Sea Water Chemistry

CHAPTERVI
Chemistry of Sea water

.......................................................... ...... .... ................................ ......
I f suspended sol i d materi al of ei ther organi c or i norgani c ori gi n i s
excl uded, sea water may be consi dered as an aqueous sol uti on contai ni ng
a vari ety of di ssol ved sol i ds and gases. Determi nati on of the chemi cal
nature and concentrati ons of the di ssol ved substances i s di ffi cul t for
the fol l owi ng reasons: (1) some of the di ssol ved substances, such as
chl ori de and sodi um i ons, are present i n very hi gh concentrati ons, whi l e
othera, certai n metal s for i nstance, are present i n such mi nute quanti ti es
that they have not been detected i n sea water, al though they have been
found i n mari ne organi sms or sal t deposi ts; (2) two of the major consti -
tuents, sodi um and potassi um, /i re extremel y di ffi cul t to determi ne
accuratel y; (3) i t i s vi rtual l y i mpossi bl e i n some cases to separate rel ated
substances such as phosphate and arsenate, cal ci um and stronti um, and
chl ori de, bromi de, and i odi de. I n these cases the combi ned el ements are
determi ned together and usual l y reported as i f they represented onl y
one; that i s, cal ci um and stronti um are often cal cul ated as {cal ci um,
and chl ori de, bromi de, and i odi de as chl ori de.
Because of the compl ex nature of the di ssol ved materi al s i n sea water
a speci al l y devel oped techni que i s usual l y requi red to determi ne the
concentrati on of any consti tuent. The standard methods for the
quanti tati ve anal ysi s of sol uti ons whi ch are gi ven i n textbooks general l y
cannot be appl i ed to sea water wi thout adequate checks on thei r accuracy.
Thi s i s parti cul arl y true when deal i ng wi th el ements present i n extremel y
l ow concentrati ons, because the el ements occurri ng as i mpur i ti es i n the
reagents may be i n amounts many ti mes those found i n the water.
Constancyof Composition
I t has been found that, regardl ess of the absohdeconcentrati on of the
total sol i ds, the ratios between the more abundant substances are vi rtual l y
constant. The i mportance of thk resul t cannot be overemphasi zed,
as upon i t depends the val i di ty of the chl ori ni ty: sal i ni ty: densi ty rel a-
ti onshi ps and, hence, the accuracy of al l concl usi ons based on the di s-
tri buti on of densi ty where the l atter i s determi ned by chemi cal or i ndi rect
physi cal methods such as el ectri cal conducti vi tyy or refracti ve i ndex.
165
166 CHEMISTRYOF SEA WATER
Therel ati ve uni formi ty i n the composi ti on of theses water was estab-
l i shed by the i nvesti gati ons of Forchhammer, Natterer, and Di ttmar,
Al though Forchhammer anal yzed a l arge number of sampl es, hi s i nvesti -
gati ons were not compl ete because he di d not determi ne certai n of the
abundant el ements. Natterer made more detai l ed anal yses, but i t was
Di ttmar who l ai d the sol i d foundati on for the present knowl edge of the
composi ti on of sea water.
Di ttmar (1884) made careful determi nati ons on 77 water sampl es,
representati ve of al l oceans, whi ch had been col l ected on the voyage
around the worl d of H.M.S. Challenger. He determined the halides,
sul phate, magnesi um, cal ci um, and potassi um. On composi te sampl es
he found the rati o of bromi ne to chl ori ne and esti mated the carbonate.
Fr om the sums of the chemi cal equi val ents of the negati ve and posi ti ve
i ons, he cal cul ated the sodi um by di fference. Thi s procedure was
fol l owed because he was unabl e to achi eve sati sfactory di rect determi na-
ti ons for sodi um. The resul ts of Di ttmars work showed that there
were no si gni fi cant regi onal di fferences i n the rel ati ve composi ti on of
sea water; consequentl y hi s average val ues coul d be used to represent
the rati os between the major di ssol ved consti tuents. I n tabl e 33 are
TABLE33
DITTMARS VALUES FOR THE MAJOR CONSTITUENTS OF SEA WATER
(Valuesin grams per kilogram, /00)
Ion
cl- . . . . . . . . . . . .
Br- . . . . . . . . . . . .
so,- . . . . . . . . . .
(208. . . . . . . . . .
HCOa- . . . . . . . .
F- . . . . . . . . . . . . .
H8B03. . . . . . . . .
Ma++. . . . . . . . . .
(-Ja++
1
f$r++
K+. . . . . . . . . . . .
Nab+. . . . . . . . . .
Total . . . . . . . . . .
Original values
cl = 19/00
18.971
0.065
2.639
0.071
. . . . . .
. . . . . .
. . . . . .
1.278
0.411
0.379
10.497
34.311
%
55.29
0.19
7.69
0.21
. . . . .
. . . . .
3:72
1.20
1.10
30.59
Recalculated, 1940
atomic weights
Cl = 190/00
18.971
0.065
2.635
0.071
. . . . . .
. . . . . .
i:292
0.411
0.385
10.498
34.328
70
55.26
0.19
7.68
0.21
. . . . .
. . . . .
3:76
1.20
1.12
30.58
1940values
01 = 19/00
18.980
0.065
2.649
i:iii)
0.001
0.026
1.272
0.400
0.013
0.380
10.556
34.482
.
%
55.04
0.19
7.68
o:ii
0.00
0.07
3.69
1.16
0.04
1.10
30.61
gi ven Dittmars average val ues i n the uni ts i n use at the present ti me and
referred to a chlorinity of 19.00 O/OO. The percentages of the vari ous
i ons are al so shown,
CHEMISTRYOF SEA WATER 167
Si nce 1884 the modi fi cati on of atomi c wei ghts has affected the
numeri cal resul ts reported by Di ttmar. Correcti ons for these changes
may be made (Lyman and Fl emi ng, 1940) as shown i n the recal cul ated
val ues i n tabl e 33. I n the l atter tabul ati on the sodi um has been recal -
cul ated by di i ?erence.
I t i s i nteresti ng to compare Di ttmars resul ts wi th those obtai ned by
modern methods of anal ysi s as shown i n the l ast col umns of the tabl e.
The sources of these data are i ndi cated i n tabl e 35. I t i s i mmedi atel y
seen that there are smal l di fferences for most of the el ements determi ned
by Di ttmar and that certai n other i ons have been added to the l i st of
major consti tuents. The bound carbon di oxi de i s reported as bi carbonate
i on i nstead of as carbonate, stronti um i s gi ven by i tsel f i nstead of i n
combi nati on wi th cal ci um, and fl uori de and bori c aci d have been added.
The cl ose agreement between the resul ts of Di ttmar and those
obtai ned recentl y i s remarkabl e when we consi der the compl exi ty of the
probl em and the great advance i n knowl edge of anal yti cal chemi stry.
However, al though the di fferences are smal l , they are si gni fi cant, and
hence the i mportance of l )i ttmars work i s that i t showed the constancy
of the rati os between the major consti tuents, and not that i t l ed to
accurate numeri cal val ues of these rati os.
I n tabl e 33 the composi ti on i s shown by referri ng the substances
to a standard concentrati on, Cl = 19.00 /00, and by means of the rati os I
between the di fferent i ons and the total di ssol ved soI i ds. I n most
i nstances i t i s preferabl e to use a thi rd method; namel y, to gi ve the rati os
between the vari ous substances and the chl ori ni ty or the chl orosi ty
(p. 52), and these rati os are known as Cl -rati os and chl orosi ty factors,
respecti vel y. The Cl -rati o i s the amount of any i on or substance per
uni t (gram) of chl ori ni ty, and i s obtai ned by di vi di ng the concentrati on
i n grams per ki l ogram by the chl ori ni ty, or the concentrati on i n grams
per 200-l i ter by the chl orosi ty. Mul ti pl i cati on of the Cl -rati o by a gi ven
chl ori ni ty or correspondi ng chl orosi ty wi l l gi ve the concentrati ons as
grams per ki l ogram or per l i ter, respecti vel y. Concentrati ons i n mi l l i -
gram-atom uni ts are al ways on a l i ter basi s, and, i f di vi ded by the chl oros-
i ty, yi el d the rati os that are cal l ed chl orosi ty factors. I t may be noted
that a chl orosi ty factor mul ti pl i ed by chl ori ni ty yi el ds the concentrati on
i n mi l l i gram-atomsper ki l ogram.
The uni formi ty of rel ati ve composi ti on i n the oceans i s the resul t of .
ci rcul ati on and mi xi ng. These operati ons are conti nuous, and tend. to
el i mi nate regi onal di fferences i n composi ti on, whatever the cause. Di s-
turbi ng agenci es bri ng about changes that are smal l compared to the
bul k of the substances present and consequentl y wi l l not materi al l y
affect the rel ati ve concentrati on of the major consti tuents. Further-
more, many of the di sturbi ng processes that tend to modi fy the rel ati ve
composi ti on are reversi bl e. For exampl e, the secreti on of cal ci um
carbonate by organi sms, whi ch reduces the quanti ty of cal ci um i n sol u-
ti on, takes pl ace at a certai n season or i n certai n parts of the sea, but
upon the death of the organi sms the cal ci um carbonate may di ssol ve i n
other regi ons. Al though smal l regi onal di fferences may resul t from such
processes, the efl ?ectsare l argel y neutral i zed by mi xi ng. On the basi s of
paral l el determi nati ons of densi ty by means of i nterferometer (p, 54)
and chl ori ne ti trati on, Lotte i ?l ol l er (Bei n, Hi rsekorn, and Mol l er, 1935)
has shown that very smal l systemati c di fferences exi st i n the composi ti on
of water masses of the North Atl anti c, but as yet these are si gni fi cant
onl y as refi ned means for traci ng water masses of certai n characteri sti cs.
The constancy of composi ti on i s, as al ready emphasi zed, of the
greatest i mportance. Not onl y i s i t the basi s of the chl ori ni ty: sal i ni ty:
densi ty rel ati onshi ps, but i t al so affords a means of esti mati ng the
concentrati ons of al l of the major consti tuents when the concentrati on
of any one of them i s known. Furthermore, resul ts of studi es cm the
composi ti on or the physi cal properti es of sea water i n any I ocal i ty are
general l y appl i cabl e to the water i n any other part of the oceans.
Except i n speci al areas, such as i n the Bal ti c Sea, the Bl ack Sea, and
off the mouths of l arge ri vers, i t i s not necessary to consi der that the
water represents speci al l ocal types wi th properti es that di ffer from those
of sea water i n general .
Neverthel ess, i t shoul d be remembered that the
composi ti on i s not absol utel y constant even for the major consti tuents
l i sted i n tabl e 33. Vari ous factors whi ch wi l l be di scussed i n detai l
l ater are al ways operati ng and al ways tend to modi fy the rel ati ve abun-
dances. Ri vers i ntroduce di ssol ved materi al i n proporti ons that are
markedl y di fferent from those i n the sea, and they al so i ntroduce sedi -
mentary materi al that reacts i n vari ous ways wi th the di ssol ved con-
sti tuents. The formati on and mel ti ng of sea i ce may bri ng about a
modi fi ed di stri buti on of the di ssol ved substances.
Thus far, comment has been l argel y r estr i cted to those consti tuents
of sea water that are present i n l arge, or at l east rel ati vel y constant,
proporti ons. I f we consi der those el ements whi ch are present i n smal l
quanti ti es and whi ch are uti l i zed by mari ne organi sms, the concept of
constant composi ti on i s no l onger general l y val i d, because the concentra-
ti ons of these el ements vary wi del y, parti cul arl y near the surface. A
great part of the work i n chemi cal oceanography i s now devoted to
.
determi ni ng the space and ti me vari ati ons i n vari abl e consti tuents,
and much thought i s di rected toward the sol uti on of the probl ems
rel ated to the processes that control the observed di stri buti on.
UnitsUsed in Chemical Oceanography
I n chemi cal oceanography most of the numeri cal resul ts are expressed
as concentrati onsthat i s, as the amounts of vari ous consti tuents i n a
certai n quanti ty of sea water. Obvi ousl y many dXferent combi nati ons
CHEMISTRYOF SEA WATER
169
of mass and vol ume uni ts are possi bl e and, i n fact, a great vari ety have
been used. I n order to avoi d confusi on and to make the resul ts of
di fferent workers di rectl y comparabl e, i t i s desi rabl e that a standardi zed
system of uni ts for reporti ng resul ts i n chemi cal oceanography be fol -
l owed. Such a system has been proposed by the I nternati onal Associ a-
ti on of Physi cal Oceanography (1939).
Onl y two uni ts are to be used for expressi ng the quanti ty of sea
water: ei ther (1) the ki l ogram or (2) the amount of water whi ch at 20 C.
and pressure one atmosphere occupi es the vol ume of one l i ter. The
l atter uni t i s desi gnated as LZO,but i n thi s di scussi on i t wi l l be i ndi cated
as L. The system i n whi ch the consti tuents are reported as the amounts
present per l i ter i s desi gnated as the preferred one, wi th an al ternati ve
for the abundant substances that may be reported as grams per ki l ogram
of sea water. Sal i ni ty and ohl ori ni ty are always reported as grams per
ki l ogram of sea water. I t shoul d be understood that the proposed system
appl i es onl y to the reporting of anal yti cal data i n the l i terature. Any
sui tabl e uni ts may be adopted for the discussion of speci al probl ems.
For expressi ng the amounts of the ,di ssol ved consti tuents, two types
of uni ts are proposed: (1) physi cal uni ts of mass, vol ume, or pressure,
and (2) uni ts based upon the number of atoms of the desi gnated el ement,
whi ch may be present as i ons or mol ecul es ei ther si ngl y or i n combi nati on
wi th other el ements. I n certai n cases the number of chemi cal equi val ents
i s acceptabl e.
The maw uni ts most commonl y used are those of the metr i c system
and bear the fol l owi ng rel ati ons to each other:
1 ton =
IOSki l ograms (kg) = 10 grams (g)
1 gram = 10s mi l l i gr ams (mg) = 106mygrams (~g)
A measure of the number of atoms of the desi gnated el ement i s
obtai ned by di vi di ng the amount of the el ement, expressed as grams,
mi l l i grams, or mygrams, by the gram-atomi c wei ght of the el ement.
Hence,
1 gram-atom (g-atom) = 108mi l l i gram-atoms (mg-atoms)
= 106mygram-atoms (~g-atoms)
Quanti ti es expressed as gram-, mi l l i gram-, or mygram-atoms may be
converted to the correspondi ng mass uni ts by mul ti pl yi ng by the gram-
atomi c wei ght of the desi gnated el ement.
I n certai n cases (for exampl e, al kal i ni ty and hydrogen-i on concentra-
ti on) i t i s desi rabl e to report the concentrati on i n ter ms of chemi cal
equi val ents. The uni ts shal l then be
1 equi val ent (val ) = 10~mi ni -equi val ents (mi l l i val )
For expressi ng the parti al pressure of gases di ssol ved i n sea water
the basi c pressureuni t i s the physi cal atmosphere (p. 55):
1 physi cal atmosphere (atm) = 760 Torr
= 1.0133 X 106 dynes/cmZ
= 1.0133 bar
Parti al pressuresshal l be expressed i n Torr.
Vol ume uni ts are al l based upon the true l i terthat i s, the vol ume of
1 kg of di sti l l ed water at 4*C. When vol ume uni ts are used, the tempera-
ture and pressure shoul d be stated. The quanti ti es of di ssol ved gases,
when expressed as mi l l i l i ter s (ml ), shoul d be those for OC and a pressure
of 1 atmosphere, that i s, NTP.
The centi grade scal e i s to be used for reporti ng temperatures.
The uni ts to be used i n reporti ng data, proposed by the I nternati onal
Associ ati on of Physi cal Oceanography, are gi ven i n tabl e 34. I t shoul d
be noted that al l uni ts are based upon the amount of a desi gnated el ement
that may be present ei ther si ngl y (for exampl e, oxygen or cal ci um) or i n
combi nati on wi th other el ements (for exampl e, phosphate-phosphorus).
Because the 20 l i ter i s the standard vol ume uni t for expressi ng the
quanti ty of sea water, gl asswareshoul d be cal i brated for thi s temperature,
and, i f practi cabl e, measurements and chemi cal determi nati ons shoul d
be made at or near thi s temperature. I f the sea-water sampl es are not
at 20, i t may be necessary to appl y certai n correcti ons. Ful l descri p-
ti ons of the methods for maki ng such correcti ons and tabl es to faci l i tate
the transformati on are i ncl uded i n the Report of the I nternati onal
Associ ati on of Physi cal Oceanography. I n most cases the accuracy
of the methods of anal ysi s for the el ements present i n smal l amounts do
not justi fy such correcti ons.
As al ready stated, i t i s frequentl y desi rabl e to express the rel ati ve
concentrati ons as Cl -rati os or chl orosi ty factors (p. 167). These rel a-
ti onshi ps may be used to cal cul ate the quanti ty of the major el ements
present i n water of known chl ori ni ty or to check vari ati ons i n composi ti on
whi ch may be brought about by natural agenci es, pol l uti on by sewage
and i ndustri al wastes, or by other agenci es.
Compositionof Sea Water
So far, the di scussi on of the composi ti on of sea water has been based
mai nl y on the resul ts of the fundamental i nvesti gati ons of Di ttmar.
Si nce hi s ti me our knowl edge of the composi ti on of sea water has i ncreased
tremendousl y. I mproved methods of anal ysi s have been devel oped and
consequentl y more accurate val ues can be obtai ned. Tests have al so
been devel oped for the detecti on and determi nati on of el ements other
than those previ ousl y di scussed. Parti cul ar efforts have been devoted
to the study of the so-cal l ed pl ant nutri ents-that i s, those el ements
whi ch are essenti al to pl ant growth i n the sea but whkh are present i n
smal l and vari abl e amounts. I ndl vi dual el ements have been studi ed
both extensi vel y and i ntensi vel y, so that much more i s now known
TABLE34
ABBREVIATIONS AND UNITS TO BE USED IN REPORTING CHEMICAL
DATA
(Schemeproposed by the International Associationof Physical Oceanogra~hy)
Designated substance
I
Abbreviation
Ammonia-nitrogen IAmmonia-N
Argon Argon
Arsenate-arsenic Arsenate-As
Arsenite-arsenic , Arsenite-As
Borate-boron Borate-B
Calcium Ca
Carbon dioxide Carbon dioxide-C
co,
Chlorinity cl
Copper Cu
Iron Fe
Magnesium Mg
Manganese Mn
Nitrate-nitrogen Nitrate-N
Nitrite-nitromn Nitrite-N
Nitrogen (ga;) N,
Oxygen (gas) 0,
Phosphate-phosphorus Phosphate-P
Potassium K
Radioactive substances
Salinitv s
Silicate-silicon Silicate-Si
Sodium Na
Sulphate Sulphate-S
so
Hydrogen sulphide Sulphide-S
HzS
. .
Units (p = preferred, a = alternative)
mg-atom
L
P
P
P
P
P
..
P
P
P
P
P
P
Pg-atom ml at NTP
..
L L
P
P
P
a
..
P
.
~

P
.
P
P
a
a
P
P ,\
I
a
/00
-P_
.
a
a
_P_
_P_
concerni ng the regi onal di fferences i n the rati os of the major consti tuents
and i n the amounts of the el ements present i n smal l quanti ti es. How-
ever, except for Di ttmars work, there has been no careful study of the
composi ti on of a.l arge number of sampl es for. al l the.major consti tuents.
Hence, i n order to prepare a tabul ati on of the composi ti on of sea water
i t i s necessary to combi ne the resul ts of numerous workers who have
exami ned sampl es from di fferent sources. Al l avai l abl e data were
col l ected by Thompson and Robi nson (1932), and addi ti onal references
wi l l be found i n the fol l owi ng di scussi on. I n some cases the i nformati on
i s extensi ve, but for other el ements onl y a few determi nati ons have been
made on water from a si ngl e l ocal i ty. We shal l fi r st exami ne the quanti -
ti es of the major el ementsthat i s, those whi ch bear a vi rtual l y constant
rel ati onshi p to the chl ori ni ty.
I n tabl e 35 i s gi ven a compi l ati on of the major i ons that make up
over 99.9 per cent of the known dksol ved sol i d consti tuents of sea water.
The sources of these data have been di scussed by Lyman and Fl emi ng
(1940). The concentrati ons of the vari ous i ons are shown for water of
19.00 /00 chl ori ni ty, and al so the Cl -rati os. The quanti ti es are al so
expressed i n ter ms of chemi cal equi val ents per ki l ogram for water of
19.00 /00 chl ori ni ty and as mi l l i gram-atoms per 20 l i ter. Chl orosi ty
factors are gi ven for uni ts of mi l l i gram-atoms. . The carbon di oxi de
has been reported as bi carbonate.
Thi s method i s not str i ctl y accurate,
because the bound carbon di oxi de content of sea water i s vari abl e, but,
as wi l l be shown i n the di scussi on of the carbon di oxi de system, the sum
of the chemi cal equi val ents of carbonate and bi carbonate i s vi rtual l y
constant for any chl ori ni ty.
I t i s i mmedi atel y seen that the sum of the hal i des (chl ori de, bromi de,
and fl uori de) by wei ght i s greater than the chl ori ni ty. The amount of
i odi de i s negl i gi bl e. Even i f the bromi de i s cal cul ated as chl ori de,
and i f the fl uori de i s di sregarded because i t does not take part i n the
chl ori ni ty determi nati on, the chl ori de equi val ent i s 1.00045 ti mes
greater than the chl ori ni ty. The reasons for thi s apparent di screpancy
have been di scussed on page 52.
Lyman and Fl emi ng (1940) obtai ned the fol l owi ng empi ri cal equati on
for the di ssol ved sol i ds as represented i n tabl e 35:
z 0/00= 0.073 + 1.8110 Cl /oo.
Fr om thi s i t wi l l be seen that i n water of 19.00 /oo chl ori ni $y the ~O~aZ
dissoived sol i ds are 34.4816 /00, but, according to the equation used $0
cal cul ate the sal i ni ty from the chl ori ni ty (p. 51), the sal i ni ty i s 34.325
/00. Thus, the total amount of di ssol ved sol i ds i s greater than the
sal i ni ty. I f, on the other hand, the sal i ni ty i s cal cul ated from the total
sol i ds, usi ng the defi ni ti on for the former quanti tythat i s, by converti ng
the bi carbonate to oxi de and converti ng the bromi de to chl ori de-we
obtai n the sal i ni ty by defi ni ti on as 34.324 /00. Thi s agreement must
be consi dered as more or l ess acci dental , as there are many uncertai nti es
i n the anal yti cal data. Confi dence i n the val ues i s strengthened, how-
ever, by the fact that the sodi um: chl ori ni ty rati o as reported by Robi nson
CHEMISTRYOF
n
w w
000000 0 00 00
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . .
o Ao 00
. . .
. . .
. . .
. . .
. . .
,.
. . .
.,.
. . .
. . .
. .
:..
. . .
. .
. . .
. . .
.+
173
and Knapman (1941) agrees exactl y wi th the val ue that Lyman and
Fl emi ng (1940) found by dti erence. Al though the tabl e represents the
most probabl e fi gures for the composi ti on of the major di ssol ved con-
sti tuents, i t i s subject to change as addi ti onal data become avai l abl e,
The data i n tabl e 35 appl y more speci fi cal l y to surface water than
to deep water. Both bi carbonate i on and cal ci um wi l l be sl i ghtl y hi gher
i n deeper water. Furthermore, some of the other compounds not
i ncl uded i n thk tabul ati on, such as ni trate and si l i cate, may be present
i n suffi ci ent quanti ti es to di sturb the bal ance of the ani ons and cati ons
shown i n the tabl e. The Cl -rati os shoul d therefore be consi dered more
as i ndi ces than as absol ute val ues. However, i n no case wi l l the rati os
vary by more than a uni t or two i n the l ast deci mal pl ace when the water
under i nvesti gati on i s from the open sea.. Under abnormal condi ti ons,
as i n hi ghl y di l uted water, l arger departures maybe found, By defi ni ti on
the sal i ni ty i s not zero at zero chl ori ni ty; hence the rati os of certai n
el ements woul d be expected to approach i nfi ni ty at very hi gh di l uti ons
when the di l uti ng water contai ned substances other than hal i des. There-
fore, i n studi es i n areas of hi ghl y di l uted water the character of the ri ver
water shoul d be taken i nto account. As pol l uti on probl ems frequentl y
occur i n such areas, i t wi l l be necessary to determi ne the normal rati os
for di fferent di l uti ons for a speci fi c zone before any concl usi ons can be
drawn as to the nature or extent of the pol l uti on.
ElementsPresentin Sea Water
Thus far, onl y the major consti tuents of sea water have been con-
si dered, I n tabl e 36 are entered al l el ements that are known to occur
i n sea water as di ssol ved sol i ds, except hydrogen and oxygen. They are
not gi ven as i ons i n thk case but as the amounts of the i ndi vi dual el ements
whi ch occur i n water of chl ori ni ty 19.00 O/OO.The el ements are arranged
i n the order of thei r abundance. I n the fi r st col umn they are reported as
mi l l i gr ams per ki l ogram, and i n the second as mi l l i gram-atoms per l i ter.
For conveni ence, the 1940 atomi c wei ghts and thei r reci procal s have been
i ncl uded. These constants are necessary when converti ng wei ght uni ts
to gram-atom uni ts, and vi ce versa. The val ues for the major el ements
correspond to those gi ven i n previ ous tabl es and, i n general , are val i d for
surface water. For many of the el ements ranges i n concentrati on have
been i ndi cated. No doubt ranges shoul d be shown for others, but the
l ack of suffi ci ent observati ons or uncertai nty as to the rel i abi l i ty of
reported data l eaves these probl ems unsettl ed. For many of the el ements
that are present i n very l ow concentrati ons there are onl y one or two
determi nati ons avai l abl e, and i n some cases onl y i ndi rect esti mates
have been made. Hence, i n these cases the i ndi cated val ues can repre-
sent onl y the order of magni tude of the quanti ti es present. Omi tti ng
the si x most abundant el ements, onl y carbon (C02 components), si l i con,
CHEMtSTRYOF SEA WATER 175
ni trogen, and phosphorus compounds have been studi ed wi th suffi ci ent
compl eteness to provi de a fai rl y good i dea of thei r di stri buti on. Less
compl ete studi es have been made on the vari ati ons i n the amounts of
boron, i odi ne, i ron, manganese, copper, gol d, and radi um. Cadmi um,
chromi um, cobal t, and ti n have been found i n the ash of mari ne organ-
i sms, and hence i t i s i mpl i ed that they occur i n sea water, al though so
far they have not been shown di rectl y.
Forty-four el ements are l i sted i n tabl e 36, and i f we add hydrogen,
oxygen, and the i nert gases neon, hel i um, and argon, we obtai n a total
of forty-ni ne el ements that are known to occur i n sea water. Further
i nvesti gati ons wi l l undoubtedl y demonstrate the presence of others.
Certai n probl ems of the ori gi n and concentrati on of the di ssol ved sol i ds
rel ati ve to thei r concentrati on i n the earths crust wi l l be di scussed l ater.
The fol l owi ng bri ef di scussi on i s l ti l ted to those el ements that
ei ther occur i n rel ati vel y l arge amounts or whose di stri buti on has been
shown to be affected by bi ol ogi etd acti vi ty. For el ements i n the l atter
group addi ti onal data are gi ven i n chapter VI I . I n tabl e 36 references
are gi ven for those el ements not di scussed i n the text. A comprehensi ve
di scussi on i s gi ven by Thompson and Robi nson (1932), and other resul ts
are reported by Gol dschmi dt (1937) and Wattenberg (1938). The
el ements are consi dered i n the order i n whi ch they appear i n the tabl e.
Chlorine, present as chl ori de i on, i s the most abundant i on and makes
up about 55 per cent by wei ght of the di ssol ved materi al . I t i s rarel y
measured except i n combi nati on wi th other hal i des i n the chl ori ni ty
determi nati on. The bromi de and i odi de are then computed as i f they
were chl ori de. I t shoul d be kept i n mi nd that the rati o of the chl ori ne-
equi val ent of the hal i des to the chl ori ni ty i s 1.00045 (p. 52). The
chl ori ni ty i s of the greatest i mportance, not onl y as the basi s of densi ty
computati ons, but al so as the standard to whi ch those substances present
i n major amounts are referred.
Sodium is the most abundant cati on i n sea water, but i t i s rarel y
determi ned di rectl y, owi ng to the techni cal di ffi cul ti es i nvol ved i n the
determi nati on of the al kal i metal s. The average rati o to chl ori ni ty,
0.5556, as obtai ned by Robi nson and Knapman (1941) agrees exactl y
wi th the val ue that Lyman and Fl emi ng (1940) cal cul ated by di fference.
I t i s somewhat hi gher than the average of 0.5509 gi ven by Thompson and
Robi nson (1932), but i s i n fai r agreement wi th the rati o 0.5549 obtai ned
by Webb (1939) by di rect anal ysi s. The sodi um: chl ori ni ty rati o may ,
be modi fi ed near ri ver mouths.
Mqpesiuwz content of sea water has been i nvesti gated rather care-
ful l y, parti cul arl y by Thompson and Wri ght (1930). The magnesi um i s
usual l y determi ned by a speci al modi fi cati on of the magnesi um-ammo-
ni um-phosphate method. The rati o of. magnesi um to chl ori ni ty i s very
uni form.
OF SEA WATER
w
+j
ij
n
CHEMISTRY
00000000000000
00000000000000
v
Sulphur i s present i n sea water as sul phate i on, and i s i n thi s form
usual l y determi ned by preci pi tati on as bari um sul phate. An extensi ve
study of the sul phate di stri buti on has been made by Thompson, Johnston,
and Wl rth (1931). Under stagnant condi ti ons occurri ng i n certai n
i sol ated basi ns, and i n and near bottom sedi ments, a part of the sul phate
may be converted to sul phi de i on. Consi derabl e quanti ti es of sul phi de
occur i n the Bl ack Sea and i n certai n Norwegi an fjords, and i ts presence
has been reported i n many l ocal i ti es. The sul phate: chl ori ni ty rati o
may al so be modi fi ed by di l uti on wi th ri ver water, whi ch i s general l y
rel ati vel y hi gh i n sul phate. Pr ocesses of freezi ng and mel ti ng may
possi bl y affect the rel ati ve concentrati on (p. 216).
Cal ci um i s present i n much smal l er quanti ti es than ei ther sodi um or
magnesi um, but i ts di stri buti on i n the ocean has been studi ed much more
thoroughl y, mai nl y because cal ci um i s a major consti tuent of many
skel etal remai ns found i n mari ne sedi ments. By deposi ti on of such
remai ns cal ci um i s permanentl y removed from the water, but thi s
removal does not necessari l y i mpl y that the cal ci um concentrati on i s
decreasi ng, because a l arge suppl y i s mai ntai ned by the ri ver waters
fl owi ng i nto the sea. Detectabl e di fferences i n the cal ci um: chl ori ni ty
ratio have been observed. In the Baltic, Gripenberg (1937a) has shown
that the type of river water which has diluted the sea water can be
determi ned from that rati o. Furthermore, Moberg and Revel l e (1937)
have demonstrated the exi stence of verti cal di fferences i n the cal ci um:
chl ori ni ty rati o whi ch they attri bute to the removal of cal ci um i n the
surface l ayers through bi ol ogi cal acti vi ty. I nterest i n the concentrati on
of cal ci um has al so centered around the questi on of the vol ubi l i ty of
cal ci um carbonate i n sea water and the factors that control preci pi tati on
and sol uti on. I n certai n areas cal ci um carbonate i s apparentl y pre-
ci pi tated i norgani cal l y, and i n other regi ons i t apparentl y passes i nto
sol uti on. I n addi ti on to these probl ems, knowl edge of the cal ci um
concentrati on i s i mportant i n an understandi ng of the carbon di oxi de
system i n the sea, whi ch wi l l be di scussedl ater. The quanti ty of cal ci um
i s usual l y determi ned by preci pi tati on as the oxal ate under care-
ful l y control l ed condi ti ons and subsequent ti trati on wi th potassi um
permanganate. One such method has been descri bed by Ki rk and
Moberg (1933).
Webb has poi nted out that i n thi s method for the esti mati on of cal ci um
the stronti um wi l l be carri ed down, and hence the cal ci um fi gure wi l l
be too hi gh by the equi val ent amount of stronti um. As the rati o
cal ci um: stronti um i s apparentl y constant, Webb suggests that the
(cal ci um shal l be taken to mean the cal ci um after the stronti um and
bari um have been repl aced by cal ci um. Si nce the bari um i s negl i gi bl e
i n thi s case, the val ues of cal ci um wi l l be gi ven di rectl y by vol umetri c
methods, but when the quanti ti es are determi ned by wei ghi ng, correcti ons
CHEMISTRYOF SEA WATER I 79
must be appl i ed (Webb, 1938). Val ues ci ted i n thi s di scussi on are for
cal ci um al one and have been obtai ned by correcti ng the anal yti cal data
for the presence of stronti um. The eal ci urn Cl -rati o as defi ned by
Webb and correspondi ng to the val ues of cal ci um and stronti um i n
tabl e 35 i s 0.0214.
Potawium i s the fourth most abundant cati on and i s present i n
amounts of onl y d few per cent of that of sodi um. The potassi um i s
rarel y determi ned di rectl y, but apparentl y i t bears a very constant
rel ati onshi p to the chl ori ni ty (Thompson and Robi nson, 1932). How-
ever, the content of potassi um may be modi fi ed by bi ol ogi cal agenci es,
si nce some organi sms, parti cul arl y the l arge al gae, concentrate potassi um
to a marked degree. The rati o of the potassi um to chl ori ni ty may al so
be modi fi ed by di l uti on wi th ri ver water. The potassi um may react
wi th the col l oi dal and cl ay parti cl es brought to the sea by ri vers
and run-off, and consequentl y thi s agency may i nfl uence the rati o,
Certai n mi neral s formed on the sea bottom, such as gl auconi te, contai n
potassi um.
Bromine shows a very constant rati oto the chl ori ni ty and i s apparentl y
al l present as bromi de i on.
Di scussi on of the concentrati on of carbon i n sea water i s compl i cated
by the fact that i t occurs not onl y i n the form of carboni c aci d and i ts
sal ts but al soi n appreci abl e amounts as a consti tuent of organi c materi al ;
ei ther l i vi ng or dead. The detri tal organi c materi al may be ei ther
parti cul ate or i n sol uti on. The sol ubl l i ty of carbon di oxi de depends
upon the temperature and sal i ni ty of the water, and exchange of carbon
di oxi de wi th the atmosphere takes pl ace at the surface. Photosynthesi s
i n the surface l ayers reduces the amount of carbon di oxi de i n the water,
and respi rati on i ncreases the concentrati on. Consequentl y, the quanti -
ti es of carbon present as ei ther free carbon di oxi de, bi carbonate, or
carbonate wi l l show a consi derabl e range. These probl ems wi l l be
di scussed i n the secti ons deal i ng wi th the carbon di oxi de system i n the
sea. The quanti ty of carbon gi ven i n tabl e 36 was cal cul ated on the
assumpti on that onl y bi carbonate i ons were present. The organi c
carbon, whi ch i s probabl y of the order of 2 to 3 mg/L (O.15 to 0,25
mg-atoms/L), was not i ncl uded. The methods by whi ch the di fferent
carbon di oxi de components and the parti cul ate and di ssol ved organi c
carbon may be determi ned are di scussed l ater.
Nrontiwm has not been i nvesti gated i n detai l , as i t i s extremel y
di ffi cul t to determi ne quanti tati vel y. I n determi nati ons of cal ci um by
means of the oxal ate preci pi tati on, the stronti um i s carri ed down wi th
the cal ci um, and consequentl y the rati o of cal ci um: chl ori ni ty usual l y
reported for sea water represents the cal ci um pl us stronti um reported as
cal ci um. Stronti um i s a consti tuent of the cal careous skel etons of certai n
organi sms.
Boron occurs i n sea water i n a surpri si ngl y hi gh concentrati on and
bears a constant rel ati onshi p to the chl ori ni ty. Apparentl y i t i s present
as undi ssoci ated bori c aci d. There has been consi derabl e uncertai nty
as to the form i n whi ch boron occurs, but the method Qf determi nati on i s
standardi zed agai nst bori c aci d and the val ues can at l east be expressed
as equi val ent to a certai n concentrati on of bori c aci d. The determi nati on
of bori c aci d i n sea water i s based on ti trati on wi th very di l ute sodi um
hydroxi de i n the presence of manni tol . Methods have been descri bed by
Hardi ng and Moberg (1934) and by I gel srud, Thompson, and Zwi cker
(1938). The amount of boron present i n sea water i s of i nterest i n the
carbonate equi l i bri a and i n thi s connecti on wi l l be di scussedl ater. Boron
i s concentrated by certai n mari ne organi sms.
M?i con has been studi ed extensi vel y because i t i s uti l i zed by di atoms
and other si l i ca-secreti ng organi sms. Accordi ng to a tabul ati on by
Thompson and Robi nson (1932), the si l i cate-si l i con vari es by more than
one hundredfol d-namel y, from 0.0007 to 0.11 mg-atoms/L (0.02
to 3.0 mg/L). Cl owes (1938) found val ues sl i ghtl y exceedi ng .14
mg-atoms/L (4.0 mg/L) i n the deep waters of the Antarcti c. Surface
sampl es are usual l y l ow, owi ng to the devel opment of si l i ca-secreti ng
organi sms, but a progressi ve i ncrease i n si l i cate takes pl ace wi th depth,
whi ch i s ascri bed to the di ssol vi ng of sol ubl e si l i cates. However, there
i s al ways the possi bi l i ty that the water contai ns si l i con i n some compound
present i n col l oi dal form. Ri ver water contai ns a hi gh content of si l i con,
both i n sol uti on and as col l oi dal parti cl es. Di atom and radi ol ari an
oozes contai n the si l i ceous remai ns of organi sms that have devel oped
near the surface and settl ed to the bottom after thei r death. Al though
si l i ceous deposi ts of organi c ori gi n cover l arge areas, most of the si l i ceous
skel etal remai ns di ssol ve after the death of the organi sms. Si l i con
present as sol ubl e si l i cate i s determi ned cal ori metri cal l y. The method
has been descri bed by Thompson and Houl ton (1933) and by Wattenberg
(1937). Because of the rapi di ty wi th whi ch water sampl es are con-
tami nated by si l i cate that di ssol ves from the gl ass, the anal yses shoul d
be made soon after the water sampl es are col l ected. Waxed contai ners
are someti mes recommended, and i t i s al ways desi rabl e to use aged
bottl es that have been thoroughl y l eached wi th sea water. Tourky
and Bangham (1936) tested the reacti on between the mol ybdate reagent
and col l oi dal si l i ca and found that the col or devel opment was not propor-
ti onal to the amount of si l i con present. Treatment of the col l oi dal
si l i ca wi th al kal i pri or to anal ysi s yi el ded correct val ues. Experi ments
wi th sea water i ndi cated that col l oi dal si l i ca may pass i nto true sol uti on
on agei ng.
Fluorine is present i n oceani c sea water i n concentrati ons sl i ghtl y
above 1 mg/L. I t i s present as fl uori de and, accordi ng to the work of
Thompson and Tayl or (1933), bears a constant rati o to the chl ori ni ty.
&EMISTRY OF sa WATER 181
The method of determi nati on i s descri bed by these authors. Li ttl e i s
known concerni ng the rol e of fl uori ne i n the sea.
Nitrogen occurs i n sea water both i n compounds of vari ous ki nds
and as free di ssol ved ni trogen gas. Aa i t i s an essenti al consti tuent of
l i vi ng matter, ni trogen i s found i n organi c compounds both i n organi sms
and i n parti cul ate and di ssol ved organi c materi al i n amounts between
0.1 and 10.0 pg-atoms/L (p. 254). I n addi ti on, i t i s present as ni trate,
ni tri te, and ammoni a. I n routi ne observati ons onl y the i norgani c
ni trogen compounds are determi ned. Ni trate- and ni tri te-ni trogen are
determi ned cal ori metri cal l y, and the ammoni a ei ther cal ori metri cal l y
(Robi nson and -Wi rth, 1934) or by mi cro-ti trati on after di sti l l ati on
(Krogh, 1934).
The ni trate method ori gi nal l y descri bed by Harvey (1926) i s gi ven
by Wattenberg (1937). Rakestraw (1936) and Wattenberg descri be the
procedure for the determi nati on of ni tri te. Si nce the i norgani c ni trogen
compounds are subject to change after the water sampl es have been
col l ected, anal yses must be run wi thi n a few hours. Even the addi ti on
of preservati ves may not prevent changes i n the NH~and NOZ,i ndi cati ng
that purel y chemi cal transformati ons may be i nvol ved. Ammoni a
tends to di sappear i n storage, and ni tri te someti mes decreases, but at
other ti mes shows an i ncrease. The ni trate, whi ch i s more abundant,
does not show such rel ati vel y l arge changes.
Because of thei r rel ati vel y l ow concentrati ons and thei r uti l i zati on
by organi sms, the i norgani c ni trogen compounds show a wi de range i n
val ues:
Nitrate-N . . . . . . . . . . . . . . . . . . . . 0.1-43.0 M-atoms/L, 1-600 Pg/L
Nitrite-N . . . . . . . . . . . . . . . . . . . . . 0.01-3.5 pg-atoms/L, 0.1-50 pg/L
Ammonia-N. . . . . . . . . . . . . . . . . . 0.35-3.5 pg-atoms/L, 5-50 ~g/L
The di stri buti on of ni trate i n the oceans has been and i s studi ed a
great deal , as i t may l i mi t the producti on of phytopl ankton when i t i s
reduced to mi ni mal quanti ti es i n the surface l ayers. Ni trate-ni trogen
usual l y shows a subsurface maxi mum at a depth of several hundred
meters. Ni tr i te ni trogen has a pecul i ar di stri buti on and i s general l y
found i n a rather thi n stratum i n or above the thermocl i ne. Lessi i s
known concerni ng the di stri buti on of ammoni a, as i t i s not so readl y
measured as the other i norgani c compounds of ni trogen, but i t i s appar-
entl y rather uni form throughout the water col umn.
Ni trogen compounds are carri ed to the sea by ri vers and by preci pi ta-
ti on. The greater part of these are supposed to have been fi xed by
el ectri cal di scharges i n the atmosphere. Possi bl y a certai n amount of
the fi xed ni trogen i n the sea i s l i berated as free ni trogen and returned
to the atmosphere. Bottom sedi ments contai n a smal l percentage
of organi c ni trogen i n resi stant organi c detri tus, and a part of thi s i s
permanentl y l ost from the water, as i t i s found i n al l types of sedi ments,
both recent and fossi l . As the carbon: ni trogen rati o i n organi c materi al
i s rel ati vel y constant, the organi c ni trogen i s frequentl y used as a measure
of the amount of organi c matter i n mari ne sedi ments and al so i n the
water. The di stri buti on of ni trogen compounds and the ni trogen cycl e
i n the sea are dkxmssedi n chapters VI I and XVI I I .
Aluminum i s presenti n seawater i n very smal l amounts. The col l oi dal
cl ay parti cl es whi ch are carri ed to the sea contai n a l arge percentage of
al umi num, and hence anal yses of water sampl es col l ected near shore may
show the presence of al umi num, but i t i s not necessari l y al l i n sol uti on.
The val ue gi ven i n tabl e 36 i s the average quanti ty reported by Haendl er
and Thompson (1939). Thei r val ues range between 0.006 and 0.065
mg-atoms/L (O.16 and 1.8 mg/L) wi th an average of 0.02 mg-atoms/L
(0.54 mg/L).
Al though earl i er workers (Thompson and Robi nson, 1932) were
unabl e to detect rubi di um i n sea water, Gol dschmi dt (1937) has reported
about 0.002 mg-atoms/L (0.2 mg/L).
Li thi um content of sea water has been i nvesti gated by Thomas and
Thompson (1933), who found 0,014 mg-atoms/L (0.1 mg/L).
Phosphorus,whi ch i s present i n sea water as phosphate i ons, i s another
of the essenti al consti tuents of l i vi ng organi sms, and i ts di stri buti on i n
the sea i s markedl y affected by organi c agenci es. I n addi ti on to the
ni trogen and si l i con compounds, phosphate-phosphorus has been con-
si dered as one of the substances that may l i mi t producti on of pl ant l i fe.
The i norgani c phosphorus concentrati on vari es from vi rtual l y zero at the
surface, under certai n condi ti ons, to approxi matel y 0,003 mg-atoms/L
(0.090 mg/L) at subsurface l evel s when val ues are corrected for sal t
error. There i s frequentl y a subsurface maxi mum si mi l ar to that i n the
di stri buti on of ni trate-ni trogen. Phosphorus removed from the surface
l ayers by phytopl ankton i s l argel y returned to sol uti on on the death and
decomposi ti on of the organi sms. I t i s suppl i ed by ri vers, and some i s
removed from the sea, as a smal l quanti ty i s present i n most mari ne
sedi ments. I n certai n shal l ow areas, phosphati c concreti ons are found
that contai ns a rather hi gh concentrati on of phosphorus. The mode of
ori gi n of these concreti ons i s not yet known. I t has been suggested that
i n many regi ons the water i s supersaturated i n respect to tri cal ci um
phosphate whi ch, therefore, may be deposi ted i norgani cal l y (Di etz,
Emery, and Shepard, 1942),
Phosphate phosphorus i s determi ned cal ori metri cal l y. The method
has been descri bed by Robi nson and Wi rth (1935) and Wattenberg
(1937). Cooper (1938a) has di scussed the magni tude of the sal t error.
Phosphate anal yses are frequentl y carri ed out as routi ne observati ons,
and our knowl edge of the dktri buti on of phosphate i n the ocean i s fai rl y
comprehensi ve. The rather scant knowl edge we have concerni ng the
CHEMSTRY OF SEA WATER 183
amount of phosphorus present as parti cul ate or di ssol ved organi c phos-
phorus wi l l be di scussed i n connecti on wi th the phosphorus cycl e i n the
sea (chapter VI I ).
The amount of bari umi n sea water has been reported by Gol dschmi dt
(1937) as 0.0004 mg-atoms/L (0.05 rng/L). Thi s i s l ower than the val ues
reported by Thompson and Robi nson (1932). Bari um occurs i n mari ne
orga@ms and i t i s a consti tuent of most mari ne sedi ments. I n certain
l ocal i ti es the deposi ts contai n l arge amounts of bari um sul phate i n the
form of concreti ons and nodul es. The mode of formati on of these
structures i s not yet understood.
The di stri buti on and concentrati on of i odi ne i n the sea h~ recei ved
a great deal of attenti on because of i ts i mportant rol e i n the physi ol ogy
of man and ter r estr i al ani mal s. Mari ne products are an i mportant
source of i odi ne-ri ch foods, The form i n whi ch i odi ne occurs i n sea water
i s not yet cl earl y understood, but at l east part of i t i s present as i odi de
and i odate. I t i s concentrated,to a marked degree by mari ne pl ants, and
for many years sea weeds have been used as a commerci al source of i odi ne.
The di stri buti on and determi nati on of i odi ne i n sea water and mari ne
organi sms have been di scussed by Cl oss (1931) and Rei th (1930).
Arsenic content of sea water has been i nvesti gated by Rakestraw
and Lutz (1933), who report val ues rangi ng from 0.15 to 0.3 pg-atoms/L
(9 to 22 pg/L). Thi s wi de range i s attri buted to the fact that organi sms
may uti l i ze arseni c i n pl ace of phosphorus. I t i s known to be a con-
sti tuent of the ti ssues of many mari ne forms. The exact form i n whi ch
arseni c occurs i n sea water i s not yet known.
I ron i s an essenti al consti tuent of pl ants and has been consi dered
*
as one of the substances that may l ti l t the amount of pl ant producti on
i n the sea. I nvesti gati ons show that at l east part of the i ron i s not
present i n true sol uti on, as i t can be removed by ul trafi l trati on. Cooper
(1937b) has poi nted out that the amount of i ron i n true sol uti on as ferri c
or ferrous sal ts i s probabl y l ess than 2 pg/L7 whkreas the total i ron
present i s general l y about ten ti mes thi s quanti ty. The amount present
i n tbe pl ankton may be as much as 16 per cent of the total i ron of the
water. Harvey (1937) consi ders that di atoms are abl e to adsorb and
uti l i ze col l oi dal i ron. I ron i s brought to the sea i n rel ati vel y l arge quanti -
ti es i n the col l oi dal cl ay parti cl es, and consequentl y consi derabl e amounts
of i ron are found i n the mari ne sedi ments. I n many i nstances the i ron
content of the sedi ments i s even hi gh.erthan shoul d be expected, i ndi cat-
i ng addi ti on of i ron through physi cal , chemi cal , or organi c agenci es.
I n i nshore areas near the source of suppl y tbe total i ron content of the
water i s someti mes much hi gher than that found i n the open ocean.
Methods for the determi nati on of i ron i n sea water i n i ts vari ous forms
have been descri bed by Thompson and 13remner (1935a and b), Cooper
(1935), and Rakestraw, Mahnke, and Beach (1936).
Manganese i s apparentl y subject to concentrati on by mari ne organ-
i sms, Thompson and Wi l son (1935) have reported val ues between
0.02 and 0.2 mg-atoms/L (1 and 10 mg/L). The val ue ci ted by Gol d-
schmi dt (1937) i s 4 mg/L. I nterest i n manganese has been aroused by
the occurrence of manganese nodul es whi ch are wi del y di stri buted i n
certai n types of mari ne sedi ments, parti cul arl y i n the Paci fi c Ocean.
The quanti ty of copper present i n sea water probabl y l i es between
0.02 and 0.2 ~g-atoms/L (1 to 10 ~g/L) (Marks, 1938, Wattenberg, 1938).
Copper i s an essenti al consti tuent of many mari ne organi sms and i t i s
al so consi dered a factor i n the l i fe hktory of oysters, as a rel ati vel y hi gh
copper content of the water i s apparentl y necessary for proper devel op-
ment of the l arvae.
Much i nterest i s attached to the content of radi oacti ve elements i n
sea water, because deep-sea sedi ments are hi gh i n radi um, compared to
i gneous rocks, and i t i s consi dered that the enri chment must be due to
preci pi tati on from the water of radi um or i ts precursors. The radi um
content of sea water has been studi ed by many i nvesti gators, usi ng
vari ous techni ques, but i t i s onl y recentl y that methods have been suffi -
ci entl y refi ned to yi el d trustworthy resul ts. Studi es by Evans, Ki p,
and Moberg (1938) and by Pettersson and Rona (Foyn et cd, 1939) show
that the radi um content, measured by the radon emanati on techni que,
vari es between about 0.2 and 3.0 X 1013@/00 i n sea water of sal i ni ty
approxi matel y 35 /00.
The l ow val ues are found i n the surface l ayers,
and i t i s suggested that organi sms are responsi bl e for a sel ecti ve removal
of thi s el ement. Both groups of workers found that organi sms concen-
trate the radi um about one hundredfol d i n thei r soft ti ssues. Cal careous
structures show an i ncrease i n the radi um: cal ci um rati o over that i n the
water. The maxi mum val ue l i sted above-namel y 3.0 X 101$0/00
was found i n water i n contact wi th the sedi ments (Evans, Ki p, and
Moberg, 1938), and general l y the radi um content of the deeper waters
i s about 1 X 10-13O/OO.
Pettersson and co-workers (Foyn et al , 1939) have emphasi zed the
i mportance of searchi ng for the radi oacti ve precursors of radi um, as,thi s
el ement has the rel ati vel y short hal f-l i fe peri od of onl y 1690 years. Of
these el ements urani um and i oni um are probabl y the most i mportant,
but thus far onl y urani um has been exami ned. Karl i k (Foyn et at)
has anal yzed a number of sampl es from vari ous parts of the oceans and
obtai ned for oceani c water a mean val ue of 1.5 X 106 O/OO.Surface
waters have a somewhat l ower content than those from greater depths,
but Karl i k does not consi der that the data are sutl i ci entl y adequate to
show any di fferenti al removal . Studi es of the di l ute waters of the Bal ti c
Sea showed that the urani um content was a functi on of the sal i ni ty,
Foyn and Rona (Foyn et al) have sought for thorium i n sea water, but
have been unabl e to detect i t by the most refi nedmethods. By exami ni ng
very l arge sampl es they have fi xed an upper l i mi t of 0.5 X 108O/oofor
thi s el ement. Ol der and apparentl y l ess accwrate methods yi el ded
consi derabl y hi gher val ues.
The radi um content of mari ne sedi ments and the theori es concerni ng
the deposi ti on of radi um and i ts precursors are di scussedi n the chapter on
mari ne sedi mentati on.
Preparation of Artificial Sea Water
I t i s i mpossi bl e to prepare sol uti ons that exactl y dupl i cate the proper-
ti es of sea water because (1) the i ons (sal ts) i n whi ch the el ements occur
i n sea water are not al ways known, (2) el ements that occur i n sea water
i n smal l amounts are present as contami nants i n other compounds i n
quanti ti es whi ch may far exceed those that shoul d be added, and (3)
many of the sal ts whi ch must be added i n fai rl y l arge amounts are
hydroscopi c or contai n water of crystal l i zati on and are di ffi cul t to wei gh
accuratel y. The l atter di ffi cul ty may be parti al l y avoi ded by prepari ng
concentrated sol uti ons of these sal ts, determi ni ng thei r concentrati on by
chemi cal anal ysi s, and addi ng the requi red vol ume of the sol uti on.
Al though i t woul d be of great i nterest to prepare sol uti ons dupl i cati ng
al l the physi cal and chemi cal properti es of sea water, i t i s general l y
not essenti al . I n studi es of certai n of the physi cal -chemi cal properti es,
i t i s suffi ci ent to add to the sol uti on onl y the more abundant i ons. I n
other i nstancesfor exampl e, when chemi cal methods are to be stand-
ard~zedonl y one el ement or i on need be accuratel y known and other
i ons onl y approxi matel y. Furthermore, i n experi ments wi th mari ne
pl ants the major el ements may not have to be cl osel y control l ed, but i t
wi l l general l y be necessary to know the concentrati ons of the bi ol ogi cal l y
essenti al el ements that are normal l y present i n smal l amounts. I f
possi bl e, natural sea water shoul d al ways be used i n physi cal or bi ol ogi cal
studi es, but i n the l atter case i t i s someti mes desi rabl e to enri ch the
water wi th certai n of the pl ant nutri ents (p. 235). Rogers (1938) has
di scussed vari ous modi fi ed types of sol uti ons that are used i n experi -
ments on mari ne ani mal s.
I n tabl e 37 are gi ven three suggested formul ae for prepari ng sol uti ons
approxi mati ng the composi ti on of sea water. They have been adjusted
to yi el d sol uti ons of 19.00 0/00 chl ori ni ty. The reci pe of McCl endon
et ai (1917), which has been used quite extensively, contains the nitroge%
phosphorus, and silicon needed by marine plants. Additional elements
may be necessary but are probably always present as impurities. The
formulae of Brujewicz (Subow, 1931) and of Lyman and Fleming (1940]
contain only the major elements. The last-mentioned recipe corresponds
to the composition of sea water given in table 35. The other formul ae
have not been adjusted to the composi ti on presented i n earl i er secti ons of
thi s chapter. I n al l cases the reagents used shoul d be exami ned for
contami nants and, i f necessary, puri fi ed.
TmLE37
FORMWLAEFOR ARTI FI CI AL SEA WATER
McClendonet al (1917)
salt
Nail . . . . . . .
MgCl, . . . . . . .
MgSO,.. . . . .
Ca(x., .,...
KC1. . . . . . . .
NaHCO~. . . .
Nab. . . . . . .
H8B08. . . . . .
Na,Si OX.
Na,J3i ,0~. . . .
H8PO~..,,...
A12CI0.
NH,. .,...,.
Limo,. . . . . . .
g/kg
26.726
2.260
3.248
1.153
0.721
0.198
0.058
0.058
0.0024
0.0015
0.0002
0.013
0.002
0.0013
Total . . . . . ... 34.4406
Water to 1,000.0000
(cl = 19.00/00)
I
Brujewicz (Subow, 1931)
Salt
Nail . . . . . . . .
MgCl~. . . . . . .
MgSOA. . . . . .
Call, . . . . . . .
KCI. . . . . . . . .
NaHCO,.
Nab... ,. ...
26.518
2.447
3.305
1.141
0.725
0.202
0.083
34.421
Water to 1,000.000
-1
Lyman and Fleming (1940)
salt
Nail . . . . . . . . .
MgC12. . . . . . . .
Na&04. . .
CaC12. . . . . . . .
KC1. . . . . . . . . .
Nd3C0, . . . .
KBr . . . . . . . . . .
g/kg
23.476
4.981
3.917
1,102
0.664
0.192
0.096
0.026
0.024
0.003
HOBO, . . . . . . . .
SrC12. . . . . . . . .
Nab . . . . . . . . . .
I
34.481
Water to 1,000.000
DissolvedGases in Sea Water
Al l of the atmospheri c gases are found i n sol uti on i n sea water. I n
addi ti on to ni trogen and oxygen, the most abundant gases i n the ai r,
carbon di oxi de i s present i n l arge quanti ti es i n sea water, chi efl y combi ned
as carbonates and bi carbonates. Of the rarer gases, ammoni a, argon,
hel i um, and neon have been reported i n sea water, and hydrogen i s
undoubtedl y present i n mi nute quanti ti es. I n the absence of di ssol ved
oxygen, hydrogen sul phi de may be present, and i t i s possi bl e that i n
stagnati ng water other products of putrefacti ve decomposi ti on, such as
methane, may occur.
Because of i ts i mportance i n bi ol ogi cal processes the di ssol ved oxygen
di stri buti on i n the oceans has been exami ned i ntensi vel y. Besi des
bei ng an i ndex to the bi ol ogi cal hi story of the water, the general character
of the di stri buti on of oxygen i n the deeper water i s hel pful i n studi es of
currents and of mi xi ng processes. The carbon di oxi de di stri buti on i s of
equal bi ol ogi cal i mportance; i ts di scussi on begi ns on p. 192. Ni trogen
has not been studi ed very wi del y, as i t i s apparentl y chemi cal l y i nert.
Argon i s al so i nert, and i s someti mes i ncl uded wi th the ni trogen when the
di asol vod gases are determi ned gasometri cal l y. The presence of hel i um
and neon has been confi rmed by Rakestraw, Herri ck, and Urry (1939).
DETERMI ~A~I ONOF DI SSOLVEDGASES. The content of di s~ol ved
oxygen i s usual l y determi ned by the Wi nkl er method, whi ch depends
upon the oxi dati on of manganous hydroxi de by the di ssol ved oxygen.
When aci d i s added, the oxi di zed manganese reacts wi th potassi um i odi de
and sets free i odi ne, i n amounts equi val ent to the ori gi nal di ssol ved
oxygen content, whi ch i s determi ned by ti trati on wi th sodi um thi osul -
phatg. The Wi nkl er method i s si mpl e and extremel y accurate i f certai n
precauti ons are observed i n handl i ng the water sampl es and reagents
(Thompson and Robi nson, 1939).
Probl ems rel ati ng to the determi nati on of carbon di oxi de are di s-
cussed on p. 192.
Di ssol ved ni trogen cannot be determi ned by di rect chemi cal methods,
and hence gasometri c techni ques must be used. I n general , the sea-
water sampl e i s aci di fi ed and al l the gases are dri ven off by boi l i ng or by
appl yi ng a vacuum. The carbon di oxi de i s then absorbed i n al kal i ,
and the oxygen i s absorbed i n al kaI i ne pyrogal l oL The resi dual gas i s
someti mes consi dered as atmospheri c ni trogen, al though actual l y
there are other gases, pri nci pal l y argon, mi xed wi th i t. 13akestraw
and Emmel (1937) devel oped a method for determi ni ng the di ssol ved
oxygen and ni trogen content of sea water by fi r st extracti ng the gases
and removi ng the carbon di oxi de, then absorbi ng the oxygen on phos-
phorus and the ni trogen on mol ten l i thi um. The oxygen contents
determi ned i n thi s way agreed wi th di rect Wi nkl er anal yses. The ni tro-
gen determi nati ons on saturated water sampl es showed resul ts con-
si stentl y l ower than the saturati on val ues accordi ng to Fox (1907);
further studi es (Rakestraw and Emmel , 1938b) i ndi cate that Foxs
tabl es are sl i ghtl y i n error. The gases remai ni ng after the extracti on of
ni trogen are consi dered as argon.
The presence of hydrogen sul phi de can be detected by i ts character-
i sti c odor. A method for i ts determi nati on has been descri bed by Gaarder
(1916). Al though commonl y referred to as hydrogen sul phi de, a part, at
l east, wi l l not be present as free gas but as sul phl de or bi sul phi de of
some base. A hydrogen sul phi de system somewhat comparabl e to the
carbon di oxi de system must exi st, but i t has not yet been i nvesti gated.
The determi nati on of ammoni a i s d~cussed i n the secti on deal i ng
wi th ni trogen compounds.
The uni ts to be used i n reporti ng the concentrati ons of di ssol ved
gases are mg-atoms/L or (ml of gas at NTP)/L.
I n some cases i t i s of i nterest to know the excess or defi ci ency of the
concentrati on wi th respect to water of the same temperature and sal i ni ty
i n equi l i bri um wi th the normal dry atmosphere. The saturati on val ues
for oxygen and ni trogen are gi ven i n tabl es 38 and 39. I f the saturati on
val ues are known, the percentage saturati on may be cal cul ated. I n
certai n probl ems i t i s desi rabl e to know the parti al pressuresof the gases
di ssol ved i n a gi ven water sampl e, The factors for computi ng these
val ues are di scussed on p. 190.
TABLE38
SATURATI ONVALUESOF OXYGEN I N SEA I VAi ER(mlI L)*
FROM NORMAL DRY ATMOSPHERE
.,,
(Fox, 1607)
16
28.91 K.33
\
Chlorinity (0/0~
Salinity (O/OO;
Tempera-
ture (C)
17 18
30.72 32.52
15
27.11
20
36.11
8.39
7.97
7.07
6.35
5.79
5.31
4.86
4.46
I

8.76 8.64
8.32 8.20
7.36 7.26
6.60 6.52
6.00 5.93
5.50 5.44
5.06 5.00
4.63 4.58
9.01
8.55
7.56
6.77
6.14
5.63
5.17
4.74
8.89
8.43
7.46
6.69
6.07
5.56
5.12
4.68
8.52
8.08
7.16
6.44
5.86
5.38
4.95
4.52
* mg-atoms of oxygen per l i t6 = 0.08931Xml/L.
TABLE39
SATURATION VALUES OF NITROGEN N SEA WATER (ml/L)*
FROM NORMAL DRY AT: :OSPHERE
1938b)
(Rakestrawand.Emmel
\
Chlorinity (0/,,) 15
Salinity (O/O.)27.11
Tempera-
ture (C)
16
28.91
21
37.94
17
30.72
19
34.33
20
36.13
15.22
13.43
12.15
11.04
10.08
9.30
8.89
15.02
13.26
12.00
10.92
9.98
9.21
8.84
14.82
13.10
11.86
10.79
9.87
9.11
8.72
14.61
12.94
11,71
10.66
9.76
9.02
8.62
14.40
12.78
11.56
10.53
9.65
8.92
8.53
14.21
12.62
11,42
10.39
9.54
8.82
8.44
14.01
12.45
11.27
10.26
9.43
8.73
8.35
* mg-at oms of nitrogen per liter =. 0.08929Xxd[L.
The dissolved oxygen in the sea varies between zero and 0.75 mg-
atoms/L (about 8.5 ml/L), although in areas of low temperature and
intense photosynthesis the content may exceed this upper limit. Nitro-
gen, which is apparently unaffected by biological processes, varies
between 0.75 and 1.3 mg-atoxns/L (8,4 and 14.5 ml/L). The total
189
carbon di oxi de @ oceani c waters vari es between about 1.5 and 2.5
mg-atoms of C/L (34 and 56 ml /L). Argon vari es between 0.2 and
0.4 ml /L, and the content of hel i um and neon i n sea water i s about
1.7 X 10-4 ml /L. The l atter val ues apparentl y represent the saturati on
val ues. Hydrogen sul phi de, whi ch i s present i n the water under excep-
ti onal condi ti ons, may occur i n amounts of more than 1.0 mg-atom of
S/L (22 ml /L) (Strom, 1936).
FACTORSCONTROLL~N~ THE DI EWRI BUTI ON OF DI SSOLVEDGASES.
The fol l owi ng general factors control the di stri buti on of di ssol ved gases
i n the oceans: (1) temperature and sal i ni ty, whi ch determi ne the concen-
trati ons when the water i s at the surface and i n equi l i bri um wi th the
atmosphere, (2) bi ol ogi cal acti vi ty, whi ch markedl y affects the concentra-
ti ons of oxygen and carbon di oxi de, (3) currents and mi xi ng processes,
whi ch tend to modti y the effects of bi ol ogi cal acti vi ty through mass
movement and eddy di ffusi on.
Water i n contact wi th the atmosphere wi l l tend to reach equi l i bri um
ei ther by gi vi ng up or absorbi ng the i ndi vi dual gases unti l the water i s
just saturated. Al though the zone of contact i s a thi n one, convecti ve
movements due to cool i ng, evaporati on, or wi nd acti on may bri ng a
l ayer of consi derabl e thi ckness i nto equi l i bri um wi th the atmosphere.
Accordi ng to Henrys l aw the concentrati on, m, of a gas i n a l i qui d i s
rel ated to the parti al pressure, p, of the gas and to the character of the
gas and the l i qui d: m = c,p. The numeri cal vaI ue of c,, the coeffi ci ent of
saturati on (absorpti on), depends upon the uni ts for expressi ng the
concentrati on of the gas i n the sol uti on and i ts pressure, and upon the
chemi cal character of the gas and the temperature and sal i ni ty of
the water.
TABLE40
COMPOSITION OF NORMAL ATMOSPHERE
Gas
Percent of volume Partial pres-
or pressure sure, Torr
Nitrogen. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78.03 593.02
Oxygen. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20.99 159.52
Argon. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.94 7.144
C2wbond ioxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.03 0.228
Hydrogen, neon, helium. . . . . . . . . . . . . . . . . . . . . 0.01 0.088
100.00 760.000
I
Wi th the excepti on of water vapor the rel ati ve composi ti on of the
atmosphere can be consi dered for practi cal purposes as constant (tabl e
40). Thi s does not str i ctl y appl y to carbon di oxi de, rel ati vel y sl i ght
changes i n the parti al pressure of whi ch have a pronounced effect upon
the amount i n sol uti on, and hence upon the hydrogen i on concentrati on
and other properti es (p. 202). Because of the vari abi l i ty i n the water
vapor pressure, the saturati on i s al ways assumed to take pl ace from a
dry atmosphere at standard pressure, namel y, 760 Torr. The natural
fl uctuati ons and regi onal di fferences i n the atmospheri c pressure are
negl ected.
The sol ubl l i ti es of those gases, such as oxygen and ni trogen, whi ch
do not react chemi cal l y wi th the water or i ts di ssol ved sal ts decrease wi th
i ncreasi ng temperature and sal i ni ty. The sol ubi l i ti es of oxygen and
ni trogen i n sea water of di fferent sal i ni ti es over the normal range of
temperature were i nvesti gated by Fox (1907, 1909). Foxs val ues for
oxygen are sti l l the accepted standards, but hi s data for ni trogen have
been superseded by those of Rakestraw and Emmel (1938b). The
vol ubi l i ty of carbon di oxi de i s greater than that of oxygen and ni trogen
because i t reacts wi th the water. Part of the carbon di oxi de i s present
as free C02 and HAI Os, but i n sea water by far the greater part i s present
as carbonates and bi carbonate, and for the same parti al pressure the
total COZ content of sea water i s much greater than that of di sti l l ed
water or neutral sal t sol uti ons. The content of free COZ and HzCOs
decreases wi th i ncreasi ng temperature and sal i ni ty. Argon i s someti mes
i ncl uded wi th the ~atmospheri c ni trogen, and, because i ts sol ubi l i ty
di ffers from that of ni trogen, the val ues of the saturati on coeffi ci ents
wi l l be sl i ghtl y modi fi ed. Li ttl e i s known concerni ng the other gases
i n sea water; however, both hydrogen sul phi de and ammoni a are very
sol ubl e gases and thei r saturati on val ues can pl ay no i mportant part i n
thei r di stri buti on.
I n tabl e 41 are gi ven val ues of the saturati on coeffi ci ents (absorpti on
coeffi ci ents) for oxygen, ni trogen, and carbon di oxi de i n fresh and sea
water at di fferent temperatures. The val ues for oxygen are from Fox
(1909), as are al so the val ues for ni trogen i n di sti l l ed water. The other
ni trogen val ues are from Rakestraw and Emmel (1938b). The val ues for
carbon di oxi de (Buch et al , 1932) correspond to the total COZi n water of
zero al kal i ni ty or to the free COZand H&Os i n sea water. I t i s seen that
carbon di oxi de i s much more sol ubl e than the other two gases and that
oxygen i s about twi ce as sol ubl e as ni trogen.
Fr om tabl e 41 i t i s seen that wi thi n the range of chl ori ni ty normal l y
encountered i n the oceans the temperaturei s the most i mportant property
i nfl uenci ng the vol ubi l i ty (see al so tabl es 38, 39).
I n studi es of the di stri buti on of di ssol ved gases i n the sea i t i s general l y
assumed that, whatever the l ocati on of a water parti cl e, at some ti me
i t has been at the surface and i n equi l i bri um wi th the ai r. I n th&
studi es of the di ssol ved ni trogen content Rakestraw and Emmel (1938a)
have found that the water i s vi rtual l y saturated (referred to a normal
atmosphere), regardl ess of depth; therefore thi s assumpti on appears
%
191
192
val i d and al so i ndi cates that bi ol ogi cal acti vi ty i nvol vi ng ei ther fi xati on
or producti on of ni trogen cannot be suffi ci ent to affect si gni fi cantl y the
concentrati on of thi s gas i n the water, As the waters of the oceans
appear to have been saturated wi th oxygen and carbon di oxi de at some
stage i n thei r. hi story when they were at the surface, the di fferences
between the saturati on val ues (computed from the temperatures and
sal i ni ti es) and the observed contents are measures of the changes whi ch
have been effected by bi ol ogi cal agenci es. The factors i nfl uenci ng the
di stri buti on of carbon di oxi de are di scussed i n the fol l owi ng secti ons,
and the di stri buti on of di ssol ved oxygen wi l l be consi dered i n many pl aces
i n the ensui ng chapters.
The Carbon Dioxide System
Al though an extensi ve l i terature exi sts concerni ng the carbon di oxi de
system i n sea water, publ i cati ons pri or to about 1929 are now chi efl y
of hi stori c i nterest. The sol uti on of the probl ems i nvol ved awai ted
not onl y the devel opment of sui tabl e anal yti cal methods for the deter-
mi nati on of the total carbon di oxi de and the vari ous forms i n whi ch i t i s
present i n sea water, but al so the devel opment of the theory and methods
for studyi ng the hydrogen i on concentrati on and certai n general theori es
i n physi cal chemi stry. I n the bri ef di scussi on to fol l ow, onl y the sal i ent
features of the contemporary theori es wi l l be presented. These may be
adequate for many purposes, but the i nvesti gati ons are not yet cl osed.
Methods of anal ysi s requi re further refi nements, and i n many cases
fundamental constants must be more accuratel y determi ned,
Earl y i nvesti gators studyi ng the carbon di oxi de i n sea water attempted
to appl y methods si mi l ar to those used for fresh water, where the carbon
di oxi de i s l argel y present as free carbon di oxi de that can be dri ven oi l by
boi l i ng, by appl yi ng a vacuum, or by bubbl i ng through the water a
stream of COz-free gas. The use of such methods on sea water gave
vari abl e and confl i cti ng resul ts. I t was l ater found that i n order to dri ve
off al l the COZa strong aci d must be added to the water, i ndi cati ng that
at l east part of the carbon di oxi de was present as the carbonate or bi car-
bonate of some basi c cati on. Methods were then devel oped for the
determi nati on of the total carbon di oxi de and al so for measuri ng the
quanti ty present as carbonate and bi carbonate i ons. I t i s now consi dered
that the C02 can exi st i n the fol l owi ng forms i n sea water and that
under any gi ven set of condi ti ons equi l i bri a wi l l prevai l :
COz(di ssol ved) ~ H,CO, s HCO;(bi carbonate) ~ CO~(carbonate).
I f the gases i n sea water are dri ven off by some sui tabl e method,
the C02 present as di ssol ved gas wi l l be removed and the equi l i bri a wi l l be
di spl aced unti l vi rtual l y al l of the free COZand carboni c aci d are removed
and the bi carbonate i s al l converted to carbonate. I f a strong aci d i s
added to sea water, the equi l i bri a wi l l be di spl aced to~ard the free COZ;
consequentl y, i f suffi ci ent aci d i s added, al l the C02 i s set free and can be
determi nedei ther chemi cal l y or gasometri cal l y. I f an al kal i nesubstance,
such as sodi um hydroxi de, i s added to sea water, the equi l i bri a are shi fted
toward the carbonate, and the amount of carbonate i on wi l l be i ncreased.
Al though onl y a smal l fracti on of the free COZi s hydrated to form H1430~,
i n the fol l owi ng di scussi on the free C02 + H@OZ wi l l be referred to as
carboni c aci d and wri tten EI zCOS.
Fr om the foregoi ng dkwmssi oni t can be seen that the total COz i n
sea water does not fol l ow Henrys l aw for the sol uti on of gases i n inert
sol uti ons. Neverthel ess, the parti al pressureof the carbon di oxi de i n sea
water i n contact wi th the atmosphere wi l l tend to establ i sh equi l i bri um
wi th that i n the ai r. I f the pressurei s i ncreased the amount i n sol uti on
wi l l be greater, and i f i t i s reduced the quanti ty of C02 wi l l decrease.
The quanti ty present in a sampl e of water i n equi l i bri um wi th a gi ven
carbon di oxi de pressure wi l l depend on the concentrati on of carbon
di oxi de bound base and the temperature and sal i ni ty of the water sampl e.
I f these factors are kept constant, the parti al pressureof COZcan be used
as a measure of the total carbon di oxi de content of the water.
HYDRO~E~I ON CONCENTRATI ON (pH) OF SEA WATER. Sea water
i s normal l y al kal i ne. Si nce both the H+ and OH- i ons pl ay parts i n the
equi l i bri a, any understandi ng of the carbon di oxi de system requi res
knowl edge of thei r concentrati ons. Pure di sti l l ed water di ssoci ates
i nto hydrogen and hydroxyl i ons:
H20 ~ H+ + OH-.
The i oni c product [H+] X [OH], when the concentrati ons are
expressed i n chemi cal equi val ents per l i ter, vari es somewhat wi th tem-
perature, but at 25C i s 10-14(p. 198). I n pure water or i n any sol uti on
that contai ns equal concentrati ons of H+ and OH i ons, the sol uti on i s
sai d to be neutral . If the concentration of H+ i s i n excess of OH-, the
sol uti on i s aci d, and i f l ess i t i s rztkuline. The i oni c product i s a known
functi on of the temperature and sal t concentrati ons; hence, i f [H+] or
[OH-] i s known, the other can readi l y be cal cul ated. For expressi ng
the hydrogen i on concentrati on, a l ogari thmi c scal e i s commonl y used,
where pH i s the l ogari thm of the reci procal of the hydrogen i on con-
centrati on expressed as normal i ty; that i s, as equi val ents per l i ter,
pH = l og& Thus, a neutral sol uti on has a pH of approxi matel y 7,
an aci d sol uti on a pH l ess than 7, and an al kal i ne sol uti on a pH greater
than 7. I t shoul d be noted that a uni t change i n pH corresponds to a ten-
fol d change i n the hydrogen i on and hydroxyl i on concentrati ons.
The hydrogen i on concentrati on, or pH, of a sol uti on may be deter-
mi ned i n vari ous ways, but al l are essenti al l y ei ther el ectr ometr i c or
*
cal ori metri c. The hydrogen el ectrode, whi ch i s the standard for measur-
i ng hydrogen i on concentrati on, cannot be used for sea water, as i t
i nvol ves bubbl i ng gas through the sol uti on and, thus, di sturbance of the
carbon di oxi de equi l i bri um. Two other el ectr ometr i c methods are
avai l abl e-the qui nhydrone el ectrode and the gl ass el ectrode. The
qui nhydrone method i s not accurate i n the pH range normal l y encoun-
tered, and the gl ass el ectrode has not yet been extensi vel y appl i ed to the
study of sea water (Bal l and Stock, 1937, Buch and Nynti s, 1939).
Hence, vi rtual l y all of our knowl edge concerni ng the hydrogen i on con-
centrati on i n sea water i s based on cal or i metr i c methods.
Certai n organi c compounds cl assed as i ndi cators have the property
of changi ng col or over a gi ven range of hydrogen i on concentrati on.
So-cal l ed bi col or i ndi cators have one col or when i n an aci d sol uti on
and another col or when i n an {al kal i ne sol uti on. For any i ndi cator
the col or change takes pl ace over a defi ni te range i n pH, and, at the
hydrogen i on concentrati on that i s numeri cal l y equal to the di ssoci ati on
constant of the i ndi cator, equal quanti ti es of both col or phases are present
i n the sol uti on, The range i n pH for whi ch vari ous i ndi cators can be
used i s descri bed by Cl ark (1928), who al sogi ves i n detai l the methods for
prepari ng the i ndi cators. For sea water, cresol red and phenol red are
general l y used, as they cover the pH range normal l y found i n the sea.
When worki ng i n hi gh pH ranges, bromthymol bl ue i s commonl y used.
Three i mportant properti es of pH i ndi cators must be known before
they can be appl i ed to sea water: the di ssoci ati on constant of the i ndi ca-
tor, the effect of temperature upon thi s val ue, and the sal t error. The
presence of neutral i ons i n the sol uti on has a pronounced effect upon the
col or and, hence, upon the apparent pH as determi ned by i ndi cators.
Thi s i s known as the sal t.error. I n general , neutral sal ts i ncrease the
apparent dksoci ati on constant of the i ndi cator, and therefore gi ve l ow
pH readi ngs. I n practi ce a careful l y control l ed quanti ty of an i ndi cator
sol uti on i s added to a sampl e of sea water, and ei ther the col or devel oped
i s compared to a set of tubes contai ni ng the equi val ent quanti ty of
i ndi cator i n sol uti ons of known pH or the sampl e i s exami ned i n a bl col or-
i meter. The accepted cal or i metr i c techni que used for determi ni ng the
pH of sea-water sampl es and the correcti on to be appl i ed for sal t error
and temperature effects are descri bed by Buch (1937) and by Buch and
Nyni i s (1939). Because of the effects of changes i n temperature and
pressure upon the di ssoci ati on constants of carboni c aci d (p. 200) the
measured pH of a sea-water sampl e wi l l di ffer from the pH i n si tu. The
magni tude of the temperature correcti on i s gi ven by Buch (1937), and
the effect of pressureupon the pH has been studi ed by Buch and Gri pen-
berg (see Buch et uZ,1932).
The pH encountered i n the sea i s between about 7.5 and 8.4. That
i s, the hydrogen i on concentrati on ranges from 32 X 10-g to 4 X 10-9
.
equi val ents per l i ter. The hi gher pH val ues am general l y encountered
at or near the surface. Where the water i s i n equi l i bri um wi th the C02
i n the atmosphere, the PH i s between about 8.1 and 8.3, but hi gher val ues
may occur when the photosyntheti c acti vi ty of pl ants has reduced the
content of CO.2. Bel ow the euphoti c zone the pH shows a certai n
rel ati onshi p to the amount of di ssol ved oxygen i n the water. I n regi ons
where vi rtual l y al l the oxygen has been consumed, and consequentl y
where the total COSi s hi gh, as at depths of about 800 m i n the eastern
porti ons of the Equatori al and North Paci fi c, the pH approaches a
mi ni mum val ue of 7.5. Thi s i s a l i mi ti ng val ue, because no more COZ
can be formed. Bel ow the mi ni mum oxygen l ayer there i s general l y a
gradual i ncrease i n pH wi th depth. Under the pecul i ar condi ti ons that
may prevai l i n ti de pool s, bays, and estuari es, the pH someti mes exceeds
the val ues ci ted above. Furthermore, i n di l uted water and i n i sol ated
basi ns where H& i s produced the pH may approach 7.0 or even fal l i n
the aci d range.
ALKALI NI TYANDCARBONDI OXI DECOMPONENTS. The total amount
of carbon di oxi de i n sea water, present ei ther as free gas or bound, may
be determi ned gasometri cal l y after a strong aci d has been added to the
water to break up the carbonate compounds. Such a method has been
descri bed by Greenberg, Moberg, and Al l en (1932). I n order to deter-
mi ne the carbon di oxi de components--namel y,the amounts present as
carboni c aci d (i ncl udl ng the free COZ), bi carbonate, and carbonate-
ti trati ons must be made. For a gi ven sampl e of sea water the amount
of a strong aci d (usual l y HC1 about 0.01 normal ) necessary to reduce
the pH to about 4.5 i s i ndependent of the total COZ. Thi s amount of
aci d i s requi red to set free the weak aci ds whose ani ons have been bound
agai nst basi c cati ons. I t i s therefore not onl y a measure of the quanti ty
of ani ons of weak aci ds i n the sampl e, but al so of the cati ons bal anced
agai nst them. Thi s quanti ty, when expressed as the number of mi l l i -
equi val ents of hydrogen i ons (mg-atoms of H+) necessary to set free
the i ons of weak aci ds i n a vol ume of water whi ch at 20 has a vol ume of
1 L, i s known as the al kal i ni ty. Thi s quanti ty has al so been referred to
as the i?itratablebase, excess base, titration alkalinity, and bu$er capacity.
The ter m al kal i ni ty has been adopted as the standard desi gnati on by the
I nternati onal Associ ati on of Physi cal Oceanography (1939). I t shoul d
be noted that the ter m as here defi ned has no rel ati on to the hydroxyl
i on concentrati on or to the fact that sea water i s normal l y al kal i ne.
A number of methods have been suggested for determi ni ng the
al kal i ni ty, and these have been summari zed by Thompson and Robi nson
(1932) and Gri penberg (1937b). I n general , they fol l ow one of two
techni ques. Ei ther the ti trati on i s carri ed out i n the presence of the
carbon di oxi de, i n whi ch case the end poi nt i s taken at about 4.5, or
the carbon di oxi de i s dri ven off. I n the l atter case a hi gher pH, about
7.0, i s used. When the carbon di oxi de i s dri ven off, an excess of mi d may
be added, the sol uti on boi l ed to free i t of C02, and then the excess aci d
determi ned by ti trati on; or the measurementmaybe made di rectl y upon
the sampl e, whi ch i s hel d at the boi l i ng poi nt duri ng the ti trati on,
Another method has been to add a known quanti ty of aci d to the sampl e
of sea water and then to determi ne the pH (Mi tchel l and Rakestraw,
1933). I t has been i mpl i ed that al l of these methods wi l l gi ve the same
value for the al kal i ni ty, but thi s i s not necessari l y the case, and i t i s
hoped that a standard method wi l l be establ i shed,
The al kal i ni ty bears a fai rl y constant rel ati on to the chl ori ni ty.
The al kal i ni ty: chl orosi ty factor for surface water has been determi ned
by a number of workers and found to be cl ose to 0.120 when the al kal i ni ty
i s expressed i n ter ms of mi l l i gram-atoms. The desi gnati on speci fi c
alkalinity that has been used i n some cases is obtai ned by di vi di ng the
al kal i ni ty, as mg-atoms/L, by the chl ori ni ty, i n g/kg, but such a mi xed
rati o shoul d not be used. I n water from greater depths the rati o maybe
somewhat hi gher than that gi ven above, approachi ng an upper l i mi t of
0.125 near the sea floor (Wattenberg, 1933). I n bracki sh water the
rati o may be i ncreased tremendousl y i f the ri ver water i s hi gh i n bound
carbonate compounds. When the al kal i ni ty: chl orosi ty factor i s to be
used as an i ndex i n studi es of i ndustri al pol l uti on, the normal change
i n the rati o wi th concentrati on must first be establ i shed i n sampl es of
sea water di l uted wi th unpol l uted ri ver water. Observati ons by Moberg
and Revel l e (1937) and by Wattenberg (1936) have shown that i n oceani c
water the i ncrease i n the Ca: Cl factor wi th depth i s equi val ent to the
r i se i n the al kal i ni ty: Cl factor. Thi s i ndi cates that changes i n the
al kal i ni ty and calcium are of common origin-namely, precipitation or
solution of CaCOs. Further materi al concerni ng the regi onal vari ati ons
i n the,al kal i ni ty: chl orosi ty factor i s gi ven on p, 208.
Because vari ati ons i n the al kal i ni ty: chl orosi ty factor i n oceani c
water are associ ated wi th correspondi ng changes i n the cal ci um: chl orosi ty
factor, the cal ci um content of the water may be computed from the
al kal i ni ty by the fol l owi ng expressi on:
al kal i ni ty
Ca(mg-atoms/L) = z ~ 0.465 X chl orosi ty.
Thi s procedure for esti mati ng cal ci um has been fol l owed by Wattenberg
(for exampl e, Wattenberg, 1936).
I t may be seen that the al kal i ni ty: chl orosi ty factor of 0.1205 i s the
same as the HCOZ: Cl factor gi ven i n tabl e 35, when the bi carbonate
i s expressed as mi l l i gram-atoms of carbon per l i ter, The reason for thi s
i denti ty i s that, i n prepari ng the tabl e, i t was assumed that the pH of the
water was such that onl y bi carbonate i ons were present and, hence,
woul d be equi val ent to the al kal i ni ty.
I n di scussi ons of the carbon di oxi de system i n sea water, the concen-
trati ons of the components have commonl y been gi ven i n mi l l i mol es per
l i ter. These are numeri cal l y i denti cal wi th concentrati ons gi ven as
mg-atoms/L of carbon.
Sal ts of weak aci ds contai ni ng the fol l owi ng el ements are known to
occur i n sea water: carbon, boron, phosphorus, arseni c, and si l i con. Of
these, sal ts of carboni c and bori c aci d onl y are present i n suffi ci ent
concentrati ons to affect the magni tude of the al kal i ni ty. For the present,
we shal l negl ect the bori c aci d, whi ch does not afl ect the al kal i ni ty deter-
mi nati on and whi ch has to be consi dered i n the carbonate system onl y
at hi gher pHs. The al kal i ni ty may then be taken as a measure of the
concentrati on of bi carbonate and carbonate i ons, and
[.4] = [HCOZ] + 2[C071,
where the brackets i ndi cate mol ar conceri trati ons-that i s, gram-atoms of
carbon per l i ter. The [HZC08] may be determi ned by ti trati on wi th
sodi um hydroxi de and the [CO;] by ti trati on wi th aci d, usi ng careful l y
control l ed end poi nts. The method i s descri bed by Greenberg, Moberg,
and Al l en (1932). I t i s shown l ater that the concentrati on of ei ther
HZCOSor CO; wi l l be negl i gi bl e when the other i s present i n si gni fi cant
quanti ti es. Therefore we may wri te:
[2(3OJ = [HzCO,] + [HCO;]
and [A] = [HCO~],
or
[zCo,] = [IIco;] + [co;] and
[Al = [HCO;I + fWO;l.
By substi tuti ng i n these equati ons the measured quanti ti es, the other
components may be obtai ned.
Studi es of the carbon di oxi de system based on measurementsmade by
these methods have been reported by Greenberg, Moberg, and Al l en
(1932) and Moberg, Greenberg, Revel l e, and Al l en (1934). I n fi g. 38
are shown verti cal di stri buti on curves for the carbon di oxi de components,
total carbon di oxi de cal cul ated from the ti trati ons and by di rect gaso-
metr i c measurements, and the al kal i ni ty at a stati on off the coast of
southern Cal i forni a. The total COZ obtai ned by the two methods
agrees very wel l and shows a general i ri creasewi th depth. I n the upper
l ayers there i s an appreci abl e amount of CO;, but thw decreases to zero
at 200 m, and bel ow thi s l evel HzCOa occurs i n quanti ti es whi ch i ncrease
wi th depth. The al kal i ni ty i s i ndi cated for the upper 200 m, bel ow
whi ch i t corresponds, of course, to the curve showi ng the amount of
HCOF. The i ncrease of al kal i ni ty wi th depth maybe partl y due to the
bi ol ogi cal preci pi tati on of CaCO&i n the upper l ayers, but i n thi s area
i t i s pri nci pal l y associ ated wi th the i ncreasi ng sal i ni ty.
We shal l now proceed to a d~cussi on of the l aws governi ng the
equi l i bri a between the vari ous carbon di oxi de components, the al kal i ni ty,
198
ari d the parti al pressureof COZ. Thus far i t has been assumed that the
al kal i ni ty was a measure of the equi val ents of HCO~ and CO~ i ons and
of the cati ons bound agai nst them, but thi s concept must be modi fi ed
somewhat. Hydrogen and hydroxyl i ons must al sobe taken i nto account,
and, at the hi gher pHs, the bori c aci d as wel l . Si nce bori c aci d i s a
(HCO;O; COZ) + 1.S 1.9
00
Of?+-(CG!+,C%) m (w$&L i%) = *
I
~i
-------k
. ..-
-ALKALINITY
HCO;
too -
XOZ (TITR)
; 200
g
i
g 300 -
I
- H*Co>
i
400 -
~
i
5000
! 1 1 I I 1 I I ( 1 i I 1 I
1.0 2.0 30 4,0 42 46 4s
COtimti)
w 52
Fig. 38. Vertical distribution of the all&dinityand carbon dioxide components
off southern California.
weak aci d, onl y the fi r st d~soci ati on stage need be consi dered. The
bal ance between the i ons wi th whi ch we are concerned maybe wri tten
[-41+ [H+] = [HCO;] + 2[C07] + [HzBO;] + [OH-].
I f we i ndi cate the porti on of the base (al kal i ni ty) di rectl y bound to the
carbon di oxi de components as Aco$, the rel ati onshi p may be wri tten
(Buch, 1933a,b)
where al l concentrati ons are i n gram-atoms per l i ter. K~ is the apparent
fi r st di ssoci ati on constant of bori c aci d i n sea water at the parti cul ar
temperature and sal i ni ty prevai l i ng, and Kw i s the i oni c concentrati on
product of water, [H+] X [OH], under si mi l ar condi ti ons. Accordi ng to
Buch (1938) the i oni c product i n sea water at 20 can be computed from
the fol l owi ng equati on:
pKw = 14.170 0.1517 @ + 0.0083 Cl.
pKw decreases by about 0.035 for each l -degree r i se i n temperature
(Dorsey, 1940). The expressi on pKw ,bars the same rel ati on to Kw $
that pH does to [H+] and i s the l ogari thm of the reci procal of the i oni c
product. The same conventi on i s used i n expressi ng di ssoci ati on con-
stants, The total concentrati on of bori c aci d [ zH8B08] can be obtai ned
from the chl orosi ty:
[2H,B0,] = 0.0221 X chl orosi ty X 10-s.
Accordi ng to Buch the di ssoci ati on constant of bori o ttci d can be
expressed as
pKj = 9.22 0.123@ 0.0086 Cl .
The correcti on to be appl i ed to the al kal i ni ty to obtai n Ace, i s appreci abl e
at the hi gher pH)s, as can be seen I I
from fi g. 39, where the quanti ti es S -
are gi ven ae mi l Eequi val ents per
0.4 -
l i ter.
$03
The equati on for the fi r st di s- ~ ~-
soci ati on constant of carboni c ~
~02-
aci d i s
0.1-
[H+] X [HCOFI = K{,
[HzCO,]
o
?0 80 pH 90 no
and for the second:
Fi g. 39. Concentrations ofhydroxide-
bound (AOE-)and borate-bound
[H+] X [Cozl = IK4,
(AH,ti,-) base as a function of pH in
[HCOY]
water of (21= 19.00/00at 20C.
where tl i e brackets i ndi cate mol ar concentrati ons.
By i ntroduci ng the
rel ati onshi ps
[Am,] = [HUM+ Zco;l
and [zC02] = [H2CO~]+ [HCO;I + [COFI,
i t i s possi bl e to el i mi nate HCOF and CO; from the above equati ons and
obtai n them i n the fol l owi ng form:
[H+l X [A.CO,]
(1+%) 2c02] -(l+i%)xJ4coJ=K
H+lx{(l+%)x~col- ~col}:K!
Z[ZC021 - Mm,]
2.
Extensi ve i nvesti gati ons have been carri ed out to determi ne the
magni tudes of K( and K;. These studi es have been reported by Buch,
Harvey, Wattenberg, and Gri penberg (1932), and by Moberg, Greenberg,
Revel l e, and Al l en (1934). Buch and others have fol l owed up the work,
usi ng more refi ned methods and theori es. Accordki g to Buch et al
(1932),
pK; = 6.47-0.188 ~ at 20C.
Correcti ons for temperature can be computed from the fol l owi ng expres-
sirms:
Near 20C, ApK~ = 0.006A8.
Near 5C, ApK~ = 0.009A0.
The effect of hydrostati c pressure, as expressed by means of the depth
Az i n meters, on the fi r st di ssoci ati on constant i s
ApK; = 0,48 X 10-4Az,
Buch (1938) found that the second di ssoci ati on constant of carboni c aci d
i n sea water at 20C may be computed from the fol l owi ng equati on:
p& = 10.288 0.443 {~ 0.0046 Cl.
Over the normal range of chl ori ni ty i n sea water a si mpl er expressi on i s
adeauate---namel v.
.,
px: = 10.35 0.498 &t% ;
The temperature and pressurecorrecti ons are
ApK; = 0.Ol l AO(at 200).
ApK~ = 0.012A8(at 50).
ApK: =
0.18 X 10-4Az.
For any gi ven set of condi ti ons, as expressed by means of temperature,
sal i ni ty, pressure, al kal i ni ty, and pH, the val ues of ACOZand K; and K:
can be cal cul ated. Fr om these the total carbon di oxi de and i ts vari ous
components can be computed from the fol l owi ng equati ons (Revel l e,
1934):
I n fi g. 40 are shown the vari ati ons i n the carbon di oxi de components
wi th pH, cal cul ated from the equati ons gi ven above for sea water of
Cl = 19 @/oo at $ = 20C, and at atmospheri c pressure. The COZ
components are gi ven as mg-atoms/L of carbon and as ml /L of COZ.
The parti al pressure of carbon di oxi de i s rel ated to the amount of
free CO* -1-H.ZCOS(i ndkated as HzCOa; see p. 190) i n the sol uti on:
[H,COJ
PCO*=
c, x lo~
The val ue of c, (p. 191) depends upon the temperature and sal i ni ty and
the uni ts used for expressi ng the concentrati on and parti al
tyo Ifto 1(0 0+ TQrr 0.?1
5.0 P
0.1 0.01 aool O.WOI At mos o.00001
1
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zc~
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/
%-.
0.0-.---.r-.-.-.-,-,_ .-.T-.-.-?M
. .. .....
- 0
qo 70 pH & eb
Iqo
pressure.
Fig. 40. Carbon dioxide components in sea water of
CI = 19.00O/Ooat ZOOCas a function of pH and the partial
pressure of carbon dioxide.
I n fi g. 41 are shown curves for c. at dti erent temperatures and chl ori ni -
ti es, where they represent the anmunt of I GCO$, i n mi l l i gram atoms of
carbon per l i ter of sea water, i n sol uti on under the desi gnated condi ti ons
when the parti al pressure of CO* i s 1 physi cal atmosphere (760 Torr).
At 20 and 19 0/00Cl , %i s 34.2. That i s, a parti al pressureof one atmos-
phere of CO*woul d be i n equi l i bri um wi th a sol uti on. contai ni ng 34.2
mi l l i gram-atoms of carbon as free COz + HzCO~. The data are from
Buch et al (1932).
The vari ati ons i n poo, wi th the other components i s shown i n fi g, 40.
The range i s from l ess than 0.01 to greater than 100 Torr (0.1 X 10-4 to
1000X 10-4 atm). The rel ati onshi p over the pH range normal l y
encountered i n seawater i s shown i n the i nset di agrami n fi g. 40. Between
pH 7.5 and 8.3, pco, decreases from 1.4 to 0.15 Torr (18.0 to 2.0 X 10-4
atm). The average parti al pressureof COZi n the ai r i s about 0.23 Torr;
hence surface sea water of Cl = 19.0 0/00at 20 wi l l have a pH of 8.2 i f
80,
t I 1 i I
I
Fig. 41. Absorption coefficient (c,) of
carbon dioxide in sea water as a funotion of
temperature and Chlorinity.
i t i s i n equi l i bri um wi th the
atmosphere,
Sea water i s a very favor-
abl e medi um for the devel -
opment of photosyntheti c
organi sms. I t not onl y con-
tai ns an abundant suppl y of
CO.Z,but removal or addi ti on
of consi derabl e amounts re-
sul ts i n no marked changes of
the parti al pressure of C02
and the pH of the sol uti on,
both of whi ch are properti es
of i mportance i n the bi ol ogi cal
envi ronment (p. 268). I f the
C02 avai l abl e- for photosyn-
thesi s i s assumed to be H2C08 + ~HCOZ, 0.48 mg-atoms of carbon per
l i ter may be removed from water of Cl = 19 0/00wi th an i ncrease of the
pH from 7.5 to onl y 8.5. I n di sti l l ed water or i n an i nert sal t sol uti on
of zero akal i ni ty i ni ti al l y at pH 7.5, the total C02 woul d be about one
seventh of that amount.
BUFFERACTI ONOF SEA WATER. I f a smal l quanti ty of a strong
aci d or base i s added to pure water, there are tremendous changes i n the
numbers of H+ and OH- i ons present, but the changes are s-mal l i f the
aci d or base i s added to a sol uti on contai ni ng a weak aci d and i ts sal ts
or a weak base and i ts sal ts. Thi s repressi on of the change i n pH i s
known as bu.fer action, and such sol uti ons are cal l ed bujler solutions.
Sea water contai ns carboni c and bori c aci ds and thei r sal ts and i s, there-
fore, a buffer sol uti on. Let us consi der onl y the carbonate system.
Carbonate and bi carbonate sal ts of strong bases, such as occur i n sea
water, tend to hydrol yze, and there afe al ways both H+ and OH- i ons
i n the sol uti on. I f an aci d i s added, carbonate i s converted to bi carbonate
and the bi carbonate to carboni c aci d, but, as the l atter i s a weak aci d
(onl y sl i ghtl y di ssoci ated), rel ati vel y few addi ti onal hydrogen i ons are
set free. Si mi l arl y, i f a strong base i s added, the amount of carbonate
i ncreases, but the OH- i ons formed i n the hydrol ysi s of the carbonate
i ncreaseonl y sl i ghtl y. The bufferi ng effect i s greatest when the hydrogen
CHEMISTRYof SEA WATER 203
i on conoentra.ti on i s equal to the di asooi ati on constant of the weak aci d
or base-that i s, when the concentrati on of the aci d i s equal to that of
i ts sal t.
CYCLEOF C02 B~TWEE~SEA ANDATMOSPHERE.I nvesti gati ons of
the parti al pressure of C02 i n the ocean and the atmosphere have been
made by Krogh (1904) and Buch (1939a,b). The fol l owi ng i nternal
changes wi l l i ncrease or decrease the pmi i n the surface l ayer:
Increase pm, Decrease pm,
1. Ri se i n temperature 1. Decrease i n temperature
2. Ri se i n sal i ni ty (evaporati on) 2, Decrease i n sal i ni ty
3. Respi rati on 3. Photosynthesi s
4. Preci pi tati on of CaCOa 4. Sol uti on of CaC08
5. Deep water brought to surface
The parti al pressureof COZi n the surface water can be computed wi th
suffi ci ent accuracy when the temperature, sal i ni ty, al kal i ni ty, and JPH
are known, but, before a better understandi ng of the C02 exchange
between the sea and the atmosphere can be obtai ned, a far more com-
prehensi ve study of the parti al pressure of the atmospheri c C02 must
be made. Buch (1939b) has reported a number of di rect observati ons
on the C02 content of the ai r whi ch i ndi cate that pol ar ai r i s rel ati vel y
l ow i n COZ (pc& = 0.23 Torr), compared to conti nental and tropi cal
ai r (pmt = 0.25 Torr). I t has been suggested that i n l ow l ati tudes the
ai r i s enri ched wi th COZfrom the ocean and that the general atmospheri c
ci rcul ati on carri es the COSi nto hi gh l ati tudes. There i t agai n dksol ves
i n the sea water, whi ch i n ti me bri ngs i t back toward the Equator.
ACTIVITYOF IONS IN SEA WATER. The apparent first and second
dksoci ati on constants of carboni c aci d and the fi r st di ssoci ati on constant
of bori c aci d i n sea water are l arger than i n di sti l l ed water and i ncrease
wi th i ncreasi ng sal i ni ty. That i s, the strength of these aci ds appears to
be greater, i n sol uti ons contai ni ng sal ts. These phenomena can be
accounted for on the theory of acti vi ty i ntroduced by Lewi s and Randal l
(1923) and devel oped mathemati cal l y by Debye and I I uckel . I n a
sol uti on contai ni ng a mi xture of el ectrol ytes, such as sea water, there i s a
mutual i nterference of the i ons, so that thei r acti vi ty or abi l i ty to par-
ti ci pate i ndependentl y i n some reacti on i s much reduced. Most chemi cal
determi nati ons measure the total cbneentrati on of some i on and not i ts
acti vi ty; however, certai n physi cal measurements show the acti vi ty.
For exampl e, el ectromoti ve force determi nati ons i nvol ve the acti vi ty
of the hydrogen and other i ons. Si mi l arl y, the measurement of the
vapor pressure of a sol uti on of a nonvol ati l e compound i s an i ndi cati on
of the acti vi ty of the sol vent. The acti vi ty wi l l be l ess than that of the
pure sol vent under si mi l ar condi ti ons. The parti al pressure of d~sol ved
gases i s a measure of thei r acti vi ty.
204
The acti vi ty coeffi ci ent y i s rel ated to the acti vi ty a of an i on as i n the
fol l owi ng exampl e:
~=+x [H+] = a=+.
Hence, a~+i s the acti vi ty of the hydrogen i ons expressed as gram-atoms
per l i ter and [H+] i s the stoi chl ometr i c concentrati on,
I n the studi es of the carbon di oxi de system i n sea water, the total
C02, al kal i ni ty, and carbon di oxi de components are measured chemi cal l y,
and hence the val ues represent the stoi chi ometr i c val ues and not the
acti vi ti es. On the other hand, the hydrogen i on concentrati on i s deter-
mi ned cal ori metri cal l y or el ectrometri cal l y, and these methods yi el d the
acti vi ty of hydrogen i ons di rectl y. Therefore, i n the equati ons rel ati ng
the CO..Zcomponents a~+ coul d have been i nserted i nstead of [H+].
The di ssoci ati on constants have been referred to as apparent di ssoci ati on
constants, i n contrast to the thermodynamic constants that would be
obtained at infinite dilution, where the activity coefficients (y) are unity.
The apparent dissociation constants are indicated by the symbol prime
()for example, @.
I?or carbonic acid the thermodynamic second
dissociation constant can be written
~2 = C&+ x ~~(),- x [CO*-]
THCO,-X [HCO;-]
and thi s i s rel ated to the apparent di ssoci ati on constant (Moberg et al,
1934):
pK2 = pK; + log ~-.
.
Similarly,
pKz = pK; + log -.
The val ue of 7E,c0, depends upon the relative volubility of COZin
pure water and in sea water at the same temperature and upon the
activity of the water in the two cases:
The subscri pt o i ndi cates val ues at i nfi ni te di l uti on, and the subscri pt s
the val ues at the concentrati on under consi derati on. The val ues of
coand c, can be obtai ned from fi g. 41, and e, and eo(the vapor pressures)
can be computed (p. 67).
Fr om the empi ri cal equati ons rel ati ngpK[ and pK~to the temperature
and chl ori ni ty, we know that at 20 and zero chl ori ni ty the thermo-
dynami c val ues are pKl = 6.47 and pKz = 10.288, and, at 19.00 0/00Cl ,
pK{ = 5.97 and pK~ = 9.02. 13y substi tuti ng these val ues and Y~@O,
CHEMISTRYOf SEA WATER 205
(i n thi s case 1.131), i t i s possi bl e to determi ne the acti vi ty coeffi ci ents for
the carbonate and bi carbonate i ons. Thi s substi tuti on yi el ds
%coa-
= 0,36,
Ycma-
= 0,019.
Thus, i n sea water of 19.00 O/OoCl at 20, onl y about one thi rd of the
bi carbonate and one fi fti eth of the carbonate i ons are acti ve. Thi s
wi l l be consi dered agai n wi th reference to the vol ubi l i ty of CaCOS.
Empi ri cal equati ons have been presented whi ch rel ate pK{ and pK~
to the cube root of the chl ori ni ty. I t has been shown (Buch et al , 1932,
Moberg et al, 1934) that these equati ons are general l y val i d for sal t
sol uti ons other than sea water i f the i oni c strength i s used i nstead of
chl ori ni ty as a measure of concentrati on. The i oni c strength (p) of a
sol uti on i s obtai ned by fi r st mul ti pl yi ng the concentrati on of each
i ndi vi dual type of i on, i n mol es per ki l ogram of sol vent water, by the
square of i ts val ence, and then taki ng hal f the sum of these products
(Lewi s and Randal l , 1923, p. 373). Lyman and Fl emi ng (1940) have
shown that the i oni c strength of sea water i n the normal range of con-
centrati on may be computed from the expressi on
P
= 0.00147 + 0.03592 Cl + 0.000068 C12.
Moberg et al (1934) have summari zed the perti nent data, but no sati s-
factory expressi ons have yet been devel oped to show the manner i n
whi ch the acti vi ty coeffi ci ents of the di fferent i ons i n sea water change
wi th concentrati on.
VOLUBI LI TYOF ClaCOS. The sol ubl l i ty of an el ectrol yte, such as
cal ci um carbonate, may be expressed by a volubility product. The vol u-
bi l i ty product i s i denti cal wi th the i oni c product (i f concentrati ons are
expressed as mol es per l i ter) when the sol uti on i s i n equi l i bri um wi th the
sol i d sal t and, therefore, saturated. The val ue of the vol ubi l i ty product
depends upon temperature, the concentrati on of other i ons (sal i ni ty), and
the hydrostati c pressure. I f, under a gi ven set of condi ti ons, the i oni c
product i s kwsthan the vol ubi l i ty product, the sol uti on i s undersaturated;
i f the i oni c product i s greater the sol uti on i s supersaturated, and i f
sui tabl e nucl ei are present, preci pi tati on wi l l proceed unti l the i oni c
product equal s the vol ubi l i ty product.
The vol ubi l i ty product of CaCO@C.W,) i n di sti l l ed water at 20 i s
5.0 X 10-g. I n sea water of chl ori ni ty 19.00 O/OO and at the same tem-
perature, the cal ci um content i s 10,23 mg-atoms/L, and at pH 8.2 the
carbonate i on concentrati on i s 0.26 mg-atoms/L of carbon. Therefore
the i oni c product i s
[Ca++] X [COF] = 10.23 X 0.26 X 10-6 = 2.66 X 10-,
whi ch i s 530 ti mes greater than the sol ubi l i ty product i n di sti l l ed water.
I f vol ubi l i ty data for dkti l l ed water are to be appl i ed to sea water, i t i s
necessary to take the acti vi ty of the i ons i nto account. I t has been
shown (p. 205) that the acti vi ty of the COTi ons i s about 0.02, and i ntro-
duci ng thk correcti on reduces the apparent supersaturati on to about
tenfol d. Si nce no data are yet avai l abl e for the acti vi ty of the Ca++
i ons i n sea water, i t i s i mpossi bl e to appl y vol ubi l i ty products determi ned
for di sti l l ed water to test the rel ati ve saturati on of cal ci um carbonate
and other sal ts i n sea water.
I t i s therefore necessary to determi ne empi ri cal l y the concentrati ons
of Ca++and COZ that can exi st i n contact wi th sol i d CaCOS. Worki ng
at 30 and i ncreasi ng the COTcontent by l oweri ng the total C02, Revel l e
and Fl emi ng (1934) obtai ned preci pi tati on of CaCOg as aragoni te needl es
and s~herul i tes. The cal ci um content of the ~ol uti on was determi ned
.
9XI0-,
1 t ,
6?dC# -
P
& -
Q
.
T
& -
3xlo- -
b
06.0 70 8.0 PH 9.0 10.0
Fig. 42. Ioni~ product [Ca++]X
[COS-]in sea water of Cl = 19.000/00at
20C as a function of ~H. The hori-
di rectl y, and the CO? was cal cu-
l ated from measurements of the
pH, al kal i ni ty, and chl ori ni ty.
The average of three experi -
ments gave K&eo8 = 2.4 X 10-8
at 30C. Wattenberg has carri ed
out a number of studi es on the
sol ubl l i ty of cal ci um carbonate i n
sea water. Hi s general procedure
was to add CaCO~crystal s to sea
water, and i n some i nstances to
i ncrease the pcos. The sea-water
sampl es were then pl aced i n seal ed
fl asks and agi tated unti l equi l i b-
ri um was establ i shed. The cal ci -
zontal lines indicate the volubilityproduct
urn content of the water was
according to Wattenberg (0.62 x 10-s),
and according to Revelle and Flernin~
(3.2 X 10-).-
pH determi nati ons.
l owi ng val ues for the
18.5 to 19.5 0/00:
Temperature, C O
Kk800,. . . . . . . . . 8.1
cal cul ated from the al kal i ni ty
measurements (p. 196), and the
COTwas obtai ned wi th the ai d of
Wattenberg and Ti &merman (1936) gi ve the fol -
apparent vol ubi l i ty product i n sea water of Cl =
5 10 15 20 25 30 35
7.9 7.4 6.8 6.2 5.5 4.7 3.8 X 10-7
At 30 Wattenbergs val ue i s onl y one fi fth of that obtai ned by Revel l e
and Fl emi ng. No sati sfactory expl anati on of thi s di fference has yet
been offered. I n fi g. 42 the i oni c product i n sea water of Cl = 19.00 0/00
at 20 i s pl otted agai nst pH. The val ue of K&co$ for thi s temperature
obtai ned by Wattenbergnamel y, 0.62 X 10-Qwoul d i ndi cate that
supersaturati on exi sts at al l pHs above about 7.5. Surface water i n
equi l i bri um wi th the atmosphere haa a pH of about S.2 and woul d be
about si xfol d supersaturated. The K&cot obtai ned by Revel l e and
Fl emi ng, on the other hand, i f corrected to 20, woul d be 3.2 X 10-$,
whi ch woul d i ndi cate that surface water i s about saturated wi th CaCO~
under these condi ti ons. I t hardl y seems l i kel y that surface sea water
can be as hi ghl y supersaturated as Wattenbergs val ues woul d i ndi cate.
As an expl anati on i t has been suggested that the cal ci um carbonate may
not be free as i ons but may be present i n some compl ex, or possi bl y m
coI l oi dal cal ci um carbonate. On the other hand, i t may be that the
empi ri cal l y determi ned val ues of I&co$ are not appl i cabl e to sea water
because of l ack of equi l i bri um or faul ty experi mental techni que. Further
studi es must be made before these poi nts can be deoi ded.
Smi th (1940) has investigated the cal ci um carbonate deposi ti on that
takes place in the shallow waters overlying the Bahama Banks. He
found the alkalinity to be much reduced, and from measurements he
computed the ionic produet, [Ca++] X [COZ]. Mi ni mum val ues of the
product that he consi ders approach the vol ubi l i ty product were found to
fal l between the val ues of Revel l e and Fl emi ng and those of Wattenberg.
Acoordi ng to Wattenberg (1936), K&Co, at 20 changes wi th the
chl ori ni ty i n the fol l owi ng way:
Cl)voo . . . . . . . . . . . . . . . ..o 5 10 15 20
Kc*Co, . . . . . . . . . . . . . . . . . . 0.05 1.8 4.0 5.0
6.2 x 10-T
That i s, i n sea water the apparent vol ubi l i ty product of CaCOs i ncreases
wi th chl ori ni ty and decreases wi th temperature.
Revel l e (1934) and Wattenberg (1936) consi der that hydrostati c
pressure has no si gni fi cant effect upon the val ue of K&m,. However,
i t shoul d be remembered that, because of changes i n the di ssoci ati on
constants of carboni c aci d, pressure does modi fy the rel ati ve amounts of
13CO~ and COT i n the water. Hence, water that i s saturated at the
surface wi l l be sl i ghtl y undersaturated i f subjected to hydrostati c pres-
sure, even i f the total CO~ and cal ci um contents remai n unal tered.
Conversel y, bottom water sa@rated wi th (2aC08 will be supersaturated
when brought to the surface.
Al though our knowl edge of the val ues of K&@o,under di fferent condi -
ti ons i s i ncompl ete and uncertai n, i t i s possi bl e to show the effect of
changes i n the condi ti ons upon the i oni c product, thus obtai ni ng an
understandi ng of those agenci es that wi l l favor preci pi tati on or sol uti on.
Revel l e (1934) has shown that, i n surface water, i ncrease of the sal i ni ty
and the temperature, and decrease of the pmi that i s, the total COs
contental l tend to i ncrease the i oni c product and therefore favor
preci pi tati on. The sal i ni ty effect i s rel ati vel y smal l , and hence areas of
hi gh or ,ri si ng temperature and of acti ve photosynthesi s wi l l be those
where preci pi tati on of CaCO~i s most l i kel y to occur. Opposi te condl -
ti ons wi l l favor sol uti on.
In the deep water the range i n temperature and sal i ni ty i s smal l , and
therefore the vari ati ons i n pco, wi l l have the most pronounced effect.
Accordi ng to Wattenbergs studi es (1933) the deep waters of the Atl anti c
Ocean are vi rtual l y saturated wi th cal ci um carbonate. Areas over-
l yi ng red cl ay show sl i ght undersaturati on, and those overl yi ng cal -
careous deposi ts (gl obi geri na ooze) show ei ther saturati on or sl i ght
supersaturati on.
Certai n types of cal careous sedi mentary materi al , both recent and
fossi l , do not show any evi dence of organi c ori gi n. These are someti mes
consi dered to be chemi cal deposi ts. I n certai n areas, mi croorgani sms
undoubtedl y pl ay an i mportant part i n establ i shi ng condi ti ons that
resul t i n the i nci dental preci pi tati on of carbonates. I n tropi cal seas,
thi s process may occur i n shoal -water areas, coral reefs, l agoons, and
mangrove swamps (Fi el d, 1932). Al though mi croorgani sms can produce
condi ti ons favori ng the preci pi tati on of cal ci um carbonate, i t i s con-
si dered that they are effecti ve agents i n thi s process onl y i n and on the
sedi ments i n the envi ronments l i sted above. Smi th (1940) has found
that over the Great Bahama Bank CaC03 i s preci pi tated, under con-
di ti ons of heati ng and excessi ve evaporati on, on nucl ei suppl i ed by the
sedi ments. The fi nel y di vi ded CaCO~i n certai n deep-sea sedi ments i s
thought to ari sefrom the break-down of the shel l s of forami ni fera (p. 982)
and not from preci pi tati on i n situ.
DISTRIBUTION OF ALKALINITY, pH, AND CARBON DIOXIDE COM-
PONENTS. I n the precedi ng di scussi on i t has been assumed that the
al kal i ni ty: chl orosi ty factor i s constant, and the val ue 0.1205 (mi l l i -
equi val ents per uni t Cl ) has been used i n computati ons. Thi s i s i n
agreement wi th the average of a l arge number of observati ons made by
Wattenberg (1933) i n the Atl anti c Ocean and those reported by Revel l e
(1936) for the upper l ayers of the Paci fi c Ocean. Wattenbergs val ue i s
commonl y gi ven as the speci fi c al kal i ni tynamel y, as mi l l i equi val ents
per uni t chl ori ni ty, i n whi ch case i t i s 0.123. A number of di fferent
methods (p. 195) have been empl oyed fm measuri ng al kal i ni ty, but
there i s no defi ni te proof that they al l yi el d si mi l ar val ues. Hence, i t i s
di ffi cul t to compare the resul ts obtai ned from vari ous parts of the oceans
by dbl erent workers. However, the fi ndi ngs of Wattenberg (1933),
Mi tchel l and Rakestraw (1933), and Revel l e (1936) al l show that there
i s a somewhat hi gher al kal i ni ty: chl orosi ty factor i n the deeper water
than there i s i n the surface l ayers. The i ncrease i n the factor usual l y
amounts to about 0.005. Wattenberg exami ned a number of water
sampl es col l ected i mmedi atel y over the bottom, and i n these he found
an even l arger factor. The l ow val ues i n the surface waters are ascri bed
to removal of cal ci um carbonate by organi sms possessi ng cal careous
skel etons. Smi th (1940) has suggested that, at l east i n certai n l ocal i ti es,
there may be-i norgani c preci pi tati on i f sui tabl e nucl ei are present when
the wai er i s undergoi ng heati ng and evaporati on. Whether or not
cal ci um carbonate di ssol ves agai n whi l e si nki ngthrough the water col umn
depends upon the degree to whi ch the water i s saturated wi th thi s com-
pound. The producti on of CO~ by metabol i c acti vi ty at subsurface
l evel s wi l l favor sol uti on. Thi s producti on al so occurs i n the sedi ments
and probabl y accounts for the sharp i ncrease i n al kal i ni ty i mmedi atel y
over the bottom, whi ch was detected by Wattenberg. Revel l e (1936)
has offered evi dence whi ch i ndi cates that the al kal i ni ty: chl orosi ty factor
i s hi gher i n the North Paci fi c Ocean than i t i s i n the Atl anti c. The
greater al kal i ni ty may be attri buted to the l ower dksol ved oxygen con-
tent of the i ntermedi ate and deep waters of the North Paci fi c. The
l ower oxygen content i s i ndi cati ve of a hi gher content of carbon di oxi de,
and hence greater sol ubi l i ty of cal ci um carbonate. Wattenbergt~ data
i ndi cate that the vari ati on i n the al kal i ni ty: chl orosi ty factor wi th
depth i s much l ess i n hi gh l ati tudes, where organi sms wi th cal careous
skel etons are l ess abundant or are l ackl ng and where verti cal mi xi ng
produces more uni form condi ti ons. That the change in al kal i ni ty i s
anal ogous to vari ati ons i n cal ci um content of the water has been poi nted
out by Moberg and Revel l e (1937). Ri ver water contai ns rel ati vel y
l arge proporti ons of cal ci um carbonate, and i n regi ons of marked di l uti on
there are great i ncreases i n the al kal i ni ty: chl orosi ty factor. I t may
al so be modi fi ed by the formati on and mel ti ng of sea i ce (p. 216).
The pH of sea water i n contact wi th the ai r wi l l vary between about
8.1 and 8.3, dependi ng upon the temperature and sal i ni ty of the water
and the parti al pressure of carbon di oxi de i n the atmosphere. I n areas
of great di l uti on l ower val ues may occur. At subsurface l evel s, where
exchange of carbon di oxi de wi th the atmosphere i s i mpossi bl e, the pH
wi l l vary wi th the extent to whi ch the COZcontent of the water i s mod-
i fi ed by bi ol ogi cal acti vi ty. I n the euphoti c ~one, hi gher pHs are
usual l y found; bel ow thi s they decrease to a mi ni mum correspondi ng i n
general to the l ayer of mi ni mum oxygen content, and then i ncrease
agai n toward the bottom. Al though vari ati ons i n the sal i ni ty affect
the pH, the predomi nant factor i s the total carbon di oxi de content or i ts
parti al pressure.
Unfortunatel y, di fferences i n techni que and i n the constants used i n
arri vi ng at pHs from cal or i metr i c measurements make i t di ffi cul t to
compare the resul ts of di fferent workers. The most extensi ve studi es
made, on the di stri buti on of pH i n the oceans are those of the Meteor
(Wattenberg, 1933) i n the Atl anti c Ocean and those of the Carnegi e i n
the Paci fi c Ocean. The dktri buti ons of pH and di ssol ved oxygen al ong a
l ongi tudi nal profi l e i n the eastern Atl anti c Ocean are shown i n fi g. 43.
The rather cl ose si mi l ar i ty of the i sol i nes can easi l y be seen, and si mi l ar
patterns woul d be gi ven by the parti al pressure and total COt content,
al though i n thk case the rel ati ons woul d be i nverse ones. The tempera-
ture and salinity of the water are of secondary importance in determining
the pH. In the North Pacific, where the oxygen content is low at
intermediate and greater depths, when compared to the Atlantic, the
pH is somewhat lower and approaches 7.5 where the oxygen content is
reduced to less than a few tenths of a milliliter per liter.
In stagnant
basins (Strom, 1936) where large amounts of H&! are present, the pH
may approach 7.0. The total COZ content of water in contact with the
air is chiefly dependent upon the alkalinitythat is, the salinity--and
Fig. 43. Distribution of @I and dissolved oxygen in the eastern part of the
Atlantic Ocean. The locations of the sections are shownin the ma~ on the left-hand
. si de. The verti cal and hori zontal scales are di fferent i n the two- secti ons. (After
Wattenberg.)
to some extent upon the temperature. Regional variations in the partial
pressure of carbon dioxide in the atmosphere may cause some variations.
13elow the surface the total carbon dioxide content and, hence, the
magnitude of the different components are primarily determined by the
changes in the carbon dioxide content resulting from photosynthesis or
respiration. If the temperature, salinity, and depth, and two of the
following variablespH, alkalinity, or p~o,are known, all components
may be computed from equations given on p. 200.
Volubility of Salts in Sea Water
The vol ubi l i ty of cal ci um carbonate i n sea water has been exami ned
i n some detai l , but rel ati vel y l i ttl e i s known about the other consti tuents.
Because of the compl ex nature of sea water and the effect of other i ons
upon the acti vi ty of any one, the sol ubi l i ty product of a si ngl e sal t i n
di sti l l ed water cannot be appl i ed to sea water. Cooper (1937b) consi ders
that most of the i ron i n sea water i s not i n true sol uti on, but i s present
i n some col l oi dal form, as the vol ubi l i ty product for the hydroxi de i s
extremel y smal l . Wattenberg and Ti mmernumn (1938) studi ed the
sol ubti ti es of magnesi um and stronti um carbonates and magnesi um
hydroxi de i n Beawater. The data i n tabl e 42 are from thei r work. I t i s
i nteresti ng to note the great i ncrease i n the apparent sol ubfi l ty produots
i n sea water, whi ch i s due to the reduced acti vi ty of the parti ci pati ng
i ons. For compari son, the i oni c products for sea water (19.00 0/00Cl ,
?3= 20) at pl i l 8.2 have been computed.
The apparent supersaturati on
of the cal ci um carbonate i s di scussed i n the preodi ng pages. The i oni c
products of the other sal ts do not approach thei r vol ubi l i ty products.
At pH hi gher than 9.o the i oni c product of Mg(OH)2 will exceed the
sol ubi l i ty product, and hence removal of C!O~may resul t i n preci pi tati on
of magnesi um hydroxi de as wel l as t~e carbonates.
Thompson and hi s co-workers (for exampl e, I gel srud and Thompsop,
1936)have carri ed out extensi ve phase-rul estudi es of sol uti ons contai ni ng
some of the sal ts i n sea water, but so far they have not extended thei r
i nvesti gati ons to natural water.
Some i ndi cati on of the great sol ubti l ty of the major consti tuents
i s afl orded by data on the separati on of sal ts when sea water i s frozen
(p. 217). Somewhat si mi l ar data may be obtai ned from the evaporati on
stud~esby Usi gl i o (Thompson and Robi nson, 1932), whi ch agai n bri ng out
the fact that sea water i s far from saturated wi th most of the consti tuents.
TABLE42
THE VOLUBI LI TYPRODUCTSOFGERTAI NSALTSI N DI STI LLEDWATER
AND SEA WATER
(From Wattenberg and Timmermann, 1938)
K
salt Di sti l l ed
water
CaC08 . . . . . . . . . . . . . . . . . . . . . . . . . 0.5x 10-$
MgCOs.3H20................... 0.1 x 10-~
SrCOa. . . . . . . . . . . . . . . . . . . . . . . . . . 0.3 x 10-
Mg(OH)Z....................... 1 x 10-1
K
Sea water
S==352;40,
.
50 x 10-S
3.1 x 10-4
500 x 10-9
5 x 10-11
Ionio produot
cl = 19.0~lw,
o = 20
pH = 8.2
270 x 10-S
0.14 x 10-4
39 x 10-9
0.02 x 10-11
The Oxidation-Reduction Potential of Sea Water
The oxi dati on-reducti on potenti al i s a measure of the abi l i ty of one
chemi cal system to oxi di ze a second. I t i s general l y expressed i n vol ts
rel ati ve to the normal hydrogen el ectrode. Those substances or sol uti ons
havi ng hi gh potenti al s are abl e to oxi di ze those wi th l ower potenti al s.
Al though consi derabl e work has been done on the oxi dati on-reducti on
potenti al s i n l i vi ng organi sms, l i ttl e i s known about the condi ti ons
prevai l i ng i n the water. The potenti al i n sea water has been consi dered
212
by Cooper (1937a) to be associ ated onl y wi th the parti al pressure of
oxygen and the pH of the water. Under condi ti ons of l ow oxygen
content or when hydrogen sul phi de i s present, organi c compounds
d~sol ved i n the water may have to be consi dered. The oxi di zi ng or
reduci ng condi ti ons must be consi dered i n two parts: namel y, the intenmty
as expressed by the potenti al , and the capacity, or the poi si ng of the
system, whi ch i s a measure of the abi l i ty to oxi di ze or reduce a certai n
amount of materi al wi thout si gni fi cantl y changi ng the potenti al . The
poi se of an oxi dati on-reducti on system i s somewhat anal ogous to the
bufferi ng capaci ty i n hydrogen i on concentrati on. The oxi dati on-
reducti on potenti al i s general l y determi ned el ectrometri cal l y, al though
i n certai n cases speci al cal or i metr i c i ndi cators can be used (Mi chael i s,
1930, Hewi tt, 1937).
The oxi dati on-reducti on potenti al of the envi ronment i s i mportant
to organi sms. So-cal l ed aerobi c bacteri a thri ve at a Kl gher potenti al
than mi cro-aeropbi l es, and anaerobi c bacteri a can exi st onl y when the
potenti al i s l ow. Hence, i n stagnant water and muds where there i s no
oxygen and the potenti al i s l ow, onl y anaerobi c forms can exi st. The
potenti al i s al so of geol ogi cal i mportance, as the character of certai n of
the consti tuents of the sedi ments wi l l be determi ned by the prevai l i ng
oxi di zi ng or reduci ng condi ti ons (p. 996).
InorganicAgenciesAffecting the Compositionof Sea Water
The factors that may modi fy the absol ute and the rel ati ve concen,
trati ons of the substances i n sea water are exchange wi th the atmosphere-
i nfl ow of ri ver water, freezi ng and mel ti ng of sea i ce, and bi ol ogi cal
acti vi ty. Bi ol ogi cal processes and thei r effects upon the dktri buti on of
vari ous el ements are consi dered i n chapter VI I .
EXCHANGEWI THTHEATMOSPHERE.The dktri buti on of sal i ni ty i n
the oceans, and hence the concentrati ons of the major el ements, i s mai n-
tai ned by agenci es that are descri bed el sewhere, but one poi nt must be
consi dered at thi s ti me. Over the sea and al ong i ts shores, spray i s
conti nual l y bei ng swept up i nto the ai r, and as the spray representsactual
parti cl es of sea water with its dissolved salts, this process affords a
mechanism for the removal of salts from the sea. A large portion of the
spray undoubtedly falls back into the water or is carried down by rain
(Kohler, 1921). However, winds blowing toward the land will carry
with them their content of salt, which may be deposited on the land
directly or carried down by the rain. Observations by Jacobs (1937)
on the chloride content of the air near the sea showed concentrati ons
rangi ng between 0.07 and 0.5 mg of chl ori de per cubi c meter of ai r. The
amount i ncreased wi th the wi nd vel oci ty and was greatest wi th onshore
wi nds.
A consi derabl e proporti on of the di ssol ved materi al carri ed to the
sea by ri vers i s <cycl i c sal t- that i s, sal t that has been carri ed i nl and
by the atmosphere and then deposi ted or carri ed down by rai n and snow
(Cl arke, 1924, Knopf, 1931).
Besi des the exchange of sal ts that takes pl ace between the atmosphere
and the ocean as descri bed above, there i s an exchange of di ssol ved
gases and ni trogen compounds whi ch may modi fy the quanti ty of these
substances present i n sea water that i s i n contact wi th the atmosphere.
The factors that affect the exchange of gases are descri bed el sewhere.
The exchange of water between the atmosphere and oceans was taken up
i n chapter I V.
Rai n water contai ns rel ati vel y hi gh concentrati ons of ni trogen
compounds, whi ch are bel i eved to be formed from the consti tuents of the
atmosphere by el ectri cal dkwharges; hence the atmosphere suppl i es to
the ocean, ei ther di rectl y through rai nfal l or i ndi rectl y through run-off
from the l and, a certai n amount of fi xed ni trogen. Whether thi s i ncre-
ment i n the amount of fi xed ni trogen i s bal anced by deposi ti on of organi c
ni trogen i n sedi ments or by the l i berati on of gaseous ni trogen through
the decomposi ti on of ni trogen compounds i n the sea i s not yet known.
EFFECTS OF RIVERS ON THE COMPOSITION OF SEA WATER. The
run-off from l and i s but a part of the cycl e of l eachi ng. The preci pi tati on
on the l and contai ns onl y the cycl i c sal ts, dksol ved atmospheri c gases,
and ni trogen compounds. Thi s water acts upon the rocks, contri buti ng
to the mechani cal break-down of the sol i d materi al and extracti ng from
them thei r more sol ubl e consti tuents. The nature and quanti ty of the
vari ous el ements di ssol ved depends upon the character of the r ocks
or soi l s wi th whi ch the water comes i n contact on i ts way to the sea.
Because the l eachl ng i s carri ed out by water of l ow sal t concentrati on
yet rel ati vel y hi gh i n carbon di oxi de compounds, i t i s capabl e of di ssol vi ng
materi al s that woul d not pass i nto sol uti on i f they were i n contact wi th
sea water. I n addi ti on to dksol ved materi al , ri vers carry to the sea
col l oi dal and parti cul ate materi al i n tremendous quanti ti es. A con-
si derabl e part of thi s debri s i s dropped to the sea bottom near shore, and
much of the fi ner materi al coagul ates and settl es when mi xed wi th sea
water. Sea water reacts i n vari ous ways wi th the col l oi dal and fi nel y
di spersed materi al , and some of these reacti ons may affect the rel ati ve
composi ti on of the di ssol ved consti tuents. I nteracti on between the
di ssol ved consti tuents of sea water and the sedi mentary debri s may be
subdi vi ded as fol l ows: (1) sol uti on of the consti tuents of the sedi ment,
(2) adsorpti on on the sedi ment, (3) i oni c exchange, and (4) reacti ons to
form new substances. Li ttl e i s known concerni ng the i mportance of
these processes.
Fr om the magni tude of the l and area drai ned by ri vers emptyi ng
i nto the sea and from the composi ti on of the sal ts di ssol ved i n ri ver waters,
Cl arke (1924) has esti mated that ri vers contri bute to the sea each year
2.73 X 10smetr i c tons of d~sol ved sol i ds. By wei ghti ng the composi ti on
of the water of di fferent ri ver systems i n proporti on to the total suppl y of
di ssol ved materi al , he obtai ned the average composi ti on of ri ver water
shown i n tabl e 43. Compari son wi th the composi ti on of the d~sol ved
sol i ds i n sea water shows, when referred to the hal i des, that there i s an
excess of al l of the substances reported. Hence, the effect of ri ver waters
wi l l be to modi fy the rel ati ve composi ti on of the di ssol ved sol i ds i n sea
water. Possi bl y a rel ati vel y l arge proporti on of the carbon di oxi de and
ni trate shoul d be regarded as cycl i c. I n addi ti on, i t shoul d be recal l ed
that the cycl i c sea sal ts, carri ed i nto the atmosphere as spray and then
deposi ted or carri ed down by preci pi tati on onto the l and, wi l l enter the
compi l ati on. I f we assume that al l of the chl ori de i n the ri ver water i s
cycl i c, the amounts of the other el ements must be modi fi ed i n the propor-
ti ons i n whl eh they occur i n sea water. I t i s hardl y possi bl e that thi s
assumpti on i s enti rel y correct, but i t may yi el d val ues that are cl oser to
the truth. The average composi ti on of ri ver water adjusted i n thi s
way for cycl i c sal ts i s i ncl uded i n the tabl e.
TABLE43
PERCENTAGE COMPOSITION OF DISSOLVED SOLIDS
IN RIVER AND SEA WATER
Ion
(207.. . .. . . . . . . . . . . . . . . . . . . . . . . . . .
SOY. .. . . . . . . . . . . . . . . . . . . . . . . . . . . .
N;+.., . . . . . . . . . . . . . . . . . . . . . . . . . . .
K+. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
(Fe,Al)~O,. . . . . . . . . . . . . . . . . . . . . . . .
Si02. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Sr++, H8BOa,Br- . . . . . . . . . . . . . . . . .
Ri ver water
(wei ghted
average)
35.15
12.14
5.68
0.90
20.39
3.41
5.79
2.12
2.76
11.67
......
100.00
Sea water
0.41(HCO;)
7.68
55.04
i .i i
3.69
30.62
1.10
.............
o.ii
[00.00
Ri ver water
less cyclic
salts)
35.13
11.35
0. 00
2:%
3.03
2.63
2.02
2.75
11.67
. . . . .
89.75
I t i s not known whether the addi ti on of di ssol ved sol i ds bri ngs about
progressi ve changes i n the rel ati ve composi ti on of the sea sal ts or whether
there i s any progressi ve al terati on of the total sal t content or sal i ni ty.
I n any event, both processes must be exceedi ngl y sl ow. The total
amount of di ssol ved sol i ds contri buted by the ri vers each year i s onl y an
i nfi ni tesi mal fracti on, 5.4 X 10-8, of the total dksol ved sol i ds i n the ocean,
CHEWSTRY OF SEA WATER 215
Even thi s smal l fracti on does not represent a net gai n, as there are many
processes whi ch remove materi al from sol uti on. Certai n el ements
accumul ate i n the mari ne sedi ments and are preci pi tated ei ther through
physi cal reacti ons or by bi ol ogi cal acti vi ty. Thi s i s parti cul arl y true
of the cal ci um and magnesi um carbonate whi ch form cal careous deposi ts
and of the si l i con whi ch i s found i n organi c si heous deposi ts (radl ol ari an
and di atom oozes). The sodi um and potassi um may ,be removed from
sol uti on by adsorpti on on, or i oni c exchange wi th, the, cl ay parti cl es
brought to the sea by ri vers. However, i n the l atter case some other
el ement wi l l be rel e~ed to the water i n equi val ent amounts. Other
aspects of thi s probl em are consi dered i n connecti on wi th mari ne sedh
ments and geochemi stry, but i t must be admi tted that most questi ons
rel ated to changes i n composi ti on of sea water are sti l l unsol ved. I n
deal i ng wi th these i t must al so be consi dered that the amount of water
may be ohangi ng. Essenti al l y, al l the ri ver water i s cycl i c, but i t i s
known that juveni l e water of subterranean ori gi n i s conti nual l y bei ng
added to the surface water. I n addi ti on, the amount of water repre-
sented by the i ce caps may be vari abl e. Gol dSchmi dt (1933) has esti -
mated that for each square centi meter of the earths surface there are
2731 of water subdi vi ded as fol l ows:
Seawater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...268.45 1
Fresh water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.1
Conti nental i ce. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.5
Water vapor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.003
The average composi ti on of the ri ver water i s of i nterest i n consi deri ng
the effect on the oceans as a whol e and over l ong peri ods, but parti cul ar
i nvesti gati ons must be concerned wi th the effects brought about by
i ndi vi dual ri vers whose dwol ved sol i ds may cl i ffer markedl y i n com-
posi ti on and concentrati on from the average. Datae can be obtai ned
from Cl arke (1924) or si mi l ar sources; as an i l l ustrati on, val ues for
several of the l arge Ameri can ri vers are gi ven i n tabl e 44.
Fr om these exampl es i t can be seen that the composi ti on of i ndi vi dual
ri vers may di ffer consi derabl y from the average. Thus, the Col umbl a
Ri ver i s l ow i n chl ori de and the Col orado Ri ver i s hi gh, and the l atter
ri ver i s hi gh i n sodi um and sul phate and bel ow average i n cal ci um and
carbonate. The effect that di l uti on wi l l have upon the chl orosi ty faotors
wi l l therefore depend upon the character of the ri ver water.
Thus far we have consi dered onl y the more abundant el ements i n
the ri ver water. Undoubtedl y, al l el ements are carri ed to the sea
ei ther i n sol uti on or as fi nel y di vi ded parti cul ate materi al . The hi gh
producti on of pl ant and ani mal l i fe whi ch frequentl y occurs near the
mouths of ri vers has someti mes been ascri bed to the pl ant nutri ents
i ntroduced by the ri vers. Ri l ey (1937) hae found that the Mi ssi ssi ppi
Ri ver water contai ns hi gher concentrati ons of phosphate and ni trogen
compounds than the surface sea water i n the Gul f of Mexi co, and that
thi s has a di rect effect upon the amount of l i fe i n the waters off the
mouth of the ri ver. Fr om studi es i n the Engl i sh Channel , Atki ns (1923)
concl uded, on the other hand, that the ri ver water had l i ttl e effect upon
the i mmedi ate producti on, as most of the nutri ents were used up by
organi sms l i vi ng i n the ri vers.
EFFECTSOF FORMATI ONANDMELTI NGOF SEA I CE ON THE Coi w-
POSI TI ONOFSEAWATER. A l aboratory study of the freezi ng of sea water
was made by Rhger, whose resul ts have been reported by Krummel
(1907) and Johnstone (1928). I n these experi ments sea water was
TAZLE44
PERCENTAGECOMPOSI TI ONOFDI SSOLVEDSOLI DSI N RI VERWATERS
(Data from Clarke, 1924)
I I
I on Aver age
Mi ssi ssi ppi Col umbi a
Ri ver Ri ver
co?. .. . . . . . . . . . . . . . . . . . . . . . 35.15 34.98 36.15
so; . . . . . . . . . . . . . . . . . . . . . . . . 12.14 15.37 13.52
cl- . . . . . . . . . . . . . . . . . . . . . . . . . 5.68 6.21 2.82
NO; . . . . . . . . . . . . . . . . . . . . . . . . 0.90 1.60 0.49
Cab++. . . . . . . . . . . . . . . . . . . . 20.39 20.50 17.87
Ma++. . . . . . . . . . . . . . . . . . . . . . .
3.41 5.38
Na+
4.38
. . . . . . . . . . . . . . . . . . . . 5.79
K+
1
8.33*
8.12
. . . . . . . . . . . . . . . . . . . . . . . . . 2.12 1.95
(Fe,Al),O, . . . . . . . . . . . . . . . . . . . 2.75 0.58 0.08
Si09. . . . . . . . . . . . . . . . . . . . . . . . 11.67 7.05 14.62
Annual contribution of dissolved solids
(metric tons) . . . . . . . . . . . . . . . . . . . . . . . 100,000,000 19,000,000
Salt content (g/1). . . . . . . . . . . . . . . . . . . . . 0.166 0.0924
*Sum.
Col orado
Ri ver
13.02
28.61
19.92
i o:35
3.14
19.75
2.17
. . . . . . . . . .
3.04
13,416,000
0.702
cool ed i n the l aboratory, and at vari ous temperatures bel ow the i ni ti al
freezi ng poi nt the i ce and preci pi tated sal ts were separated from the
mother l i quor. Sea water of sal i ni ty 35.0 0/0, begi ns to freeze at 1.91C
(p. 66). At fi rst, pure i ce crystal s separate, and, as the concentrati on
of the bri ne i s i ncreased, the temperature must be further reduced to
bri ng about the formati on of addi ti onal i ce. AS the temperature i s
l owered and the concentrati on of the bri ne i s i ncreased, the vol ubi l i ty of
certai n of the di ssol ved sal ts i s exceeded. At 8.2 the NaJSXl )k begi ns
to separate and conti nues to do so wi th further cool i ng. At 23 the
NaCl begi ns to crystal l i ze. I n addi ti on, a certai n amount of CaC08
preci pi tates. Ri ngers anal yses of the i ce (i ncl udi ng the i ce crystal s
and the preci pi tated sal ts) and the bri ne when the temperature had been
reduced to 300 are as fol l ows:
CHEMtSTRYOF SEA WATER 217
one ki l ogram of sea water, i ni ti al sal i ni ty 35.05 O/oo,yi el ded:
Iceerystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...931.9 g
NaClcrystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20.23
Na&30tcrystaI s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.956
CaCO~mystal s.., . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Trace
Bri ne . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43.95
The bri ne contai ned 23.31 g of H20 and
Nab+. . . . . . . . . . . . . . . . . . . . . . . . . 1.42g cl-...........................7.o3g
Mg++. ,.. .l . . . . . . . . . . . . . . . . . ..l .31 Br- . . . . . . . . . . . . . . . . . . . . . . . ...0.08
K+ . . . . . . . . . . . . . . . . . . . . . . . . . .. O.38 SO~. . . . . . . . . . . . . . . . . . . . . . . . .. O.O3
ca++ . . . . . . . . . . . . . . . . . . . . . . . ..o.39
From these data it is readily seen that, when the temperature of the ice
and brine is lowered to 30, there are marked differences in the relative
composition of the salts in the ice and in the brine. If the cooling is
continued to 50, there is further separation of ice and salt crystals, but
some very concentrated brine is still present.
From these experiments it would appear that the formation of sea
ice might have a pronounced effect upon the relative composition of the
salts in the water, The brine from which it formed would be modified in
one direction, and, if melting took place in water other than that from
which the ice formed, the effect would be in the opposite direction.
However, the formation of sea ice in nature is not reproduced by these
laboratory experiments. Let us suppose that, in a region where the
depth to the bottom is moderate or great, sea water of normal composition
is subjected to cooling at the surface. The resulting increase in density
gives rise to convection movements that continue until the water at the
surface reaches the freezing point, and then ice will begin to form. The
brine, being of greater concentration but having virtually the same
temperature, will sink and new water will be brought toward the surface
and into contact with the ice. At first, isolated, elongated ice crystals
are produced, but as the freezing continues these forma matrix in which a
certain amount of the brine is mechanically included. The ice crystals
themselves are at this stage probably pure ice. If the freezing proceeds
rapidly, the brine will accumulate in separate cells within the body of the
ice and, as the temperature of the ice near the surface is reduced, more
i ce crystal s are formed, the cel l s decreme i n si ze, and the concentrati on
of the bri ne i n the cel l s i ncreases (fi g. 16, p. 72). Thi s may conti nue so
far that sol i d sal ts crystal l i ze i n the cel l s. Fr om this it can be seen that
there is not necessarily any relative change in the composition of the
dissolved salts in the sea water and in the sea ice (ice crystals plus the
enclosed brine).
The salinity of the ice, using the same definition as applied to sea
water, has been shown to depend upon the rate of freezing. Malmgren
(1927), from the observations made by the ik?aud Expedition, gives the
fol l owi ng average val ues showi ng the rel ati on between the sal i ni ty of new
i ce and the ai r temperature, where the l atter i s used w a measure of the
rate of freezi ng.
Air temperature tlalinitg of ice
(c)
(/00)
16 . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . 5.64
28 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.01
30 . . . . . . . . . . . . . . . . . . . . . . . ....... . . . 8.77
40. ,,, ,,, .,, , .,, ., .,, ., ...,..., .,,,,.,.,,,. 10.16
The sal i ni ti es are based upon chl ori ni ty determi nati ons made on sampl es
of the mel ted i ce. The sal i ni ty of the surface water was about 30 /oo.
The effect of the rate of freezi ng i s al so shown by the anal yses of sampl es
obtai ned i n Apr i l from an i ce fl oe that had started to form the precedi ng
November:
Distance from surface of ice (cm). . . . 0 13 82
Salinity of ice (O/,,),. . . . . . . . . . . . . . . . . 6.74:.28 5.31 2~.84 4:.37 3.48 9~.17
The l ower sal t content of the deeper i ce i s rel ated to the sl ower rate of
formati on. When i ce i s formed wi th extreme rapi di ty, i ts sal i ni ty wi l l
approach that of the water from whi ch i t i s produced.
Accordi ng to Rkg&s experi ments the cool i ng of i ce contai ni ng cel l s
of bri ne l eads to formati on of addi ti onal i ce crystal s and, i f the tempera-
ture i s reduced suffi ci entl y, to separati on of sal t crystal s wi thi n the i ce.
Wi th very rapi d freezi ng, bri ne and sal t crystal s may accumul ate on
the surface of the i ce, maki ng the surface wet at temperatures of
30 to - 40C and greatl y i ncreasi ng the fri cti on agai nst sl ed runners
or ski s.
I n such rapi dl y frozen i ce the cel l s contai ni ng the bri ne are l arge or
numerous. I f the temperature r i ses, the i ce surroundi ng thp cel l s mel ts
and the separated sal t crystal s are di ssol ved, but before compl ete sol uti on
has taken pl ace the bri ne cel l s may joi n, permi tti ng the bri ne to tr i ckl e
through the i ce. Under these condi ti ons some of the sol i d sal ts may be
l eft i n the i ce, and the composi ti on of the water obtai ned by mel ti ng wi l l
di ffer from that of normal sea water. I f, on the other hand, the tempera-
ture of the i ce i s rai sed to OC, al l sal ts di ssol ve, the cel l s grow so l arge
that the i ce becomes porous, al l bri ne tr i ckl es down from the porti ons
of the i ce above the sea surface, and the exposed ol d i ce becomes fresh
and can be used as a source of potabl e water.
Anal yses by Wi ese (1930) i ndi cate that the processes that have
been descri bed may be effecti ve i n changi ng the rel ati ve composi ti on of
the sal ts, He found that the sul phate and al kal i ni ty factors were greater
i n the i ce than i n the water and were greater i n ol d i ce than i n newl y
frozen i ce. Thi s i ndi cates that smal l amounts of sul phate, probabl y
present as Na&OA, have remai ned i n the i ce du;i ng the process of agei ng
and, probabl y, that the rel ati ve amounts of CaCOs have changed.
Resul ts of the ~aud Expedi ti on, reported by Md.ngren (1927)
and Sverdrup (1929), are not i n agreement wi th the fi ndi ngs of Wi ese.
Chl ori ni ti es of water obtai ned by mel ti ng i ce were systemati cal l y hi gher
when determi ned by ti trati on than when computed by means of Knud-
sens 13ydrographi cal Tabl es from observati ons of densi ty. Thi s
di screpancy was i nterpreted to mean that the sea i ce contai ns an excess
of chl ori des, but i t may ari se from the appl i cati on of Knudsens Tabl es
to water that has been di l uted by essenti al l y di sti l l ed water, as expl ai ned
on p. 59. The fact that the SOA/Cl rati o ww nearl y the same i n the
i ce and the sea water (Mal mgren, 1927, p. 9) supports the l atter expl ana-
ti on and i ndi cates that no changes i n rel ati ve concentrati on had resul ted
from processes of freezi ng and mel ti ng. The probl em, however, cannot
be consi dered sol ved, and i t offers opportuni ti es for further l aboratory
i nvesti gati ons and observati ons i n the fi el d.
Geochemistryof the Ocean Waters
The total quanti ty of di ssol ved sol i ds present i n the waters of the
oceans can be esti mated by assumi ng an average sal i ni ty of 35 0/00
and assumi ng that the vol ume of the ocean i s 1.37 X 108kms (p. 15).
Wi th a densi ty i n si tu of 1.04 for the ocean waters, the di ssol ved sol i ds
amount to 5 X 101 metr i c tons. Thi s i mmense quanti ty of materi al
woul d form a l ayer of dri ed sal ts 45 m thi ck over the enti re earth, or
153 m thi ck over the present l and area. The amount i n tons of any
el ement may be esti mated by mul ti pl yi ng the val ue gi ven i n the fi r st
col umn i n tabl e 45 by 1.42 X 1012. The fi gures for the vari abl e el ements
correspond to the hi gher val ues l i sted i n tabl e 36. Obvi ousl y the total
amounts of even the trace el ements are tremendous, and, i f methods of
extracti on were economi cal l y feasi bl e, the oceans woul d serve as an
i nexhausti bl e source of these substances.
Accordi ng to present theori es, most of the sol i d materi al di i kol ved
i n the sea ori gi nated from the weatheri ng of the cruet of the earth. The
probl em as to the amount of rock weathered has been treated by Gol d-
schmi dt (1933) i n the fol l owi ng way. For each square centi meter of
the surface of the earth there are 278 kg of sea water; therefore, for each
square centi meter the ocean water contai ns very nearl y 3 kg of sodi um.
The average sodi um content of i gneous r ocks i s 2.83 per cent, and i n
sedi mentary deposi ts i t i s 1.00 per cent. I n the process of weatheri ng, a
certai n amount of the materi al i s l eached away, and Gol dschrni dt
esti mates that the mass of the sedi mentary deposi ts (Y) i s 0.97 of the
ori gi nal i gneous r ocks (X) that gave r i se to them. Therefore,
Y = 0.97X, and 2.83.X 1.00Y= 100x 3.00.
Fr om thk we fi nd that for each square centi meter of the earths surface
about 160 kg of i gneous r ocks have been weathered. Therefore, approxi -
220
TABLE45
ELEMENTS IN SEA WATER AND IN THE EARTHS C
El ement
Si l i con . . . . . . . . . . . . . . . . . . . . . .
Al umi num . . . . . . . . . . . . . . . . . . .
I ron . . . . . . . . . . . . . . . . . . . . . . . . .
Cal ci um . . . . . . . . . . . . . . . . . . . . .
Sodi um . . . . . . . . . . . . . . . . . . . . . .
Potassi um . . . . . . . . . . . . . . . . . . .
Magnesi um . . . . . . . . . . . . . . . . . .
Ti tani um . . . . . . . . . . . . . . . . . . . .
Manganese . . . . . . . . . . . . . . . . . .
Phosphorus. . . . . . . . . . . . . . . . . .
Carbon . . . . . . . . . . . . . . . . . . . . . .
Sul phur . . . . . . . . . . . . . . . . . . . . .
Chl ori ne . . . . . . . . . . . . . . . . . . . . .
Stronti um . . . . . . . . . . . . . . . . . . .
Bari um . . . . . . . . . . . . . . . . . . . . . .
Rubi di um . . . . . . . . . . . . . . . . . . .
Fl uori ne . . . . . . . . . . . . . . . . . . . . .
Chromi um . . . . . . . . . . . . . . . . . . .
Zi rconi um . . . . . . . . . . . . . . . . . . .
Copper . . . . . . . . . . . . . . . . . . . . . .
Ni ckel . . . . . . . . . . . . . . . . . . . . . . .
Vanadi um . . . . . . . . . . . . . . . . . . .
Tungsten . . . . . . . . . . . . . . . . . . . .
Li thi um . . . . . . . . . . . . . . . . . . . . .
Curi um. . . . . . . . . . . . . . . . . . . . . .
Cobal t . . . . . . . . . . . . . . . . . . . . . .
Ti n . . . . . . . . . . . . . . . . . . . . . . . . .
zi nc . . . . . . . . . . . . . . . . . . . . . . . .
Yttri um . . . . . . . . . . . . . . . . . . . . .
Lanthanum . . . . . . . . . . . . . . . . . .
Lead . . . . . . . . . . . . . . . . . . . . . . . .
Mol ybdenum, . . . . . . . . . . . . . . . .
Thori um . . . . . . . . . . . . . . . . . . . . .
Cesi um . . . . . . . . . . . . . . . . . . . . . .
Arseni c . . . . . . . . . . . . . . . . . . . . ..
Scandi um . . . . . . . . . . . . . . . . . . . .
Bromi ne . . . . . . . . . . . . . . . . . . . . .
Bor on . . . . . . . . . . . . . . . . . . . . . . .
Urani um . . . . . . . . . . . . . . . . . . . . .
Sel eni um . . . . . . . . . . . . . . . . . . . .
Cadmi um . . . . . . . . . . . . . . . . . . . .
Mer cur y . . . . . . . . . . . . . . . . . . . . .
I odi ne . . . . . . . . . . . . . . . . . . . . . . .
Si l ver . . . . . . . . . . . . . . . . . . . . . . .
Gol d . . . . . . . . . . . . . . . . . . . . . . . .
Radi um . . . . . . . . . . . . . . . . . . . . .
P = present
Sea water
s =350/00
(mg/kg)
4
0.5
0.02
408
10,769
387
1,297
. . . . . . . . . . . .
0.01
0.1
28
901
19,353
13
0.05
0.2
1.4
P
. . . . . . . . . . . .
0.01
0.0001
0.0003
. . . . . . . . . . . .
0.1
0.0004
P
P
0.005
0.0003
0.0003
0.004
0.0005
<0.0005
0.002
0.02
0.00004
66
4.7
0.015
0.004
P
0.00003
0.05
0.0003
0.056
0.0,3
Potenti al suppl y
i n OOOgof r ock
(mg/kg of sea water)
165,000
53,000
31,000
22,000
17,000
15,000
13,000
3,800
560
470
300
300
290
250
230
190
160
120
120
6(
60
E
39
26
24
24
24
19
11
10
9
6
4
3
3
3
2
2
0.4
0.3
0.3
0.2
0.06
0.003
0.0,6
UST
Per centage
i n
sol uti on
0.002
0.001
0.0001
1.9
65
2.6
10
?
0.002
0.02
3J
6700
5
0.02
0.1
0.9
?
?
0.02
0.0002
0.0005
?
0.2
0.002
?
?
0.02
0.002
0.003
0.04
0.005
0.01
0.05
0.7
0.001
2000
240
0.8
1
?
0.001
25
0.5
0.3
0.05
matel y 600 g of rock have been weathered for each ki l ogram of water
i n the oceans. Of the total sodi um, 65 per cent has accumul ated i n
the seawater and 35 percent has been deposi ted i n sedi mentary rocks.
The 600gof i gneous rock have been, therefore, a potenti al suppl y of the
consti tuent el ements to the sea, al though i n most cases onl y a part of
themateri al hasactual l y d~sol ved orremai ned i nsol ati on. Usi ng 600g
as the amount of rock weathered and fol l owi ng Gol dschmi dts esti mate
(1937) of the composi ti on of the earths crust, the suppl y of el ements
l i sted i n tabl e 45 i s obtai ned. A number of the mi nor consti tuents of
r ocks are not i ncl uded i n thi s tabul ati on. The percentage i n sol uti on
has been obtai ned by dl vi dl ng the amount of each el ement present i n
sea water by the potenti al suppl y. Thi s procedure has been fol l owed by
Gol dschmi dt (1937).
Exami nati on of tabl e 45 shows that the el ements may be grouped
i n three cl asses, dependi ng upon the percentage i n sol uti on: (1) Sul phur,
chl ori ne, bromi ne, and boron occur i n amounts greater than those whi ch
coul d have been suppl i ed by the weatheri ng of the 600 g of rock. Gol d-
schmi dt consi ders that these el ements were present i n the pri meval
atmosphere as vol ati l e compounds and that they accumul ated i n the
ocean waters i n the earl i est ti mes. (2) Cal ci um, sodi um, potassi um,
magnesi um, carbon, stronti um, sel eni um, and i odi ne, whi ch form rel a-
ti vel y sol ubl e compounds, are present i n sea water i n amounts greater
than 1 per cent of the potenti al suppl y. (3) The remai ni ng el ements,
whi ch are present i n smal l amounts.
I t i s stri ki ng that si l i con, al umi num, and i ron, the most abundant
el ements i n i gneous r ocks (oxygen i s actual l y the most abundant, but
does not have t~be consi dered here), are present i n sea water i n extremel y
smal l amounts. Thus, the rel ati ve abundance of the el ements i n sea
water di ffers markedl y from that i n the earths crust. Wi th a few
excepti ons, al l of the el ements have been potenti al l y avai l abl e i n much
l arger amounts than are actual l y present i n sol uti on. The rel ati ve
composi ti on of ri ver water di ffers from that of sea water, and, i n addi ti on
to the di ssol ved consti tuents, ri vers i ntroduce l arge quanti ti es of parti cu-
l ate materi al that woul d pass i nto sol uti on i f the sea water were unsatu-
rated wi th respect to these substances.
Therefore, i t appears that
factors operati ng i n the sea i tsel f must control the concentrati ons of many
of the el ements that are potenti al l y avai l abl e i n l arge amounts. These
factors are vol ubi l i ty, physi cal -chemi cal reacti ons, and bi ol ogi cal acti vi ty.
Our present knowl edge i s i nadequate to desi gnate whi ch process or
processes may control the concentrati on of a gi ven el ement. Therefore,
the fol l owi ng remarks wi l l merel y i ndi cate the character of the factors
that may be i nvol ved.
Certai n el ements may be present i n such amounts that the vol ubi l i ty
of thei r compounds may l i mi t thei r concentrati on,
I n these caees,
addi ti onal amounts brought to the sea i n sol uti on by ri vers -wi l l be
removed by chemi cal preci pi tati on. The quanti ti es of other el ements
may be control l ed by physi cal -chemi cal processes that are, however,
more compl ex than the preci pi tati on of some si mpl e sal tfor exampl e,
the reacti ons whi ch may take pl ace between the di ssol ved substances
and the col l oi dal and parti cul ate materi al i ntroduced by ri vers.
I ncl uded
among such processes are i oni c adsorpti on, base exchange, and the
formati on of compl ex mi neral s. Such reacti ons may remove from
sol uti on i ons that woul d not be preci pi tated i n absence of col l oi dal or
parti cul ate materi al . Bi ol ogi cal acti vi ty i s undoubtedl y of great
i mportance i n control l i ng the concentrati ons of many of the el ements i n
the sea. Cycl i cal processes,i n whi ch el ements are removed from sol uti on
but are l ater rel eased by metabol i c acti vi ty, need not be consi dered.
However, a certai n amount of the materi al bui l t up by organi sms fal l s
to the sea bottom, becomes a permanent part of the deposi ts, and i s
therefore removed from sol uti on. The concentrati on of el ements carri ed
down i n thi s way may be consi dered to be at l east partl y control l ed by
the acti vi ty of mari ne organi sms. The character of the skel etal struc-
tures and of the detri tal organi c matter deposi ted i n thi s way i s di scussed
i n chapters VI I and XX. Organi sms remove from sol uti on el ements
that woul d not otherwi se preci pi tate, and, i f condi ti ons are such that
some of thi s materi al becomes a permanent part of the sedi ments, i t i s
obvi ous that bi ol ogi cal acti vi ty must pl ay an i mportant part i n control l i ng
the composi ti on of the water. Not onl y the major consti tuents of
skel etal structures such as cal ci um, carbon, si l i con, and so on, but ni tro-
gen, phosphorus and many el ements present i n the sea i n smal l con-
centrati ons are al so accumul ated by mari ne organi sms.
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CHAPTERVI

Chemistry of Sea water

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