.443 8.91 1.24E-09 -8.907 K_2
9.220 8.594 0.0029 27.031 8.59 2.552E-09 -8.593 K_B
Don't delete --> 8.491 6.376 0.0018 34.439 6.38 4.216E-07 -6.375 Ks_calc
this section! 8.317 6.197 0.0018 31.639 6.20 6.359E-07 -6.197 Ks_arag
13.929 13.109 ? ? 13.10902 7.78E-14 -13.109 K_w
Don't delete --> ? ? 1.57 0.027061 -1.568 a_0
this section!

25) as computed by Mook et al. 1974

6), by combining 2 and 3

1) (but note they excluded their 20°C 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!

Page
 Don't delete -->
------------------ --------- --------- --------- --------- --------- --------- --------- ---------

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

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

Ks_calc
Ks_arag

Setup solution to cubic equation:

B/CO2 Alk/CO2

sumB/CO2 Alk/CO2
0.2111 1.18653
### #DIV/0!
-4.798E-24 A0 #DIV/0!
-1.585E-15 A1 #DIV/0!
2.785E-07 A2 #DIV/0!
1.1865285 A3 #DIV/0!
Q
-6.57E-15 #DIV/0!

Page
--------- --------- ------------- --------- ---------

Page
 avgs and typ values

CO2 Alk
Global Ocean Avg. (@S=34.7) 2260 2375
Warm surface waters (Pre-Anth 1920 2290
Cold surface waters 2140 2310

Page 9
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 spreadsh
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

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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 foun `

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

n(10) added

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