.. , 

DEPARTMENT OF THE INTERIOR 

FRANKLIN K. LANE, Secretary 

UNITED STATES GEOLOGICAL SURVEY 

GEORGE OTIS SMITH, Director 

PROFESSIONAL PAPER 120-A 

NEW DETERMINATIONS OF CARBON DIOXIDE IN 

WATER OF THE GULF OF MEXICO 

BY 

ROGER C. "VELLS 

Published lune 20, 1918 

Shorter contributions to general geology, 1918 . 

(Paaes 1-16) 

WASJIINGTON 

GOVERNMENT PRINTING OFFICE 

1918 
. ,, 

• 

, 

DEPARTMENT .OF THE INTERIOR . ' 

FRANKLIN K. LANE, Secretary 

UNITED STATES GEOLOGICAL SURVEY 

GEORGE OTIS SMITH, Director 

Professional Paper 120___:.A 

NEW DETERMINATIONS OF CARBON DIOXIDE. IN 

WATER OF THE GULF OF MEXICO 

BY 

RO.GER C. '\IVELLS 

Published June 20, 1918. 

Shorter contributions to general geology, 1918 . 

(Pages 1-16) 

W ASJ-IINGTON 

GOVEU.NMENT PRINTING OFFIOE 

1918· 
.. ~ .-.. · 

CONTENTS. 

Page. 

Introduction ........................................................................................... . 1 

Defmition of terms ...... _ ... ·- .. ·- ...... · .. -................... -........................ · ....................... . 2 

Determination of total carbon dioxide .................................................................... . 3 

Theoretical amount of carbon dioxide in sea water .......................................... · ............. . 5 

Comparison of results with equilibrium conditions .•. : . ................ ~ .............. ; ............... : ... . 6 

Determination of total carbonate and bicarbonate ........ : .. ~ .... ·_ ........................................ . 7 

- Discussion of results for the total carbonate and· bicarbonate.-.... -......... ; ............................... . 9 

Calculation of carbonate and bicarbonate .. : ... :: ........... _-_:.· .. :.·.~ ...................... ; ............. . .11 

Summary ........ · ..... - . -......... : ............................. _ ... _____ .. .- ........ ~ .. _ 16 

ILLUSTRATION. 

Page. 

FIGURE 1. Curve showing variation of loosely combined carbon dioxide in surf~ce sea water with temperature. 13 

N OTE.-The papers· included in the annual volume "Shorter contributions to general geology" are issued 

separately, with the final pagination, as soon as they are ready. The last paper will include a volume title-page, 

table of contents, and index for the use of those who may wish to bind the separate parts. A small-edition of 

the bound volume will also be issued, but copies can not be supplied to those who have received all the parts. 

II 

• 
• 

i 

#I 

\ 

SI-IORTER. CONTRIBUTIONS. TO GENERAl.~ GEOLOGY-, 1918. 

NEW. DETEH.MINATIONS OF CARBON DIOXIDE IN WATER OF THE GULF 

OF MEXICO. 

By RoGER c. WELLs. , 

INTRODUCTION. how nearly saturated the wj1ter is with respect 

Although the carbon dioxide in sea water to that substance. · 

is the subject of a very extensive literature I have been enabled to make the determi.na 

and 1nany determinations of it have been tions described in this paper through the inter 

made, recent advances in geochem.istry _have est and cooperation of T. W. Vaughan, of 

brought out new relations that require further the United States Geological Survey, and 

determinations in order to show the con- I-I. F. Moore, of the Bureau of Fisheries 

nection, if any exists,. between the history of :Mr. Vaughan pointed out the need of such 

the water, its temperature, its- geographic 'determinations, particularly for American 

location, the life it contains, and its saturation waters, and Mi·. Moore authorized the collection 

with calciun1 and 1nagnesiun1 compounds. In of the ~amples, which were actually collected 

1914 Clarke ~nd Wheeler/ in a paper on crinoid by W. W. Welsh and ·shipped in "citrate of 

skeletons, poii1ted out for the first time that magnesium" bottles to the chemical laboratory 

the proportion of magnesium carbonate in of the Geological Survey for analysis. It is a 

crinoids is in son1e way dependent on ·tempera- great pleasure to express appreciation for the 

ture. This observation led to the publication assistance offered by all those who .helped to 

of. a nun1ber of papers presenting facts· and mttke the study possible. 

th.eori~s bearing on the subject. 2 There is no question that the water of the 

Even em·lier the investigations of Vaughan 3 G:ulf of Mexico IS essentially similar to that 

on coral reefs and those of Branner 4 on the of the open ocean. · An analyais of the salts 

stone reef~ of Brazil had led to the consideration In water off Loggerhead Key, near Florida, 

of physical factors in the deposition of calcium m.ade by George. Steiger in the chemicallaboracarbonate in certain locali~ies. Johnston has tory of the United States Geologi~al Survey, is 

pointed out that the deposition of calcium shown 'in Table 1, together with Dittmar's 

carbonate by organic agencies may be closely mean of 77 a~alyses of ocean water .. 

related to the inorganic factors that determi1;1e TABLE 1.-Ana.lyses of oceanic sa.lts.a 

• Clurko, F. W., und Wheeler, W. C., Tho composition of crinoid 

skclclons: U. S. Gcol. Survey Prof. Pupcr 90, pp. 33-37, 1915. 

2 Wells, n. C., 'l'ho solubility of mugnosium carbonate in natural waters: 

Am. Chom. Soc. Jour., vol. 37, pp. 1704-17,07, 1915. · Johnston, Jo.lu~, The 

solublllty-nroduct constunt or culcium and rriugncsium carboimtcs: 

ldom, pp. 2001-2020. Wells, n. C., Tho solubility of calcito in water 

In contuct with tho utmosphcrc, and its variation with temperature: 

Wushington Acud. Sci. Jour., vol. 5, pp. 617-622, 1915. Johnston,. John, 

und Williamson, K D., 'fho comploto solubility ourvo of calcium carbonate: Am. Chcm. Soc. Jour., vol. 38, pp. 975-983,·1916. Johnston, 

John,.Merwln, H. K,_und Williamson, E. D., Tho several forms of 

calcium carbonate: Am. Jour. Sci., 4th scr., vol. 41, pp. 473-512, 1916. 

Johnston, 'John, and Williamson, E. D., Tho rOlo of inorganic agencies 

In thn deposition of Cl\lclum carbonate: Jour. Geology, vo\.~4, pp. 729-

74!), l!)l(l. 

8 Vl\ughun, 'f. W ., Tho prosont status of tho investigations of tho origin 

of banior coral roofs: Am. Jour. Sci., 4th sor., vol. 41, pp. 131-135, 1916. 

Soo also Curnoglo Inst. Washington Pub. 133, pp. 173-177, 1910; Pub. 182, 

l>P· 69-78, 1!)1•1: Yoar Book 14, p. 222, 1916, a~1d Pub. 213, p. 227, 191S. 4 13ran!10r, J. C., Stone reefs on tho northeast coast of Brazil: Gcol. 

Soc. Amorlct\ Bull., vol. 16, pp. 1-12,.1905. 

Cl .... ." .... __ . _ .. _· __ .... _. ____ . _ _. 

Br .... ------------·------------- S04 ........ · ................. _ ... _ 

g~~:::::~----·----~~ ~: ~ ~ ~-~ ~ ~ ~ ~:::::::: K ....... ~--------. -·- :. --.----- .. -- Ca ............... : .............. . 

h1g.------.-----.------.------.--

1 2 

55. 24 

.17 

7. 54 

. 34 

30.80 

1. 10 

1. 22 

3. 59 

100.00:. 

55. 29 

.19 

7. 69 

-21 

·30: 59 

1. 11 

1. 20 

3.72 

100.00 

. a Clarke, F. W., Tho data of geochemistry, 3d cd.: U.S. Geol. Survey 

Bull. 616, p. 123, 1916. · 

1. Saltsin waterofGulfofMexico; GeorgeSteiger,analyst. 

2. Salts in ocean water, mean of 77 analyses; W. Dittmar, analyst. 

1 
2. SROR.TER CONTRIBUTIONS TO GENERAL GEOLOGY, 1918 •. . . 

Although the analysis of Gulf water cited 

in this table shows the essential similarity 

of the water to sea water, it· seems likely 

·that the .total carbon dioxide .has· 'been stated 

-a~ C03 •. The .value stated amounts- to 0.091 

. gram C02 per liter, whi.ch i~ about that of 

ordinary sea water .. · Dittnuir's figure, on the 

other hand, does not account for all the C02 

normally present in sea water. · It is generally 

believed that carbon dioxide, in so far as.it con..: 

stitutes part of the salts in sea water, is _present 

both as. carbonate and as acid carbonate, 

commonly termed "bicarbonate." It was to 

ascertain the relative proportions of carbonate 

and bicarbonate in the water that the deter-

:rllinations recorded in this paper ·were made. 

Such determinations have also been made by 

Dole/ . by titration· methods, on water- from 

Southwest Channel, Tortugas, Fla. Dole's 

results are as follows: 

Gram C02 as HC03 : per liter._ 

Highest. . . . . . . . . . . . . . . . . . . . . . . . . 0. 088 

Lowest.......................... . 059 

Mean ............ _.,............. . 069 

C02 as C03 : 

· . Highest ....... : . . . . . . . . . . . . . . . . . . 022 

Lowest .............. ·_ . . . . . . . . . . . 011 

Mean ..... ·...................... . 017 

Total C02 : · 

Highest ........... · ........... ·. . . . 099. 

Lowest ........... :............. . 080 

}.fean........................... . 086 

Titration.. method?, however, have been 

called· in question by Johnston, 2 and for that 

reason it seemed especially desirable to apply 

·new methods ·where possible. The pres~nt 

contribution by no means exhausts the subject. 

Further determinations are needed i11 connection witi1 the alkalinity of the water determined 

at the source. 

DEFINITION OF TERMS.· 

Much of the haze that has long befogged the 

·subject of the carbonates in sea water. is due to 

the di:ff~rent meanings given to the same terms 

by different investigators. It is surprising 

how· tenaciously old terms persist in spite of 

well-proved facts warranting their abandonment. .Some of these terms are so indefinite 

' Dole, R. B., Some chemical characteristics of sea water at Tortugas 

and around Biscayne Bay, Fla.: Carnegie lust. Washington Pub. 182, 

. p. 73, 1914. . . . . . 

2. Johnston, John, Determination of carbonic acid,- combined and free 

in solution, partic'ularly in natural waters: Am. Chern.- Soc. Jour., vol. 

38, p. 947, 1916. 

that they convey . n<? exact meaning . unless 

-they are repeatedly defined by the author who 

uses them. . ~he word "salinity," for example, 

is used by some Writers to include only part of 

the salts that exist in sea water and by others · 

to i~clude them all: . The word "alkalinity" is 

used by some as a measure of the combined 

carbonate and bicarbonate concentration ex.:.. 

pressed in the same unit, and -by others to indi~ 

cate the hydroxide o~ hydrogen ion concentration. There are many modes ·of attack in this 

probl-em, but nearly every one involves some 

theory, so that it becomes most necessary to 

keep clearly in view how mucli is fact and how 

much is theory and not to coi1fuse the two so 

that neither is of any assistance. 

. In the present paper sea water is held to be 

a "phase" in the sense of the phase rulethat is, a liquid capable of· dissolving certain 

solids and gases up to the point of "saturation." Carbon dioxide is one of the gases that 

can thus be dissolved in sea- water, and the 

determinations made (see Table 2) ·give the 

total carbon, dioxide. that can be extracted fro~ 

the water after the addition of acid-that is, all 

the carbon dioxide that exists in the water in· 

any form. 

As already stated -most of the carbon dioxide 

in sea water is commonly considered to be 

presen~ as ·bicarbonate and carbonate, thus 

constituting the acid radicles of corresponding 

salts. Thus practically all the dissolved matter 

in sea water can be thought of as a group of 

salts the sum of whose basic radicles. is chemically equivalent to the sum of their acid radicles. This equiv~lence holds very closely for 

the al)alyses cited in Table ·1 when the various 

forms in which carbon dioxide is combined are 

correctly stated. Nothing leads to greater 

confusion, however, than to attempt to make an 

arbitrary combination of ·:the various acid and 

basic constituents determined by analysis, 

and for this reason it is well torealize that such 

an expression as ''the solubility of calcite in 

sea water:' does not imply that calcium carbonate exists as such in· sea water any more 

than that carbon dioxide exists as such, although -both· substances are doubtless present 

in these forms to. some extent. When such 

compounds ·are added to. sea water they react 

with other-substances and enter into the complex kinetic equilibrium that exists in the 

/' 

• 

,., 
•• 

CARBON DIO~IDE _IN W ATl~R O:t!, THE GULF OF -MEXICO: 3 

w~ter between all the salts and their ions, poured.irito a graduated 250 cubic centimeter 

hych·ates, and hyclrolytic products. The single flask and then into the distilling flask, and the 

word "carbonaten will therefore express the· boiling was begun immediately. The results 

gt'oup constituting the c·arbonate radicle (C03 ), obtained are stated in Table 2. 

which would have to bQ taken in the form of a The locations given in Table 2 correspond to 

. salt with the various other salts to malse up an the following station nuinbers of the Bureau of 

artificial sea water. The term "bicarbonate'' Fisheries: 

will have a similar meaning. The che1nical L t a . 29o 38' N 1 I . ; ong. 37o o' \x" ,., ·., s a t t' wn 104 . 4 7. 

symbols .. for these radicles will be C03 and Lat: 29° 53' N., long. 87° 7' w., station 10448. 

IIC03• When ions ·are meant the symbols Lat. 30° 5' N., long. 8.7° l2' W., stat.~on 10449. 

will· bear additional signs for the electric 4 miles northwest_ of Pensacola Light, ·station 10450. 

charges, thus: C03- and I-IC03-. The same Sample 1, obtained near Fowey Rocks Light, 

syn1bols ~nclosed in brackets are generally outside Biscayne Bay, F~a.,. was a portion of· 

used to represent concentrations in gram water collected at regular intervals between 

1nolecules, or 1nols, per liter, thus: [C03] or· July 26 and August 3, 1915/ and had stood.for 

[C03-]. · part of the time to April, 1917, in a green glass 

TAnLt~ 2.-'l.'otal carbon diox·ide in samples of wciter front the Gi.tlj of J,fexic9. 

Sample Location. Depth. TemperNo. ature. Chlorjne. Total C02 

~Meters. .o c. 

Grams per 

liter. 

Gram per 

liter. 

1 La.t. 25° 35' N., long. 80° 61 W .... : ............................ 0 .................. 20:37 0.106 

2 Ln.t. 29° 38' N., long. 87° O'W ............................ · .... .. 0 18.9 20.21 .093-

3 ..... do ................................................. · ..... . 4 ...•. do ................................................. :.· ... . 50 19.4 20.23 .092 

100 18.5 .................... ·········· 5 ..... do ....................................................... . 150 13.3 20.20 .099 

G ••••• do .......... ~ ............................................ :. 210 10.2 19.94 .100 

7 Lat. 29° 53' N., lon'g. 87° 7' W ............................ · .... . 0 20.0 20.52 .092 

8 ..... do ....................................................... . 25 20.1 20.39 .092 

9 ..... do .......................................... ·.·· ......... . 50 19.6 20.40 . 094 

10 ..... do ....... · ................................................ . 100 18.2 20.52 .100 

11 ..... do .................•..................................... 130 15.8 20.40 .098 

12 Ln.t. 30° 51 N., long. 87° 12' W .... · .................. ; .......... . 0 18.3 20.48 .095 

13 ..... do ............................................... : ........ · 20 18.4 20.38 .092 

14 4 miles northwest· of Pensacola Light ........................ : .. · 0 16. 7 18.34 .088 

15 ..... do ...................................................... . 10 16.4 19.66 .092 

DETERMINATION OF TOTAL CARBON DIOXIDE .. ·bottle with considerable air space. The result 

The total carbon dioxide w:as determined- by for the total C02 in this sample may have 

boiling 250 cubic centimenters of the water, been affected by exposure of the sample before 

after the addition of hydrochloric acid, for analysis. The other samples were collected 

10 to 15 minutes, driving out. the gas with a in January,· 1917, preserved in "magnesium 

stream of pure air and collecting it in weighed citrate" bottles with practically no arr space, 

tubes contt:Uning soda lime, the apparatus and analyzed in April, 1917. 

used being that generally employed in the The r~sults seem to show that the total 

analysis of carbonate rocks. 1 The water had content of carbon dioxide increases slightly 

been preserved and shipped, after collection, "rith. increase of depth. The average content 

in "citrate of magnesiu1n" bottles, with only a for the samples of surface waters is 0.092 gram · 

Yet')' smoll bubble of air space. After· the per liter. The average for all samples is 0.094 

bottle was opened a portion of the sample was gram per liter. Naturally it is interesting to 

1 Hlllobrond, W. ]<'., Tho analysis o£ carbona to and silicate rocks: •2 Dolo, R. 13., and Chambers, A. A:, Salinity~[ ocean water at Fowey 

U.S. Goo!. Survoy l3ull. 422, p. 180, l!JlO. Rocks, Fla.: Carnegie Inst. W~hington Pub. 213,· p. 284, 1918. 
4 SHORTER CONTRIBUTIONS TO GENERAL G~OLOGY, 1918. 

compare these figures with those obtained· by the total carbon dioxide is a little higher th~u 

in intermediate waters, for reasons that are 

·discussed on page 11. The average for th~ · 

bottom· waters is 0.101; that for the intermediate waters is 0.095. 

other investigators.· · 

Dittmar gives only four determinations on 

surface .waters that are comparable with these, 

and aU of them involve determinations of the 

"loosely combined" carbon dioxide·, which 

were made by J. Y. Buchanan by a method that 

is ~ot generally considered to yield exact results.- I-Iowever, they are as follows: 1 

Tornoe found the· average in 78 analyses of 

sea water to be 0.096. gram of carbon dioxide 

per liter, and ·results of the same order were obtained by Natterer. 2 Ruppin 3 found in the 

TABLE 3.-Dittmar and Buchanan's determinations of total carbon dioxide in s1.'trjace waters.· 

Sarri.ple Locality. Tempera- C02• No. ture. 

o C. 

Gram p.er 

liter. 

265 South Atlantic Ocean, lat. 22° 15' S., long. 35° 37' W .............................. 22.8 0. 106 

1573 South Atlantic Ocerun, lat. 23° 271 S., long. 13° 51' W ... : ........................... .25. 1 . 099 

1581 South Atlantic Ocean, lat. 19° 55'S., long. 13° 56' W .............................. 24. 7 . 093 

1687 North A.tlantic Ocean, lat. ~1 o 23"' N ., long. 31 °-15'·w .............................. 22.8 . 092 

The results· of the analyses of the 14 samples 

of Gulf water are in fair agreement with the 

four .results. of Buc:hanan's analyses ·of four 

samples of-' water from the· surface of the 

North Sea, at a depth of5 meters, 0.091 gram 

of carbon dioxide per liter, and at 460 meters 

0.095 gram. 

' Estimates by :bole of the total carbon dioxide · 

. open ocean. in the Gulf water at Tor~ugas are given on 

TABLE 4.-Dittmar and Buchanan's determinat1:ons of total carbon dioxide in deep waters.· 

s·ample Locality. Depth. Tempera- C02 N.o. • ture. 

Fathoms: o C. 

Gram per 

liter. 

21 North Atlantic Ocean, lat. 23° 10' N ., long. 38° 42' W .................. B 2, 720 2. 5 0.096 

66 North Atlantic Ocean, lat. 19° 41' N ., long. 65° 71 W ....... ; ........... B.3, 878 ............. .112 

120 North Atlantic Ocean, lat. 32° 54!.N ., long. 63° 221 W ............... ·.·. B 2,360 2.4 .102 

283 South Atlantic Ocean, lat. 29° 351 S., long. 28° 9' W ................... 1,000 2.8 .109 

353 Indian Ocean, lat. 46° 46'S., long.:45° 31' W ......................... B 1, 375 2.0 .118 

378 Indian Ocean, lat. 60° 52'S., long. 80.0 201 W .................. , ...... B 1,260 ................ .128 

383 Indian Ocean, lat. 65° 42' S.,.long. 79° 49' W~ ... : ............... ; .... B 1,675 ................. .149 

(556) South Pacific Ocean, lat. 14° 71 S., long. 153° 43' E .................... : B 2,450 2. 2 .·101 

594 West Pacific Ocean, lat. 5° 24'S., long. 130° 37' E .. ·_ .................. 400 6.4 . 094 

791 North Pacific Ocean, lat. 11° 24' N., long. 143° 16' E .......... · ......... B·4, 475 1. 8 ~ 086 

912 North Pacific Ocean, lat. 36° 231 N ., long. 174° 31' E .................... B 2, 775 1.6 . 090 

1221 South Pacific Ocean, lat. 32° 36'S., long. 137° 431 W ................... B 2,375 1. 7 .103 

1300 South Pacific Ocean, lat. 38° 71 S., long. 94° 4' W ...................... B 1, 500 1. 8 .102 

678 West Pacific Ocean, lat. 5° 471 N ., lorig. 124° 1' E ..................... 50 25.4 . 081 

1270 South Pacific Ocean, lat. 39° 13' S., long. 118° 49' E ................ : .. B 2,250 1.4 .100 

·1313 South Pacific Ocean, lat. 38° 6' ·s., long. 88° 2' E ................. ·.~ .. B 1,_825 1.8 .108 

1356 South Pacific Ocean, lat. 32° 50' S.,.long. 77°.61 W ..................... 50 12.0 :102 

1388 South Pacific Ocean, lat. 42° 43'S., long. 82° 11' W .............. ·.· .... B 1,450 2. 0 .112 

1405 South Pacific Ocean, lat. 48° 271 S., long. 74° 30' W .................... B 345 7. 8 . 097 

1438 South Pacific Ocean, lat. 52° 45'S., long. 73° 46' W .................... B 245 7. 8 .1.02 . 1494 South Atlantic Ocean, lat. 35° 39'S.; long. 50° 471 W ................... B 1,900 0.6 . 098 

1697 North Atlantic Ocean, lat. 26° 211 N ., long .. 33° 37' W .................. B 2,.965 3 . .1 . 092 

1707 North Atlantic Ocean, lat. 32° 411 N., long. 36° 6' W .................... 400 9.8 .. 091 

.. .. 

The resultf:! obtained by combining the data 

of Dittmar and Buchanan for deeper waters 

.are given in Table . 4. Most of these we1:e 

".bottqm" waters (marked "B"), in which 

page 2, ·but it should be noted that Dole did 

not directly determine the total carbon dioxide. 

1 ()hailenfler Rept., Physics and chemistry,· vol. 1, p. 215, 1884. 

2 Clarke, F. W., Tho data of geochemistry, 3d ed.·: U. S. Gcol. Survey 

Bull. 616, p. 144, 1916. 3 I\.uppin, E., Die Alkalinitiit des Mcerwasser8: Zeitschr. anorg. 

Chemie, vol. 66, p. 122, 1910. 

. '. 

J 
• 

CARBON DIOXIDE IN WATER .OF T'HE GULF Ol!"' MEXICO. 5 

Dolo also obtained ftgures rnnging fr01n 0.055 

.to 0.109 in Biscayne Bny, the. lowest beipg 

for water in Featherbed Bank, at 26.4 ° C., and 

he concluded from the salinities that evaporation was going on in the shallow water of the 

bay at the ti1ne his samples were taken. This 

action should also be .accompanied by a loss 

of carbon dioxide, as actually observed. His 

average for· the ~otal carbon clio:x:ide is 0.084 

gram per liter. 

THEORETIC.AL AMOUNT OF CARBON DIOXIDE IN 

SEA WATER. 

If there n.re sources of carbon dioxide in the 

· deep sea and the circulation of the water is 

slight, one 1uight expect, theoretically, to find 

very considerable concentrations o'f carbon 

dioxide in such water. The pressure of the 

wat~r would hold far larger pr.oportions of any 

gas in solution than could remain dissolved at 

.at.mospheric pressure or smaller· partial pressures. As'very little is known about the extent 

to which moving crentures transfer carbon 

dioxide from place to place, the regulation of 

the concentration at depth would appear to be 

governed chiefly by the supply of carbon dioxide and by the rate of circulation of the water. 

At the surface, on the other hand, there is a 

tendency toward an equilibriurn between the 

water and the atmosphere in respect to carbon 

dioxide, which Schlosing believed to be the 

governing factor in determining the carbon 

dioxide content of . the atmosphere. This 

OCJUi.libriutn can be studied in the· laboratory 

. and the results compared with those obtained 

by observations made in different .parts of the 

ocean. 

The equilibrium referred to .may also i,llvolve 

·the solution or deposition of calcium carbonate. 

A water in contact with calcium carbonate 

should theoretically dissolve more carbon dioxide fro:m the atmosphere than one without access to calcium carbonate, but my own experiments on tluf;) point indicate that sea water 

exposed to a normal atmosphere·' gives off car-

'liOn dioxide at all temperatures above the very 

lo,vest, so that under surface conditions sea 

water in and between the temperate zones must 

be regarded as satm·ated with calcium· car:... 

bonate. Therefore, laboratory experiments 

dealing with the equilibrium at ordinary temperatures yield the same results in the presence 

·and in the absence of calcium carbonate. 

In 1916 I performed two experiments with 

sea water to determine its total content of 

carbon dioxide at two definite temperatures, 

1° c. and 28° c., after prolonged agitation of 

the water with outdoor air, an excess of calcite also being present in the water. The mean 

partial pressure of C02 was 0.000318 atmosphere, according to my determinations, and 

the two normalities fotind for C03 + IfC03 were 

0.00236 and 0.00196, respectively. The result 

for total C02 at 1~ C. was 0.101 gram per liter, 

and that at 28° C. was 0.078 gram. These 

results agree essentially with those calculated 

by the formula of Fox, 1 which gives 0.100 and 

0.075, 'respectively. 

Fox's formula, expressed in the terms used 

in the present discussion, is 

Total C02 (grams per liter) =na+pb 

where n=the normality of C03 +HC03, a= 

value given in Table 5, p =partial pressure of 

C02 in • atmospheres, and b =value g1ven Ill 

Table 6. 

TABLE 5.-Values of "a" for a solution of normality 1 at 

different temperatures and partial pressures of C02 • 

J>. oo. 20. 10°. 160. 20°. 28°. 

---------------- 0.0002 40.42 40.08' 38. 70 37. 69 37.00 35. 64 . 0003 42.09 41. 79 40.58 39.67 39.07 37. 86 . 0004 43:11' 42. 83 41. n· 40. 87 40. 31 39. 19 . 0005 43. 77 43.51 42.47 41. 69 . 41. 17 40. 13 ~ 0006 44. 37 44. 15 43. 24 42. 56 42. 11 41.21 

TABLE 6.-Values of "b" for· 'different salinities and twtperatures. 

.[Chlorine in grams per thousand.] 

Ternpera- Cl=O. Cl=2. Cl=10. Cl=18. Cl=20. ture 

(o C.). 

---------

0 3 .. 39 3. 34. ''3. 16 2.98 2. !)3 

'·4· 2. 91 2. 87- 2. 69 ·2.·.53 2. 50 

. 8 2. 53 2. 50 2. 34 2. 18 2. 14 

12 2.21 2. 18 2. 07. 1. 96 ' 1. 93 

16 1. 95. ],. 92 .1. 81 1. 70 1. 67 

20 1. 73· 1. 71 1. 63 1. 56 1. 54 

24 1. 54 1. 53 1:47 1. 42 1.40 

28 1. 38 1.36 1. 28 1. 21 1.19 

1 Fox, C. J. J., OQ. tho coofficients·ofabsorption or nitrogen and oxygen 

in distilled water and sea water and of atmospheric carbonic acid in sea 

water: Faraday Soc. Trans., vol. 5, p. 82, 1909. 
6 SHORT'ER CONTRIBUTIONS TO GENERAL .GEOLOGY, 1918. 

COMPARISON ·oF :RESULTS WITH EQUILffiRIUM 

CONDITIONS. . 

We are now in a position to comparethe.de-

. termi:riations of the· total carbon dioxide in 

the samples of Gulf wat:er with those representing equilibrium with the atmosphere. For 

··this purpose: I shall use ·0.000318. atmosphere 

for the average carbon dioxjde content of the 

atmosphere. 1 The normalities required in the 

calculation were determined as described in 

succeeding.pages and are stated in Table 10. 

The comparison is shown in Table 7. 

Other data than · th1s eomparison (see p. 5) 

in_,Cline me to the view that surface sea water 

is g~nerally fully satlirated 'with· respect to 

atmospheric conditions; if so, there is some. 

small constant error in the determinations or 

in one of the factors on which ·the c~nnparison 

is based. The most interesting feat:ure of the 

comparison is the fact that 'the deeper waters 

·seem to be as near to an eq~ilibrium with the 

atmMJ)here, for their temperature, as the surface waters; That being true, what -is the 

source of their carbon dioxide~ It' seems difliTABLE 7.-Comparison· of total carbon dioxide found in the ·Gulf 'Waters with that representing equilibrium 'With the . . _ atmosphere. · . . . . . . 

Sample 

No. Locality. 

2 Lat. 29° 38' N., long. 87° O' W ............... -.· .....•........ 

. ~ : : : : : ~~: :.:: : : : : : : : : : : : : : : : :-: : : : : : : : : ~ : : : : : ': : : : : : : : : : : : : : : : ~ : 

6 ..... do ..................................... -.· .....•. · ... -·.·· 

7 Lat. 29° 53' N., long. 87° 7' \V .............................. . 

8 , .... do ........................ --- .......... -... -.... -.. -:,-

9 .... ~do .... · .. ·: ..................... -- ................ · ....... . 10 ..... do .......................... ; ......... -...... · ........ . 11 ..... do ............ ·.· ......... · .......... ': .............. · .... . 

. .. J:?epth. 

· Meters. 

0 

50 

150 

210 

0 

25 

50 

100 

130 

12 · Lat .. 30° 5'N.·, lmig. 87° 12'\V ............ : ................ ". 0 

13 ..... do ................... · . . . . . . . . . . . . . . . . . . . . . . . . . . . . • . . . . . 20 

14 4 miles northwest of Pensacola Light"·.· .......... '........... 0 

15 ..... do .. · ...... · ....... -................ '.:··................... 10 

T T l Co co~ for 

empera- ota · 2 eqmlibture. found. rium. 

oc. 

Gram per 

liter. · Gram per 

liter. · 18.9 0.093 0.094 

19.4 . 092 .098 

13.3 . 099 .099 

10.2 .. ~oo .100 

20.0 ~ 092 .095 

20. 1 . 092 . 094 

'19.6 . 094 .098 

18.2 .100 . 098 

15.8 . 098 -~9 

18.3 .095 . 097 

18.4 .092 .097 

16. 7 . 088 .091 

16.4 . 092 - .. 097 

The agreement between the last two columns cult to account for' this adjustment by assumor' Table 7· is striking. In content of C02 the ing that portions of the water have come from. 

Gulf waters appear to be very nearly in equi- cold regions where they were _in contact with 

libriu~ with the atmosphere-so nearly that the atmosphere and have transported carbon 

the probable experimental error in the ·deter- dioxide all that distance: A portion of water 

minations ·of the normality of· C03 +HC03 in passing from the polar regions might lose 

would account for a positive or negative differ.:. and gain carbon dioxide a number of times 

ence between ma,ny of the figures in the two befqre arriving in the Gulf of Mexico. · Has the · 

columns. The same might be said of an error water of the Gulf of Mexico access to more 

. in the carbon dioxide content of the atmospher~ .immediate. sources of carbon dioxide than the 

used in the calculations o"r in the. other factors atmosphere~ Where the facts are so· suggesentering into the comparison. From. the data tive it is natural to seek for some hypothesis to 

of Table 7 I do not feel warranted in conCluding explain them, and the most plausible .one 

· that any of the waters is either saturated or appears to be that ·living forms either carry or 

uns'aturated with carbon dioxide under atmos- supply the carbon dioxide necessary to mainpheric conditions, but all the samples are evi- tain equilibrium. 

dently very near the condition of equilibrium. Even Dittmar's results for carbon dioxide in 

1 The higher value, 0.000353, recently published by Kendall, is for 

laboratory air. See Kendall, James, Th~ specific conductivity of pure 

water ·in equilibrium with atmospheric carbon dioxide: Am. Chern. 

Soc. Jo1lf., voL 38~ p. 14901 1911;), 

the cold bottom waters of the ·ocean {Table 4) 

are approximately equal to the requirements 

for eqUilibrium wit~· the atmosphe~e, although· 

• 
• 

OARBO_N DIOXIDE IN WATER OF THE GULF . OF MEXICO. 7' 

a few of· the individual detern~nations show. ·Although .carbonic aCid is coinnionly'considered 

variations in one direction or the other. Inas- ·to exert no action upon methyl orange, it really; 

much as the figures given by Dittmar include as has long been kn,own, develops a marked 

Buchanan's determinations and as the oth~r shade of red, and on this fact depends Kuster's 

factors on which the above comparisons: rest method of titrating to the same shade as that 

are the work of 1nany investigators, it n1ust be ·produced in. water saturated. with carbonic 

admitted that the Close approach of these acid:2 His method gives corrept results with 

waters to equilibrium with the atmosphere is relatively concentrated solutions of bicarbonreally re.markable, as is also the fact that this ates. In_ the present case, however, the conrelation is·found in waters as deep as 3,000 centration of bicarbonate is very small and the· 

fathoms. It seems as if organic agencies must solution is far from being saturated with carbon 

contribute carbon dioxide. to these deep waters, dioxide··at the true end })Oint. After neutralizfor it is difficult to see how currents in the ocean it1g \Vith acid sulphate there·· will be present 

could possibly carry carbon dioxide from ·t~e about 0:0047 gram of C02 for 50 etl.bic centisul'face in the colder regions to all the localities meters of sea water. Evidently,. the proper 

in the ocean that have been investigated and end point is indjcated by the color produced by· 

could produce by :mere mixture samples ap.:. this amount of C02 in the same volume ofwater 

pro·aching so closely the requirements -for equi- as 'that finally present in an actual determinalibriunl. Buchanan 1 writes on this point: tion. Experiment showed that this amount of 

Down to neru·ly 2,000 fathoms life is still abundant; C02· effects. a scarcely perceptible .·change in 

below .this .depth, however, the_amount rapidly. decreases methyl orange. If titration· is carried to the 

till, at about 2,800 fa.thoms, it is, for carbonic acid produc- first petceptible change in tint, 'or better,. to a' 

ing pmposes, practically extinct .. ' st;andard color produced by. ·the amount of 

The preceding discussion suggests that the C02 known to be ·present, .the acid used will 

COnditionS Jnaintained b)~ organic and biochem- COi'I~espond; as nearly as can· be determined, tO 

icol activity in the ocean correspond almost the total-:base balancing carbonate· and bic.arexactly with the physico-chemical conditions bonate. · . 

of equilibrium between sea water and a normal In the hope of obtaining better results with 

at1nospher~ at the tcn1peratures involved.. SOrrie other indicator than methyl OI~ange the, 

behavior·of paranitrophenol was studied. The 

DETERMQlATION OF TOTAL <;:ARBONATE AND indicator solution contained 1 gr~m 'in 250 

BICARBONATE. - . cubic centimet0rs ·of water. The tests made 

are shown in Table 8. The determination of total carbonate and bicarbonn.te is somptirp.es referred to- as that :Ofthe tc alkalinity" and .sometimes as that ofthe total· TABLE 8.:-Compari~ons of colQ'r_ in 50. ~'I.~Qi_c_ ce~tt-imet~r solutions in casseroles. base bnlancing carbo~ate and ·bicarbonate. 

Following Dittmar, inYestigators generally as- Soiution. Color. 

sunle that there is n'o free base in sea water and" ________ -_-_--_~-_-_-_. --~----_--_--_·_-_ .. _ .. -_~ _--_--_~-_---

tho.t n.cid is consumed solely in setting free carbonic n.cid · from ·carbonate and bicarbonate. 

The determinatiOI~ mentioned was made by titration with 0.02 normal sodium hydrogen 

sulphate. Methyl orange may be used as indicator, b.ut the determinations were in fact carried. out with paranitrophenol. The results 

obtained 'in titro.ting depend somewhat on the 

end point selected. The final reaction in the 

neu £ralization is 

N ai-IC03 + N ai-IS04 = N a2S04 + H2C0s 

From this reaction it is evident that the hidicator used .. should not give an indication for 

la. ·Distilled water ....... _ . . . No color. 

2a. Distilled water, 0.0047 gram Scafcely perceptible col002, 4 drops indicator. or at first; a faint color 

appears slowly on · ·standing. 

3a. Disti1led water, 1 drop in- 1 Clearlyperceptiblecolor. 

dicator. 

lb. Distilled water. ; . :. _ ..... 2b. A solution of neutral sea salts (prepared by neti-· 

tra.lizing the· carbomi.tes 

in actual sea water with 

the calculated quantity 

of acid and boiling _out 

the carbon dioxide),· . 0.0047 gram co·2; 4 

drops indicator. 

No color. 

Scarcely perceptible col- or at first; a faint color 

appears slowly on standing. 

3b. Distilled water, 1 drop Clet:riy perceptible color. 

inclica.tor. 

I-I2COs J:>u.t for the fi~·~t ___ e~Cf~~~- of __ ~-~~-!804.. 2-!Ciistcr, F. w., Kritischo Studicn zur 'yolumctrischcn Dcstimmur.g 

-------.----------;------·-· -:------ von--,.aroonatli:iltigcn 'AlRal1ln:ugcn -·u:rd: von---A::lkatika-rbonnterr.· 

1 Uuchano.n, J. Y., Hoy. Soc. London Proc.; vol. 22, p. 483, 1874. ' Zeitschr. anorg. Che'ffiie, vol. 13, p. 1271 1897. ' 
.. 

SHORTER CONTRIBUTIONS TO GENERAL GEOLOGY, 1918. 

·The shades of color produced hy the indica- As the small samples of water available for the 

tot were found to depend considerably on the determinations . recorded in this paper did not 

quality of the distilled water used: Freshly permit more· than two titratio"ns, and some 

boiled· water, after cooling, is perceptibly more sa:mples only o~e, any single result is probably 

· alkaline than water as it comes regularly- from not :o.earer. the true value than 2 per cent. 

tli~ still pr \Vat~r~that has stood·in the labora- The solution of" NaHS04 used for titrating 

tory· some time,· on account of the difference in the samples nf sea water, to determine the total 

carbon dioxide content. Solutions made up as base bal~ncing carbonate and, bicarbonate, was 

described under 2a and 2b were used as fut- standardized with a solution containing sodiun1 

nishing- the stmidard color for the proper end carbonate· and bicarbonate -in essentially the 

point. For the greatest. possible accuracy it same proportion .and concentration as iri sea 

·would appear that the·preparation of the stand- ·water. In this way the conditions at the end 

ard should be· def~rn1d· until after the determi-· point were similar in. both· the standardization 

~ation of total C02 • It is-possible that better and the determinations. ·The results obtained 

results could be obtained jn Nessler tubes than in· the standardization· are shown in Tabl.e 9. 

in casseroles, but the glass ·of ·.certain Nessler TABLE 9.-Standardization of NaHS04 solution with solutubes was found.to be rather too soluble for the tions of NaHC03 and Na2C03 • 

purpose.· No error seemed .to be introduced in 

the very weak solutions of C02 under investi-· 

gation by working in casseroles, and the color 

showed up\vell in diffused daylight. However, 

it is' doubtful if the res.ults obtained with paranitrophenol were more accurate than those 

obtained with methyl ·orange. 

. As nearly· as could ·be determined the titrations were significant to about 1 per cent of the 

quantities being titrated, so that the combined 

normality of carbonate and bicarbonate in sea 

water ought, to be determinable within 1 per 

NaHC03 • 

Gram. 

0. 00794 .......... 

. 00794 .......... 

. 00794 .......... 

. 00794.· ......... 

. 00794 .......... 

. 00794 .... ·.· .... 

Mean ....... 

. . 

Na2C03 • 

Gram. 

0.00143 

. 00143 

. 00143 

. 0014'3 

. 00143 

. 00143 

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

NaHS04 • 

Normality 

of 

NaHS04 • 

-

c.c. 

5. 89 0.0206 

5.87' . 0207 

5.· 82 . 0209 

5. 81' ; 0209 

5. 92 . .'.0206. 

5. 86 . 0207 

............... . 0207 

·eent by this method. Practically, however, the· The results of the titrations are shown in 

attainment. of such1 accuracy would probably. the fourth coiumU: of. Table i·o. They are exrequire a number of titrations on each sample. pressed in terms of nor~ality, a_ nor1nal soluTABLE 10.-D.~termina.tions of carbonate and bicarbonate in water from the Gulf of lJfexico.. · 

·Sample 

No. Locality._ Tempera- COa+ HC03 HC03 nor- C03 nor- ture (0 0.). normality. mality. mality. 

1 Lat. 25° 35' N ., long. 80,0 6' W ... : ............ · .................... . 

2 Lat. 29? 38~ N., long. 87° 0' W ..................... :....... 18.9 

3 ..... do ............................................... ·.... . 19.4 

4 · ..... do ................................ ·................... 18. 5 

5 ... : . do ............. · ....... ' ..................... : . . . . . . . . . 13. 3 

6 ..... do .. ~ ............ ·.................................... 10.2 

7 Lat, 29° 53' N., long. 87° 71 W ........ : . .......... · ........ . 8 ..... do .......... : ............... · ........................ . 

· 9 ..... do .................................... ~ .............. · 

10 ..... do ........................................ ; .......... . 

11 ..... do.~ ......................... -.~ .............. , ...... . 

20.0 

20. 1 . 

19.6. 

18. 2 

15. 8 

·12 Lat. 30° 5' N ., long. 87° 12' w............................. 18. 3 

13 ..... do ...... · ...... , .......... ,............................ 18. 4 

16. 7 

16.4 

· Mean, exclusive of No. 1. .................................. .. . I 

0.00268 

. 00239 

. 00250 

. 00242 

·' 00245 

. 00245 

. 00242 

. 00239' 

. 00250 

.00249 

. 00249 

. 00245 

. 00245 

.'00230 

. 00241 

. 00244 

0.0021 0. 0006 

. 0018 :0006 

. 0017 . 0008 

.............. ............ . 0020 . 0004 

. 0021 . 0004 

. 0018 . 0007 

. 0018 . 0005 

. 0018 . 0007 

. 0020 . 0005, 

. 0020 . 0005 

. 0019 . 0006 

. 0017 . 0007 

. 0017 . 0006 

. 0018 . 0006 

. 00185 . 00058 

• 

., 

·~ 
• 

CARBON DIOXIDE IN WATER OF· THE GULF OF MEXICO. 9 

·tion being one containing 1 gran1 equivalent 

of reacting substance per liter-that is, as 

n1any gra1ns as the n1olecula1; weight r~duced 

to a univalent basis. As is men.tioned on 

page 3, san1ple. 1 had .stood for n1ost of the 

ti1ne frmn July, 1915, to April, 1917, in a green 

glass "acid~' bottle with some air space. The 

other san1ples were collected in January, 1917, 

·preserv'ed in bottles with practically no air 

space, and analyzed in April, 1917. Without 

doubt it would have been better if the titrations 

.could have been n1ade on shipboard immecli-. 

ately after the samples were taken. The high 

value of the carbonates in sa1nple 1 ~ay be due 

to attack .of the glass bottle. The figures for 

the other 14 samples 1nay also be slightly high 

for the ~arne reason, but if the difference between sample 1 and the others represents the 

effect of standing in glass for 17 months, the 

correction for any one of the 14 results is only 

. ·t:tbout 2 per cent of its value, a correction just 

about equal to the p~ssible experin1ental error. 

DISCUSSION OF RESULTS FOR THE TOTAL 

CARBONATE AND .BICARBONATE. . . 

Dittmar tnade determinations of the "alkalinity"-that is, the combined ·carbonate and 

bicarbonate--in ~30 ·samples of ,\rater collected 

on the (Jhalle~ge?'. 1 It was his opinion that the 

with an excess of calcite, was agitated by a 

current of outdoor air for long periods .at different temperatures, and the dissolved carbonates 

were deter~ned by. titration wit4 0.02 normal 

N al-IS04 , methyl orange being used as indicator. The results· obtained are shown in 

Tables 11 and 12. 

1'ABLE ·H.-Determinations of total C03+HC03 when calcite 

is added to sea water at 1 ° G_. and air passed daily .. 

Time. 

· Start ..... : ................ . 10 days ........ · ............ . 12 days ..... ; .............. . 14 days .................. ,. 33 days .......... : ........ . 40 days ...... ~ .. · .... : ..... . 

Carbonates 

per liter 

normality .. 

0.00247 

. 00246 

. 00241 

. 00200 

. 00200 

. 00236 

TABLE 12.-Determinations of total C()3+HC03 when calcite 

is added to sea water at room temperature and air passc.d 

daily. 

Tem- Carbonates 

·Time. pera-. per ijter ture 

(oC.). normality. 

.. 

Start ..... · .......... ... 0.00247 

10 days ............ 25. :00225 

12 days .. , ......... 25 . 00221 

14 days ............ 26 . 00215 

33 days ............ 28 . . 00199 

35 days ............ 29 . 00208 

4.0'days ............ 28 . 00196 

. results were tuiaffected by long preservation of 

the water in glass bot.tles. The mean of ·all his 

determinations gives a normality of 0.00249. 

The mean for the Gulf waters, as shown above, 

is 0.00244.. Hl.1ppin obtained on shipboard in 

the North Sea 0.00238. Dole's figures for the The results obtained show that under conwater at Tortugas (p. 2) give a normality of ditions otherwise similar there is a tendency 

0.00234. · for the colder sea. water to retain more carNow, as pointed out in the intro<Juction, bonate in solution· than the warmer sea· water. 

there is a need for study of the relation between What was not expecte-d, however, is. the fact 

the solubility of calcium and magnesium com- that the colder water ·did ·not dissolve. fresh 

po~mds and. temperature. In .1915 I investi- calcite but appears rather to have remained 

gated the solubility of magnesium and calcium almost unchanged during the 40 days,. run.· 

carbonates in pure water and determined the In other words, sea .water appear8 to be so far 

relation between the ·solubility· of calcite· in saturated with· respect to calcium ·carbonate 

water in contact with·the atmosphere and the that in contact with the atmosphere at 1° C. 

temperature. (For reference see p:l.) Fur- it neither has nor acquires .an appreciable 

ther determinations seemed ·desirable for .solvent .action . on calcite. At . higher ternsen water, and such determinations have peratures it undergoes a slow diminution in its 

now been made . on a portion of the water- content of carbonates . on being agitated· in· 

collect'ed at Fowey Rocks Light, outside contact ~vith outdoor air. 

Biscri.yne Bay, Fla .. The water, in contact To compare with the above determinations, 

· • Dittmo.r, W., Challenger H.cpt., Physics and chemistry, vol. 1, p.'l24, 

1884. 

I had, fortunately, been able to make a few. 

titrations at sea. At two points in the 
. Caribbean~ Sea,' 'it 'bout~ latitude· 13° N., longi-. TABLE' .14._.:;_Ruppin's deterrn{nat·ions of. COa+HCOa·fo'r 

'tti.rle'·-s'I 0 W-~· the noriri~lity of the carbonates . watei. of the North Sea, deptlJ, 5 rnetds. 

Date. Tempera~ COa+HCOa· ture 

( 0 C.)·. normality. 

was'found to be 0.00236 and 0.00238 at 25° C. 

Water f:rbm .. the Pacific. off Payta, Peru, at 

24o·. C:,_ gave 0 .. 00226. These figures are ·a 

little higher than those found· in the laboratory 

after a few days' agitation and suggest a ·con: Feb. 18, 1907 .'.: .. :.............. · 4. 5 o. 00236 

ditio. n ..qf saturation, :under a_tmo_spheri,c con- May 6' 1907 · .·. · · · · · · · · · · · · ·.· · · · 6· 0 · 00236 . May 10, 1907 ... , ..... :. . . . . . . . . 6. 2 . 00232 

·.ditions, although ·they· thro.w no light o11 the May 8, 1907.................... 6. 4 . 00240. 

variations. with temp._erature. May ·

5, 1907 · ·: · · · ·. · · · · · · · · · · · · · 6. 7 · 00237 May 12, 1906 ...... .'............ 7. 5 . 00242 

·Let us now consider all the data available on May 19, 1906................... 9.1 . 00241 

surface·· sea water to see if the results show a: Nov do~'.~~?~.-~~:~--·.·.-.-~-~:::::::: ~: ~ : ~~~~~ definite.· relation between the normality of Mayll, 1906 ... : ... ·............ 9. 4 . 00242 

carbonate--ana bimirbonate and the ·tempera- Novr}~'-~~~~---_.~:~.·-·_·_:_.~::::::::: 1i:~ :~~~~~ ture.: . Nov. 13, 1906.' ....... .'........... 12. 4 . 00240 

Of Dittmar's, i30 results .the .. 1-;1:. for .surface Aug. 17,)906 ··.· · .·. · · · · · · ·: · · · · · 15· 

1 · 00232 

Do......................... 15. 3 . 00236 

.waters are reproduced in Table ;13, .after Aug. 15,'1906 ..... ·.............. 15.9 . 00239 

recalbulation to the terms ·used here. Do.························ 16· 

2 

1 

___ ~_ 02 4 

It is.:difficult .. to see much if.any regularity. Mean.· ............... : ..... · ... ·.· .. . ~- 00238 

.with .. ~eg~rd to temperature i11 .the r(3sults. 

·giy~n iri Table 13. · .There is a slight indication. Apparently, t~~n, .PJthough the variation in 

that· the normality of C03 +I-IC03 decreases the normality of C0 +HCO~ with temperature 

with rising temperature; but the results-are too' can be shown jn the laboratory, it. is not very 

few and,. t~.o ·unreli~ble .to show the re~ation: evident ii1 published determinations _'for surwith! ce:r:tainty.. : face water of the open ocean. 

Sample No: 

384 

127.1 

1471 2~ . . '9 

.1700.' 

168-7-

265. 

. 327 ·. 1581; 

'1573" ·2or: 

·.,,;1127·· 

6'68 r, ···-

. • :; t 

I - • • 

.. r~BLE.l3.-Dittrnar's fl.etefmineltions of COa+HCOa for· surfiwe waters. 

~ . 

Indian o'cean, lat. 65° 42'S., long. n)o 4~v E.· .. .: .... : ....... ~-~ ..... · ............. . 

-South Pacific Ocean, lat. 38° 56'S., long. 116° 8' W ... · ....... ~ ... .-~ ............ . South Atlantic Ocean, lat. 41° 3!)' S., long.·54° 481 W .... · ... ~ .... : .............. . 

North .A:tlantic Ocean, lat. 27° 24'·N ., long. 16° 551 W ............................ . .Nortli'Atlantic Ocean, 'lat. 24° 22' N., long. 24° 111 W ....... ~ ........ : .. ·~ ....... . 

North Atlantic Ocean, lat. 30° 201 N., long. 36° 6' W ..................... ~: ...... ·.· North Atlantic Ocean, lat. 21° 331'N., long. 31° 15' W ........................... . 

South. Atlantic Ocean, lat. 22° 15' S., l01ig. 35°.37' W ........................... . Indian Ocean, lat. 36° 48'S., 1!) 0 24' E .......... ~ ........ .': ................. :: .. South Atlantic' Ocean, lat. 19° 55' S.,.long. 13° 56' W ............ ; ~ ......... · ..... .. South Atlantic Ocean, lat. 23° .27' S., long. 13° 51' W ................. : . ...... :. ~ 

North Atlantic Ocean, lat. 10°. 25' N.; long. 20° 30' W ............ : . .... ~ ... .' ..... . 

~outh Pacific Ocean, lat. 3? 48'S., long: 152° 56' W ....................... ·.· ...... . Near ~hilippinelslands, lat. 9° 101 N., long. 124° 25' E ......................... . . . . . . .. . . . . . . . . . .'· . ~ . 

Tempera- ture COa+HC03 

o 0 ) normality. ( .. 

-l.l 

11.9 

.15. 3 

18. 0 . 19.4 

21.9 

22.8 

22.8 

22.8 

24.7. 

25. 1 

25.5 

26. 1 

~7.2 

0.00~55 

. 00234 

. 00235 

. 00286 

. 00260 

. 00248 

. 00248 

. 00260 

. 00253 

. 00250 

. 00246 

. 002'41 

. 00240 

. 00234 

Mean-.~- ....................... ~ .......... · . .- ............... · ... _. ....................... " .. . 00249 

·Further.· d~teri:iii.nati~fis· were made in the- Analyses of some of .the warmer and nearly 

No!'th. Sea by Ruppin:qn the Pos~idon. 1 Some inClosed. seas,. on the other hand, show a deofli.is .results ·are shown in Table l( . - crease in the carbona~e content. Natterer 2 

·rp_ R1.tpp1~'s iesilts, also, ·no ~·elation between . found that' in the -Red Sea, for instance, the 

the .. ::carbonah3'-'con£(:mf:·an.d: the" temperature carbonates are low aild the deposition of solid 

can be ~scovered. · · 'earbonates takes place. It 'is evident that 

'·• chiefly in such portions of the ocean or in the •. I Ruppin,. ·R.,. Die Alkatinititt des 1\ieerwassers: Zeitschr. anorg: 

C?einic~ ,;or·; ~6, ·p, i22, 19~0. · 1 · 

t' ~ 

2Natter~r, K., ;Monatsh. Chemie, vol. 20,,p. 1, 1899. 

• 
'. 

• 

CARBON. DiOXIDE I'N WATER OF THE GULF OF MEXICO. Tl 

polar regions will there be foU.nd m~rked. ma.1ii- Table 15 · contains a_ summary· of the- confestation:s of the tenip·erature effect on the :not- 'elusions so far suggest~d concerning 'the 'total 

mality of COs +.liCbs. · C02 and the normality of the bases balancing 

In l)ittmar's determinations· for cold bottom COs and HCOs:with reference to a coridit!on 

waters, however, high values of the normality, o_f equilibrium with the ·atmosphere.· 

are found. But as themeanofhis figures for the: · The conclusions concerning ocean water· do 

surface waters of Table 13, 0.00249, agrees with: ·not involve· the greatest· depths or the cold 

the mean of n.ll his determinatim~s, it follows: ·polar region~. It will be· seen that' by postuthut the intermediate samples act~ally show a: lating a slight. deficit of C02 and bases in the 

lower nor~ality of carbonates than either sur-: intermediate ocean waters these waters ·will be 

face or bottom samples. I obtal.n from his· ready to increase their C02 if they come into condata 0.00243 for 49 samples from inte_:p~nedi-· tact with· the bottom. As a matter of fact, 

ate depths. Moreover, the mean for '25 sam-! ·however, they must be surrounded by exte'nples at temperatures below 11° is exactly the. sive layers _of water in which ·equilibrium ·p~e~ 

TAm,E 1.5.-Conclusions suggestcdf~~m the investiga:tion ·with .reference to a condition of equilibrium with the atmosphere. 

Depth. Bases. 

0 t .. r t t !Surface ................. ·Slight excess ........... ·...... Slight-excess. 

c_ean ']a. ·er~ ~c~Ofrth 0 re- Intermediate........... Slight deficit.................. Slight deficit. . f;IOHSt own o,' a oms. Bottom ................. Equilibrium or excess ......... Equilibrium or excess . 

G. If r ,~- · t {Surface......... . . . . . . . . Slight excess................. Slight excess. ,u o .~.n.exwo wa er....... I t d' t Eqm'li'b · E "l'b · · n enne 1a e ........... " . num ........ _. .... _. .. ~. jqu11 rmm. 

san1e as the mean for 24 samples at tempera- ·vails, as the surface and bottom concentrn.-

turf?S above. 11°. The value 0.00243 would tions· are excessive. It is interesting to recall 

therefore appear to be the. most representative in this connection that the waters of the southvalue of the iwrinality for the whole ocean. ern and western Pacific· seem to _be defic-ient in 

But the variation with.temperature, except for , both earbon. dioxide and bases balancing COs 

the bottom samples, do~s not appear in Ditt- ~nd HCOs. These v~ry general concl:usions 

inar's results. Surh a variation, however, is are the best that can be drawn· from all the 

found in the Gulf waters. It may be that' in 13vidence. In any actual series of samples, 

the intermediate waters of_ the open ·ocean however, variations seem to occur which s'tgthere is lacking a source of the bases or possi- gest that there may well be local ·variatiqn.s 

bly of C02 • On the bottom tl~ere may be a due to _organic activity that operates faster 

source of carbon dioxide in the decay of or- than the. mixing of the wat.er .. · Chemi-cal tests 

garlic mn.tter and of_ the bases in the inorganic· n .. re commonly mn.de on comparatively small 

material, which would expl~in high results for samples of the water, and it may be that 

bottom sampl_es. 'fhe slight excess in the greater c<:mstancy would be obtained if larger 

COs +l-ICOs normn.lity for the surface waters·, .samples could ·be employed. · 

liowever, is more difficult ~o account for. If 

it ~.s due to additional bases, where do they CALCULATION OF CARBONATE AND · · BiCARBONATE. corrie from~ Poaaibly river water or organic 

life at the surface.:_sucl~ as algae-aetas comp~- The u.mounts of carbonate and bicarbonate 

tent sources of the bases. ':fhe atmosphere or present_ may first be calculated on the assumporganic life could furnish the carbon dioxide, tion that all the C02 found is cqmpined fi.S 

but in view of the experiments whose results 90s and HCO~ balancing bases. Thus, for 

are given in Tables 11 and 12 sea water does water· 7 in _Tables 2 and lO let x=normality 

not appear to be in a coi1dition to receive car- of COs and y=normality of HC03. Then 

bon dioxide from the atmosphere except at . 22x + 44y = 0. 092 

the very coldest _temperatures. ·This leaves and x+ y=0.00242 

river water and organic life ·as the chief prob- 'yl;t.ence y=0.0018 i:md-x=0.0007. 

able agencies contributing carbon dioxide to · The results thus obtained for the 15 samples 

the surface waters of the ocean. are shown in the last two columns of Table 10. 
··12 SH_ORTER C0NT'RIBUT10NS TO GENERAL GEOLOGY,- ):Ql8. 

-The.se -results ave.rf.l.ge, ·as ·_they _stand, Q.0018 . therefore .. _ a ·few: :illu~trativ.:e: .c:alculat_ions n1ust 

'for·:.the bicarbonate normality and 0.0006 for suffice: -~Jo.hns:ton: gives- t_he fo])owing figures 

·the -carbonate· normality:· Dole's· average "re- for the free carbon dio~de_when: [B+] _eq~als 

sult$_fo.r· Tor.tugas water, .obtained._exclusively 0.001,-'which· is. compar~ble with the normality 

by titration. methods,· are. 0.0016 -~nd 0.0008, of HCOs...found in.se11.'water: . 

. :r:espectively·(from 0.069 and 0.017gram C02 in .. , .---_· -'---,-------, 

the two .forms; see p. 2);· _From Dittmar's 

figure of" 0..092 gram. per liter·for :the total' C02 

. in water of .. the North Atlantic at 22.8° C. 

·:(T~ble ·. 3)' ~and :a· normality of. 0.00243 for 

HC0s+C03 , I ·obtain·O.OOl8 and 0.0006 for the_ 

normalities ·of HCOs and. COs, respectively, 

.. which are· identical with.· the figures for the 

~Gulf surfac·e water, givenin.Table 10. 

·Let :us n.ext ·consider the magnitude of the 

erro'~ i~tr~duced by. neglecting free carbon dioxide in th~ above calculations. . The combination of Dole's mean values for COs il.nd 

· HCOs with ~y n1ean value for the total C02 

in surface Gulf water gives 0.006 gram per 

liter free·. C02 •.. If_ this. figure correctly represents the free coli it would·leave for sample 7, 

for ex~mple, 0.092-0.006 = 0.08,6 gram coli for 

t.he HCOs and. COs. The calculation ,y-ill th~_n 

. be as on pagel1: 

22x + 44y = 0.086 

·and x+ y.=o:oo242 ... . 

.whence y =0.0015;· the ilormality of HCOs, and 

X =0.0009, the normality of Co3 balancing an 

equivalent . amount of. base. These results 

·differ-- markedly f~o:m those firSt . obtained, 

namely, 0.0018 and-0.0007 for thenor~alities 

of HCOs and CQ~ respect~vely, and show 

clearly. th~ order of th~ uncertainty involved 

-in·. the. c.oncentrati91)S .. und~r d~scussiqn. lt 

should be noted, however, that the uncertainty 

is no longe.r. in the amount of total C02 but 

only in the separat~ c-oncentrations of -the 

three forms in whici;t the C02 is conventionally 

stated: 

Johnston1 states that the free carbon dioxide 

can,_be calcul.~ted if .the t.otal.ion con.centration 

9Lbase, l~+]'; ~nd. ~he. hydrogen-ion concentration, [H+], · .are k:rio.wn. The hydrogen-ioi1 

concentration c~n be Q.etermined.by indic.ators 

or: by .the hydrogen electrode, but for several 

reasons it was not determined in the waters 

:unde:r'·syrutiny .. · The :de-termination ·of [B+] 

involves some_ theory and uncertainty, and 

1 Johnston, John, The determination of carbonic acid,- combined and 

.. free, in. solution, particularly in.natural waters: Am. Chern. Soc. Jour., 

~-ol..38, p. 955,_1916. 

10-6 

10-7 

10-8~ 

. ,10~. 

Free carbon 

.dioxide . 

· .:Gr~m per liter. 

0.130. 

.013 

. 0013 

.00016 

. For [B+] =0.01 ~he .. correspo~ding values are 

.ten times. those given above .. · 

Suppose that in sample 7 [I-I+]= l0-7 and 

[B+]=0.002, then free 002 =0.026 grap1 per 

.liter, leaving Q:092 ;--""0.026 = 0.066 gram for 

I-IC03 +COs. The·. calc~la tion will then be, as 

before, 

22x+ 44y = O.OG6 

and · x + · ·. y·= 0.00242-

·whence y~ O.OOb6,·.the :normality of I-IC03 ; and 

x = 0.0018, the· norn;t.ality of COs· These results may- p~obably be :.;egarded. as ·ext~eme, 

n.s '[H+] for sea·.water may be as low as or lower 

than 10-s .. - If.. [H+J =lO-s. the free. C03

· will be 

0.0028 gram, . making HC03 = 0.0016 ·. and 

C03 = 0.0008 .. If [B+]. is less than 0;002 the 

quantity of free C02 .will be less; . 

I:ri a paper on th~ alkalinity of sea. water 

Sorensen and Palitzsch: 2 ·record detern1inations on a. series .of 24 sa~plel; .od: surface wat~r 

from the . A tl~n ti? in whicl?. [H +] . ranges .. from 

10-6.84 to lo--:-·7,81. 

Recent.- determinations by Gaarder s yield 

valu~s fo~ [OH-]. running- fro~ 0.5 X 10-7 

to 25 X 10:--7 ; , or, for···20°, ·[II+]= ~.3.X.1_0....,7 

to 2.6X 10-9

, which is. somewhat less acid 

than that obtained by Sorensen and Palitzsch. 

According to the d~terminatlons of McClendon 4 the water at --Tortugas. gives [I-I+]= 

l0- ·~ to 10-8•

2• 

D Sorensen, ·s. P. L., and Palitzsch, S., Sur.le mcsurago· de la concentration en ions hydrogene de l'eau de mer: Lab. Carlsberg.Compt. rend. 

tr~v., voi. 9, p. 8, 1910. . . · _. . . 

·a Gaarder, Torblorn, Hydroxyl number of pure water and soa water: 

Tidskrift Kemi Farm. Terapi, vol. 13, pp. 93-105, 135-137, 152-15~, 169-

172, 181-187, 19S-201, 1~16. . . . . 

c McClendon, J, F., Experiments with To_rtugus sea water: Carnegie 

Inst. Washington Year Book 15, p. 207, 1916. Sec also Mayer;. A. G., 

Observations upon the alkalinity of the,surface-watcr of the tropical 

Pacifi~: Nat.·Acad. Sci. Ptoc., vol. 3, p: 5-18; 1917: · 

• 

-~ 

,. 
• 

~· 

CARBON DIOXIDE IN WATER OF THE GULF OF MEXICO. 13 

Some further light is thrown on this problem 

by the compm·ison brought out in Table 7. 

It was shown that the Gulf waters appem· to 

be very near equilibrhnn with the atmosphere. 

That being true, we may evaluate the free C02 

by the second term of Fox's equation. (p. 5). 

as that term is intended to represent the C02 

present ·in ·physical solution, the average 

partial pressure of C02 for all the. waters 

being tal\:en as, say, 0.00032 atmosphere. 

The free C02 thus calculated ranges from 

. 0.0005 to 0.0006 gram per liter.- Although 

I-Ie.ru·y's law is now known to be inapplicable 

_with' exactness to Yery dilute solutions of C02, 

the figul'es just given are far smaller than 

those calculated aboYe for [l-l+] = J.0-7 and 

10~. Further in:vestigation is 1ieeded to clear 

. up this discrepancy. · 

In view of the uncertain factors here noted 

the figures in-Table 10 1nay be allo~ecl to stand 

as preliminary estirnates of. the proportions 

of carbonate and bicat·bonate. In future 

determinations it "\vill be desirable .to evalut).te 

[II+] nlong with the otller determinations and 

correct for the free C0 2 as far as possible. 

It would obYiously be incorrect to. calculate 

the COs and I-ICbs sepm·ately from the total 

C02 without correcting for the free C02 when 

the total C02 is exceptionally high and · the 

total I~rcos +COs low, but such high total C02 

seems to be the exception in warm ocean 

water. If we assume a mean value of 0.003· 

gram per ·lite~· of .free C02 in all the samples 

of Gulf wn.ter analyzed, the men.n Yalues for 

the I-ICOs and COs normalities fm~ the Gulf 

water woul_d be 0.0017.and 0.0007 respectively. 

As a mattet of fact, howeYer, the free C02 

varies from one snmple to another, like the 

other concentrations, and a complete statement for each sample woul~ require the 

determination of at least three unknown qunntities-better four, in order to check the results. 

An examination of the results for the carbonate and bicarbonate giYen in Table 10 

shows that there is a slight increase of the 

bicarbonate concentration and a sligh~ decrense of the carbonate c<;:mcentration indi-

. cated with incre~se in depth, or~ one may say, 

with decrease in temperature. The Yariation 

·is not great but appears to be real; if it is 

real, an increase in temperature corresponds 

to a decrease in total C02 , in the total C03 + 

I-IC03, and in HCOs, and· an increase in COs· 

These relations correspond to the known 

effect of temperature on the solubility of 

carbon dioxide in water, on the solubility of 

~.alci.utn carbonate in water, and on the 

hydrolxsis · of cm·bonates. An increase in 

total C02 therefore corresponds to an increase 

in I-ICOs but not in C03 • 

For the sake of completeness, Buchan,an's 

determinations, made during the cruise of the 

Challenger, of the amount of carbon dioxide 

eliminated from sea water ·by boiling are 

presented. for comparison. . There has long 

'Qeen some u~certai~ty "~ to the . exact significance of the results, 1 but they must be of 

0.060 

~ 

~ ~ 

-~ 

~ 

""" X 

~ 

~ X 

X ~ 

.. 

:;;! 

'Q -~ .050 

i 

j 

~ 

t 

~ .040 

~ 

0 0 0 .030 0 C: 10 20" sO'" 

Temperature 

FIGURF. 1.-Curvo showing variation of loosely combined .<'arbon 

· . dioxide In surf~cc sea water with temperature. Tho crosses represent 

tho 12 moans given in Table 16. · 

Yalue as comparative ·determinations, having 

all been made by the same method. I have 

studied Buchanan's results for surface waters 

with reference· to the eqUilibrium that should 

exist between the waters . and the atmosphere 

in respect to carbon dioxide, and I fi.nd the 

clearest indication of a relation between the 

temperature of the water and its content. of 

loosely combined carbon dioxide .. Apparently, 

also, there -is a difference between the Atlantic 

and the Pacific ·waters, but if the resuits for 

the surface waters are arranged solely accordi1lg to temperature the general relation is that 

the amount of loosely combined carbon dioxide 

is greater i:ri "the colder waters. ·(See Table 16 

and fig. 1.) · 

' Challenger Rcpt., Physics and chemistry, vol. 1, p. 103, 1884. Presumably Buchanan's results give tho C02 of bicarbonate together with 

free C02 if present. 
14 SHORTER CONTRIBUTIONS TO GENERAL GEOLOGY, 1918. 

·T:AnLE16.~Buchanan's determinations of-loosely combined carbon dioxide in s1trjace ocean water, arranged according to the : . : , .. , · . . . . . tem peratur:e' of the water. . . . . . . . 

Sample 

No ... Locality.~ : Temperature. 

. oc. 

Loose 

carbon 

dioxide. 

Gram per 

liter. 

389 South Indian Oc;ean, la~. 64° 52'S., long. 83° 12' E ................................ . 386 ·south Indian Ocean, lat. 66° 29' S.;.long. 78°'18' E-~·: .'. ·.·. ~ .......... _:_ ......... . -1.7 0.049 - .7 . 056 

396 South Indian Ocean, lat. 64° 11 S., long. 87°.411 E .... : ................... · ........ . .4 .049 

382 South Indian Ocean, lat. 64° 2' S.,.long.~.7.9° 55' E ................... ·.· ............ . 387 Southlndian Ocean, lat. 65° 10' S., long. 78° 42' E ................................ . .7 . 066 . ."7 . 052 

380 South Indian Ocean, lat. 62° 22' S.,:-long. 80° 4' E" ................................ . 1.1 .064 

415 

354 

364 

360 

417 

1272 

1287 

1378 

1390 

. 1314 

1375 

1462 

1374 

1301 

1366 

1367 

471 

1342 

1352 

497· 

949 

504 

276 

1508 

.1699 

836 

. 267 

i36 

117 

910, 

826 

926 

512 

75 

1687 

1684 

265 

119 

. . 

Mea~ . .'~ ~- ~ ... · : : · .': ~ . : .. · : . · ... ·: ~ ... ~ . : ·. ~ : . ·. ~ . · ............ · .... : ..... : : ...... ~ . . · .1. . 056 

South Indian Ocean, lat. 53° 13' S., long. 109° ·23' E ............... : .............. . :South Indian Ocean, lat. 46° 16.( s.; long~ 48° 27' E ...... ~ ....................... ~. 

4.3 . 052 

5.0. .054 

South I;ndian Ocean, lat. 46° 5;3' S., long. 51° 52' E.~ .......................... :·: .. 5.0 . 047 

;south Indian Ocean, lat. 46° 8' S., long. 49° 40' E ....... ~ ................ , ....... . ;South Indian Ocean, lat. 50° 54'S., long. 118° 3' E ......... :.: ................... . 5.8 . 051 

7.2 .054 ·, 1-----1-----

~ean .... ' ....... ! ....... : .. · ........ · ..... ~ .................. · ................ . 

!====:===== 

,South Pacific Ocean, lat. 38° 43'S., long. 112° 31' W .......... ~ ................... . :South Pacific Ocean, lat. 39° 19' S., long. 10~ 0 19' W .......... : ... ~, ............. ,. ;South Pacific Ocean, lat. 42° 19' S., long. 84° 47' W ............. .' ...... : .......... . :South Pacific Ocean, lat. 45° 31'S., long. 78~ 9' W , ................ : . ...... , ....... . ,South Pacific Ocean, lat. 38° 19' S., long. 84° 25' W ......... : ·.· ..................... : 

South Pacific Ocean, lat. 39° 41' S., long. 86° 331 W .......... · ..... : ............... . 

5.5 .052· 

11.8 . 037 

12. 5 . 042 

12. 7 . 047 

12.7 .049 

13.6 . .-037 

13.9 . 046 

. . 1-------1--------

Mean ................... ~ ...... ." .... '~ .................................... . 12.9 .043 

; South Atlantic Ocean, lat. 42° 32' S., long. 56° 29' W ................. ~ ........... .' 

:South Pacific O~ean, lat. 38 ° 59' S., long. 83 ° 53' W ......... , ...................... . South Pacific Ocean, lat. 37° 55'S., long. 93° 56' W . ." ............................. . South Pacific Ocean, lat. 36° 17' S., long. 83° 50' W" .............................. . :South Pacific Ocean, lat. 36° 58'S., long. 83° 40' W: ............................... . .South Pacific Ocean, lat. 37° 2' S., long. 160° 48' E .. .- ..................... · ....... . 

14. 2, . 039 

14.2 . 051 

14. 7 . 035 

15. 5 . 048 

15.5 .047 

15.6 .050 

1--------1--------

Mean .......... : . .............. · ......... ~ ............. ~ .................. . 15.0 .045 

SouthPacific.Ocean, lat. 33° 20'S., long. 74° 24' W .......................... : .... __ ,!=====\===== 

South Pacific Ocean, lat. 32° 50'S., long.· 77° 6' W ................................ . South Pacific Ocean, lat. 31° 23' S., long. 177° 481 W ............ · ........... :. ~ .... . North Pacific Ocean, lat. 37° 35' N ., long. 163° 461 W .............................. . 

16.9 . 036 

17.5 . 038 

17.8 . 059 

17.9 . 029 

1--------1------

Mean .. . · ... : .. . ·.: .· ..... · ................................ ·, ............. : .... ·:=====!===== 

South'Pacific Oceari., lat. 28° 25'S., long. 17.7° 93' W ........... ·.· ................. . South Atlantic Ocean, lat. 27° 54'S., long. 31° 22' W ............................. . South Atlantic Ocean, lat. 36° 55'S., long. 44° 50' W ............................. . North Atlantic Ocean, lat. 29° 50' N.,long. 35° 551 W ............................. . North Pacific Ocean, lat. 289 231 N., long. 137° 45' E .............................. . South A~lantic Ocean, lat. 24° 43'S., long. 34° 171 W ............................ :. 

17.5 . 040 

19.4 .041 

19.4 .043 

20.0 .034 

20.5 .034 

20.8 .032 

21.0 . 042 

Mean ...... · .... _.· ............................. ~·-:··.························:1-----I-:---- 20. 2 .038 

North Atlantic Ocean, lat. 37° 52' N., long. 42° 1~"W ............................... ! 

North Atlantic Ocean, lat. 34° 51' N., long. 63° 59' W ......... : .................... I 

·North Pacific Ocean, lat. 35° 55' N ., long. 171° 54' E .. ~ ....... ~ ................... . West Pacific Ocean, lat. 24° 47' N;, long. 138° 34' E ............................... . North Pacific Ocean, lat. 36° 59' N., long. 178° 56' W. ........ : ..................... . South Pacific Ocean, lat. 23° 18' S., long. 173° 26' W ....... · ....................... . 

21.1 .053 

21. 4 .045 

21. 7 .035 

21.8 . 021 

21. 9 . 027 

21. 9. . 036 

1---------1-------

Mean .... · .... ; ................ ~ ....... · ... ~ .............. · ................. · .. 21.•6 . 036 

!====!==== 

·'North Atlantic Ocean, lat. 27° 49' N., long. 64° 59' W ............................. . North Atlantic Ocean, lat. 21° 33' N., long. 31° 15' W ........ · ..................... . North Atlantic Ocean, lat. 17° 49' N., long. 28° 28' W ............... c •••••••• · ••••••• 

South Atlantic Ocean, lat. 22° 15' S., long. 35° 371 W ............................. . North Atlantic Ocean, lat. 32° 541N., long. 63° 221 ·W . ."." ...... · ...... · .............. ~. 

22.2 .048 

22.8 . 037 

22. 7 . 038 

22. 8 .059 

23. 3 . 042 

1-------1------

. Mean ...... · ............................... ~ .... · ............................. . 22.8 . 045 

• 

• 

1 

• 
• 

• 

• 

CARBON DIOX;r.DE I~ W A~ER OF T'HE GULF OF MEX~CO • 

. 'rAnLI~ 16.-.Bu.chanan's determinations pj.l,oosely comb.ined carbon dioxide in surface ocean.water, arranged according to the 

~ · .. · ·~emperal1t~e of t.he water-Continued. . .. . . . . . , 

Sample 

No. Locality. Temperature. 

oc. 

990. North Pacific Ocean, lat. 30° 51' N., long. 154° 23'.W ..................... · ......... .. 23.9 

68 North Atlantic Ocean, lat. 21° 26' N., long. 65° 16' W ....................... -....... · 515 South Pacific Ocean, hit. 20°9'S., long. 176° 471 W ...... : ............. : .. :. : . . : . . -.' 24.4 

24:5' 

1581 South Atlantic Ocean, lat. 19° 55' S., long. 13° 56' W.: ........................... . 572. West Pacific Ocean, lat. 11° 37'S., long. 142° .59' E .. , ............... · .......... · ..... I 

1573 South Atlantic Ocean, lat. 23° 27'S., lcng. 13° 51' W .............................. · 1590 South Atlantic Ocean, lat. 14° 59~ S., long. 13° 42' W ............................. . 256 South Atlantic Ocean, lat.14° 51'S., long37° 1'W ............................... .. 

24.7 

25.0 

25.1 

25. 1 

25.3. 

Loose 

carbon 

dioxide .. 

Gram per 

liter . .0.019. 

.046 

. 061 

. 038 

. 027 

. 035 

. 035 

. Q33 1--------~-------

209 

817 

214 

539 

228 

216 

l\{ean ....... · ....... .' ....................... ___ . __ ..... _ .. · .. _. _ .. _ ....... __ 

North Atlantic Ocean, lat. 7° 71 N., long. 16° 111 W ........... ~ ................... . West Pacific Ocean, lat. 21° 17' N., long. 140° 40'.E .............................. . North Atlantic Ocean, lat. 6° 15' N., long. 16° 51 W ........... · .......... , ......... . South Pacific Ocean, lat. 16° 32'S., long. 163° 12' E .............................. . North Atlantic Ocean, lat. 1° 471 N., long. 24° 26' W .................... ·.· ......... . N01·th Atlantic Ocen.n, lat. 4° 341 N, long. 13°.52' W .............................. . 

24. 7 . 037 

25. 7 .043 

25. 8 .025 

25.9 .038 

25.9 . 032 

26.0 . 043 

26.1 . 043 

1--------·1-------

l\{ean ......... ~ ......... · ....... · .................. :: ... , .... · .............. ·_ 25.9 . 037 

1====1==== 

215 

581 

557 

661 

North Atlantic Ocean, lat. 5° 48' N., long. 14° 20' W .............................. , 26.2 . 046 

West Pacific Ocean, lat. 7° 13' S., long. 134° 18' E .................................. · South Pacific Ocean, lat. 13° 50' S., long. 151° 491 E ................... _ ........... . 26.4 . 039 

26. 7 . 036 

1097 

682 

West Pacific Ocean, lat. 12° 21' N., long-. 122° 15' E ................................ . North Pacific Ocean, lat. 7° 261 N., long. 149° 22' W ..... .' ......................... . 26. 7 . 037 

26.8 .029 

North Pacific Ocean, lat. 4° 33' N., long. 127° 61 E ......................... : ....... : 26.9 . 025 

1--------·1-------

l\{ean ............... , ................................ _ .... __ ...... _ ...... . 26.6 . 035 

1====1==== 

602 West Pacific Ocean, lat.1° 42'S., long.127° 7' E· ............................ · ...... . 27.9 . 042 

760 North Pn.cific Ocean, lat. 4° 21' N ., l-ong. 145° 18' E ............................... . 28.4 .030 

1662 North Atlantic Ocean,_ lat. '7° 10' N., long. 15° 10' W .............................. . 28. 6 . 034 

1--------·1-------

l\{ean ........................................... _ ... __ ...... · .... _ ......... . 28.3 . 035 

We are now in a position to make a s~atenlent of the constituents of the salts in Gulf 

. water, say for the surface at a temperature of 

18° to 20°0., which shall include the total C02 as 

carbonate and bicarbonate. Based on Steiger's 

analysis (Table 1), it is given in Table 17; 

which includes also a si1nilar statement, based 

on Dittmar's analysis, for ocean water, say the 

open Atlantic at 1noderate depth at 18° to 20°. 

1'Anr,1~ 17.-Rm;ised analyses of salts in the G'ttlj of Mexico 

and ocean 'Water. 

Gulf of 

Mexico. Ocean. 

Cl .......... .-. . . . . . . . . . . . . . . . . . . . 55. 23 55. 21 

Br .............................. ·. . · . 17 . 19 

S04-························-··-·· 7.54 7.68 

HC03 • • • • • • • • • • • • • • • • • • • • • • • • • • • • 31 . 31 

C03 ........... : .............. :. • • • • 05 . 05 

N a. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30. 79 30. 54 

K............................... 1.10 1.11 

Ca............ .. .. .. .. . .. .. .. .. .. . 1. 22 · 1. 20 

Mg ............. · .... -.. -...... ---. --::-1-::-:0~:-: -::-:~~::-l---·-1-0=-=·~-: ~=-=~ 

Table 18 gives the results of a calculation of 

the chemical equivalence of the basic and acid 

radicles tha.t constitute the salts in the water 

based on. the percentages of the constituents 

showi1 in Table 17. 

TABLE 18.-Equivalence of basic and acid salt constituents 

whose percentages are given in Tab·ze 17. 

Basic radiReacting 

values. Acid radiReacting 

values. 

cles. cles. 

Gulf. Ocean. Gulf. Ocean. 

----

Na ......... 1. 339 1. 328 'Cl.---- .... 1. 558 1.557 K-----~-----. . 028 . 028 Br .......... . 002 . 002 

Ca .......... . 061 . 060 S04-------- .157 .160 

Mg ........ . 295 . 305 HC03 ..... . 005 . 005 

COa- .... : ~ . 002 . 002 ------ ------ Sum of ba- Sum of acid 

sicequiv- equiyalents .... 1. 723 1. 721 alents ... 1. 724 1. 726 
SHORTER CONTRIBUTIONS TO 'GENERAL. GEOLOGY, 1918. 

SUMMARY. do dot perinit a·n exact eval uatiop. of the "free " carbon 

The determinations of carbon dioxide in water of the' dioxide in the water, but a consideration of the uncertain 

Gulf of Mexico recorded in this paper show that the total factors upon which computation of the free carbon dioxide 

carbon dioxide increases with depth, that is with decreas- rests indicates that the amount is probably so small in the 

lng temperature, and the amounts found are very near Gulf water that no appreciable error is made by expressing 

·though slightly below those required for equilibrium with the total carbon dioxide found as a mixture of carbonate 

atmospheric carbon·. diqxide, as calculated by Fox's and, bicarbonate. At any rate, the constituents thus 

equation. Determinations of the total concentration of . determined, talqm in the form of saltls and dissolved in the 

base held in balance with the carbonate and bicarbonate .appropriate amount of pure water, would reproduce the 

radicles were also made; this quantity apparently increases Gulf water under the conditions existing· when the samples 

slightly with decreasing temperature. The data presented were collected. · 

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