Prog. Oceanog. 1982, Vol. 11, pp. 151-197 0079-6611/82/020151-47523.

50/0
Printed in Great Britain. All rights reserved. Copyright .@ 1982 Pergamon Press Ltd.

Glacial to Interglacial Changes in Ocean Chemistry

WALLACE S. BROECKER
Lamont-Doherty Geological Observatory and the Department of Geological
Sciences of Columbia University, Palisades, New York 10964

Introduction
Recent measurements by the groups in Grenoble and in Bern on gases bound in
samples from polar ice cores provide tantalizing evidence for a substantially lower than
present atmospheric CO 2 content during the last glacial period (Delmas et al., 1980; Berner
et al., 1980). These studies also suggest that the transition from the low CO 2 to N 2 ratios
characterizing late glacial time to the higher values characterizing postglacial time
occurred in just a few thousand years. The purpose of this paper is to explore the cause for
this change.
The f i r s t point to be made in this connection is that the cooling of the surface ocean
during glacial time was not adequate to explain the decrease in atmospheric CO 2 content
of about 100 ppm suggested by the ice core results. The CLIMAP (1976) reconstruction of
surface ocean temperature during glacial time gives a value of 2.5 C cooler than today.
The CO 2 pressure of surface ocean water falls about 13 x 10-6 atm per degree of cooling.
By itself this cooling would bring about a 33 x 10--6 atmosphere reduction in the CO 2
pressure. The 0.9°/oo increase in ocean salinity caused by the growth of glaciers would
have produced an increase in CO 2 partial pressure which would have compensated for about
two thirds of this decrease. Hence, in the absence of any change in ocean chemistry, the
atmospheric CO 2 content would have remained nearly constant.
Since the glacial and the interglacial CO 2 partial pressure values persisted for many
thousands of years, in looking for other causes it must be taken into account that the ocean
as well as the atmosphere must have changed its chemistry. The ocean contains about 60
times more carbon than the atmosphere; thus the atmospheric CO 2 content is on this time
scale slave to the ocean's chemistry. This being the case the cause of the change in
atmospheric CO 2 content almost certainly lies in a change in the ocean's chemistry. In this

151
152 W.S. Broecker

paper I explore possible causes for and indicators of paleo-ocean chemistry changes
between glacial and interglacial time.
Three chemical properties of the ocean influence the CO 2 pressure of its surface
waters: the total dissolved inorganic carbon c o n t e n t of average sea water (i.e., CO 2 +
CO3 = + HCO3-); the alkalinity of average sea water (i.e., the positive charge to be
balanced by the anions of weak acids); and the phosphate c o n t e n t of mean sea water. I will
try to document in the sections which follow that evidence exists in deep sea sediments for:
(I) a higher oceanic ~CO 2 c o n t e n t during glacial time than during interglacial time,
(2) nearly the same carbonate ion concentration for deep sea water during glacial as
during interglacial time, and
(3) a higher oceanic PO 4 c o n t e n t during glacial than during interglacial time.
As will be shown below, taken together the higher glacial oceanic ~ CO 2 and the
absence of a significant change in the carbonate ion c o n c e n t r a t i o n of deep water suggest
that the CO 2 partial pressure of the glacial ocean (and hence of air) must have been higher
than today's. On the other hand, a higher glacial oceanic PO 4 c o n t e n t would have led to a
lower surface water (and hence atmospheric) CO 2 partial pressure. The carbon isotope
evidence from deep=sea sediments to be discussed below suggests that the increased glacial
CO 2 c o n t e n t , while more than enough to balance the CO 2 partial pressure decrease due
to the glacial cooling, was much smaller than the CO 2 pressure reduction brought about by
the oceanic PO 4 increase. Together the three effects lead to a glacial age CO 2 partial
pressure in sea surface water well below its present value.
The list of possible mechanisms for the decrease in the PO# content of sea water at
the end of the last glacial period is greatly shortened by two constraints. First, no means
exist by which phosphorus can be transferred from sea to continent on the time scale of a
few thousand years. Second, the residence time of PO# in the sea is on the order of
I00,000 years (Froelich et al., in press). The first restriction requires that the phosphorus
lost from the sea at the close of glacial time went to marine sediments. The second
restriction eliminates all the factors normally associated with the maintenance of the
steady state PO4 content of the sea (i.e., continental weathering rate, vertical mixing rate
in the sea, recycling efficiency of organic residues in the deep s e a . . . ) (Broecker, 197#).
None of these could produce the rapid change seen in the CO2/N2 ratio in the ice.
One mechanism that would produce the needed rapid change in the PO4 content was
suggested to me by Garry Brass. The deposition of organic-rich sediments on the shelves
 Glacial to interglacial changes in ocean chemistry 153

(and in estuaries) during early postglacial time would do the trick. In the sections which
follow I construct a case in support of deposition of organic debris on the shelves as the
cause for the rise in atmospheric CO 2 content at the end of the last glacial period. The
destruction of these same sediments during the early glacial times led to the establishment
of the low glacial atmospheric CO 2 values.
My case will be built in two steps. First I will present evidence used to establish the
changes in Z CO 2 and alkalinity of the ocean between glacial and interglacial time. Then I
w i l l present the evidence for a change in PO 4 content.

Sedimentary Evidence for a Glacial to Interglacial Chanse in Oceanic ~ CO 2 Content

As the carbon in organic matter is deficient in 13C relative to carbon dissolved in the
sea, any net generation (or destruction) of organic matter will lead to a change in the
6 13C value for oceanic and atmospheric carbon. As about 90 percent of the ocean-
atmosphere carbon resides in the deep sea, the isotopic record for this reservoir must tell
the story. Shackleton (1977) was the first to systematically explore the 13C record in
benthic forams. In order to avoid species effects, his studies were done on the shells of a
single species. One of his records is shown in Fig. I. Shackleton found that the ~ 13C
values were less during peak glacial than during peak interglacial time. A summary of his
findings is given in Table I. As can be seen, the glacial benthics have on the average an
0.70/00 lower 613C value than do the interglacial shells.
Shackleton (1977) interpreted this change as the result of decreased forest cover
during glacial time. As summarized in Table 2, a reduction of 33% in the carbon stored in
forests and in soils (i.e., 9 x I016 moles) would lower the $13C value for the ocean-
atmosphere carbon pool by 0.70/00. Shackleton defends this interpretation by pointing out
that the areas of present boreal forests were either covered by ice or tundra during glacial
time and that the tropics were drier and hence the tropical forests were likely smaller
during glacial time. As pointed out in Table 2, the bulk of this carbon would have to have
come from soil humus rather than wood.
It is also possible that the change in the isotopic composition of oceanic carbon seen
by Shackleton was produced by the production and destruction of shelf sediments. As the

Several years ago Nobuaki Niitsur~ visited Lamont and tried to convince me that
S h a c k l e t o n ' s i n t e r p r e t a t i o n of t h e C d a t a f o r b e n t h i c f o r a m s was n o t c o r r e c t . He
m a d e a c a s e t h a t c a r b o n was t r a n s f e r r e d b e t w e e n t h e s e a a n d o r g a n i c m a t t e r s t o r e d
in s e d i m e n t s r a t h e r t h a n f r o m soils a n d t r e e s as S h a c k l e t o n p r o p o s e d . A t t h e t i m e I
was n o t p a r t i c u l a r l y r e c e p t i v e t o t h i s i d e a . D u r i n g t h e l a s t s t a g e s of w r i t i n g t h i s
paper, I remembered this incident and checked to see whether Niitsuma had published
his t h o u g h t s on t h i s m a t t e r . T h r o u g h T e h Lung Ku I f o u n d t h a t i n d e e d a p a p e r h a d
b e e n p u b l i s h e d in t h e j o u r n a l " K a g a k u " in 1977. T a r o T a k a h a s h i was kind e n o u g h t o
t r a n s l a t e t h i s p a p e r f o r m e , a n d i n d e e d a c a s e is m a d e f o r s h e l f s e d i m e n t a t i o n . Thus,
I r e f e r t o t h e N i i t s u m a h y p o t h e s i s in t h e r e m a i n d e r of t h e t e x t .
154 W.S. Broecker

+I

o -7o oo o S o
~o
I I I

• ~
o

0 (~"~ ,."-, 0'~ O~ ~ ee~

-o oo S ~
' + + ' ' "T' "? :~

("4 C~lO u'~ ~ ~

,:; .. ~,:; • ,..
O ~ 0 -- 0
o + + + ~ ~ 0 I
I

• • •

O~
0
uO
£
>'~ '~ < "Z < ~
o ~. o
0 o

t- Cz 0
0 o~ o~ 0 oo~ ~ '" o ~ o
Z ~ ,=;
+
~ c+; 6+ o
+
o o

~h
0
o~
0 ~'~ 0.-~" ~ i~

O
0 0 0 0 0 0 0

c-
n~ O
S

c~0

Z Z ~ ~ ~ ~0
0 0 0 0 0 0 0
0 ("4 ~I~ ~*~ ~0

E
E

~ o ~

0 en
I'M ~D
~n
<
 Glacial to interglacial changes in ocean chemistry 155

8Cl3 8018
0,i5 -I o, o;5 • o~p~ .~0.6t~,~iO 5 0I
IA 1.2 Y=o
j O,o
Q-
' ,1" I - ,=
2_oOj
e I e@

3 °°Io
o%
~,_ Io
o o

5-- O 0

6
-
oO O
Oo O
O

o ,~,

~P ,
.9
7- * **I ,'t~ °
• *o~ o*
8-
Io4 _-o o ,.A_ ,o
Flg I I l -'l I el

Fig. 1. 613C and 6180 analyses on Meteor core 12392 from the eastern North
A t l a n t i c from Shackleton (1977). The circles are the analyses made on
Uvergerina peregrina and the asterisks are for analyses made on
Panulina wuellerstorfi. The scales are for Uvergerina perigrinaoanalyses.
To make the Panama wuellerstorfi results compatible 1~.0 Ioo was
subtracted from the 6 C results and 0.7% was added to the 6 O results.

6 13C value for shelf sediment organic carbon of marine origin is -21°/oo while that of
wood and soil carbon is about -260/00, the amount of carbon transferred would have to
have been 11.5 x 1016 rather than 9 x 1016 moles. Were this carbon contained in sediments
averaging I% organic carbon (by weight)) then about 15 x 1019 grams of sediments must
have been moved to and from the shelves. If spread uniformly over the present shelves
(area J'3 x 1017 cm 2) this sediment would have formed a layer 5 meters thick. While this is
by no means an unreasonable amount of sediment I know of no precise way to document the
actual amount of carbon transferred between shelf and sea as the result of glacially
induced sea level changes,
The distinction between a terrestrial and a shelf origin for the 613C shift is
important because phosphorus removal from the ocean would accompany shelf deposition

JPO 11:2 - G
156 W.S. Broecker

TABtE 2. Possible interpretations for the 0.7°/oo decrease in the 813C for benthic
Iorams during glacial times.

Carbon Mass Mean ~13C 613C x Mass

Reservoir
1016 moles °/oo °/oo

SHACKLETON'S FOREST-SOIL HYPOTHESIS

Interglacial

Ocean 311 / 316

Arm 5 +0.5 +158

Forest 20 1 27 -26.0 -702

Soil 7
-554
Glacial

Ocean
Atm
- 325 -0.2 - 65

Forest 10 I 18 -26.7 -q80

Soil $ #

-505

NIITSUMA'S SHELF SEDIMENT HYPOTHESIS

Interglacial

Ocean 31~1 316 +0.5 +158

Arm

Excess Shelf I l, 5 -21.0 -223

Sediment
- 65

Glacial
Ocean
Atm 327.5 -0.2 - 65

Excess Shelf
Sediment
0 0
-65
 Glacial to interglacial changes in ocean chemistry 157

but not forest and soil formation. It is not, however, important to the carbon-alkalinity
argument for which I will assume that 10 x 1016 moles of organic carbon were removed
from the ocean at the close of glacial time.
Because the residence time of carbon in the sea is on the order of 200,000 years,
neither the excess ~CO 2 c o n t e n t nor the 13C deficiency would be significantly altered
during the course of a single glacial or interglacial episode (mean duration about 50,000
years) as the result of the steady s t a t e of carbon throughput. The removals and inputs of
CO 2 caused by sea level excursions would, however, be "compensated" over the course of
several thousands of years by the deposition or dissolution of CaCO 3. This would produce
an alkalinity change and an additional ~CO. change. It would not however produce any
additional 613C changes. This is because theZ613C in marine carbonates is almost identical
to that in sea water.
Neglecting for the moment the magnitude of the z CO2-alkalinity changes produced
by CaCO 3 dissolution, let us examine the relationship between the CO 2 c o n t e n t (and hence
partial pressure) in a sea water sample and its ~. CO 2 and alkalinity content. The CO 2
c o n t e n t is governed by the reaction

CO 2+CO3 = + H20<=>2HCO 3-

and hence the CO 2 partial pressure is given by

2
[H C O 2 ]
P C O 2 - K , [ C O 3 =]

where K' is a constant at any given t e m p e r a t u r e , pressure and salinity. In sea water

HCO 3 - m 2 [ CO 2 ] - [A ] ,

hence

(2 [z c o 2] - [A]) 2
P C O 2 == [CO3 = ]

The depth of the oceanic lysocline is closely tied to the C O 3 ion content of deep sea
water (Broecker and Takahashi, 1978). Studies of glacial sediments suggest that during
glacial times the lysocline was deeper in the equatorial Pacific and Indian Oceans
(Broecker, 1971; Luz and Shackleton, 1975) and perhaps slightly shallower in the Atlantic
(Gardner, 1975). However in no case does the shift appear to have been more than a few
hundred meters. In most regions of the deep ocean the CO B ion concentration gradient is
currently quite small. The pressure effect on the solubility of calcite increases the
equilibrium CO 3 ion c o n t e n t about 15 1Jm/kg per kilometer. Thus it appears that the CO3 =
c o n t e n t of the deep sea during glacial time lay within the limits 3 + 3 iam/kg above its
158 W.S. Broecker

present average. The current CO; ion content of deep water averages about 90 lam/kg.
This being the case then

[CO3=]G 93_+3
[ CO3 =] I 90
Since

I2[ co 2 I, [AI i/ I\[zc°2J, )2

hence

PCO2 [ ~CO2 ] G 90 90

PCO 2

where M G and M I are the masses of ocean-atmosphere carbon in glacial and interglacial
time and VG and VI are the volumes of the glacial and interglacial oceans. The mass of
carbon in the ocean-atmosphere system today is 316 x 1016 moles. The deposition of
organic carbon on shelves and estuarine sediments at the time would have decreased the
oceanic r CO 2 by about 396. If CO 2 loss to organic matter were entirely compensated by
CaCO~ deposition, the increase would have been closer to 696. I will adopt a value of 20 +
4 x 10`6 moles as the glacial to interglacial change in ocean-atmosphere carbon inventory
(the near constancy of the lysocline suggests that CaCO 3 compensation was largely
accom plished).
Taking the glacial sea level lowering to be I00 meters, the volume of the glacial sea
was .974 that of today's ocean. Thus, other factors being the same, the glacial CO 2 partial
pressure is given by

G
336 -+ 0 x 90
I
PCO 2
= I
.97//x 316 I 93+3
- 1.15 + .05

Taking the interglacial PCO to be 300 x 10-6 atm, the decrease in PCO from glacial
to interglacial would be 46 _+ 15 210 -6 atm. When combined with the temperature-induced
increase of 3 3 x 10- 6 a t m , the result is 13+ 15x I0 - 6 a t m (glacialPco =313_+ 15x 10-6
arm). Thus in the absence of a PO4 change atmospheric PCO 2 must have been
presure
slightly higher during peak glacial than during peak interglacial ti2rne.
 Glacial to interglacial changes in ocean chemistry 159

Evidence for a Glacial to Interslacial Change in Oceanic Phosphate Content

If the sink for the carbon which l e f t the ocean as organic matter at the close of the
last glacial period was mainly shelf and estuarine sediment) then phosphorus as well as
carbon would have been lost. As an indication of how much phosphorus might have been
lost the ratio of carbon to phosphorus in microorganisms (i.e., a'105 to I) can be used as an
estimate of the ratio of C to P in shelf sediments. A loss of I I . 5 x 1016 moles of carbon
would then be accompanied by a loss of I I x 1014 moles of phosphorus. Today's ocean
contains about 30 x 1014 moles of PO 4. Taking into account the .974 reduction in volume)
the glacial oceanic PO~ content is estimated to have averaged 3.1 ~m/kg (as opposed to the
present 2.2 )Jm/kg). I should emphasize at this point that I carry out this calculation only as
an indication as to what the change might be. As the C/P ratio in sediments covers a wide
range (i.e.) ~50 to 500) use of the Redfield ratio could be misleading. I am leading up to an
independent argument based on the carbon isotope record.

ISOCHEMICAL
u
COOLING
T= 2 I °C A=2271p.E/kg
S= 34.7%,, EC02=196 I/~M/k9
NO3= O/~M/k9 PCOz=295p.ATM
P04= O/=M/kg

DEEP
OPWE . WATER
FORMATION

£:,L..
S=34.7%,, '~C02=2250/~vVkg
!NO5= 32/.LM/kg PCO2=IOOOp.ATM
PO4=2.2FM/kg

86.9 ~ . ~
DEEP OCEAN

Fig. 2. Two=box model for ocean chemistry: The composition differences between
the surface and the deep reservoir are all the results of the formation of
organic tissue and CaCO 3 in surface water. The numbers associated with
the arrows give the percent of the upwelled carbon carried by CaCO~ by
organic tissue and by downwelled water. The CO~ partial pressure given" for
the deep water is that which it would have w~re it brought to the sea
surface and warmed isochemicaIly to 21.0 C. The alkalinity difference
between deep and surface water includes the contribution of NO 3
regeneration as well as that of CaCO~ dissolution in the deep sea.
160 W.S. Broecker

To understand how the amount of phosphorus dissolved in the sea influences

atmospheric CO 2 content~ the highly simplified model of the chemical cycles occurring
w i t h i n the sea shown in Fig. 2 proves useful. The ocean is divided into two well-mixed
reservoirs" warm surface water and cold deep water. As the deep reservoir is much larger
than the surface reservoir9 its properties are close to the mean for the entire system.
Water upwells from the deep to the surface reservoir. While in residence at the surface,
plants utilize P, N and C (in proportions of roughly l to 15 to 105 atoms) to make organic
tissue. The rain of this tissue into the deep sea depletes warm surface water of PO 4 (and
of NO 3) and utilizes about 10.5 percent of the available carbon. Some of the organisms
living in surface water also produce CaCO 3 hard parts. The rain of these hard parts to the
deep sea carries away about 2.6 percent of the upwelled carbon. The remaining carbon is
carried by surface currents into the polar regions where the water is isochemicaliy (at least
in the model) cooled and sinks to the deep sea. The important point to be made is that the
CO 2 pressure in surface water (300 x 10-6 atm) is much lower than that expected i f deep
water were brought to the surface and warmed isochemically to 21 C (in this case i t would
be 1000 x 10- 6 arm). The threefold difference is caused by the utilization of CO 2 by
plants. The extent to which plants deplete the ECO 2 content of surface ocean water is
dependent on the PO 4 to TCO 2 ratio in mean sea water. If the mean PO 4 content of sea
water were 3.2 rather than 2.2 lJm/kg, other factors held constant~ the CO 2 pressure would
be 200 x 10-6 arm rather than 300 x 10-6 atmospheres (see Table 3).
The production of CaCO 3 by surface-dwelling organisms also influences the CO 2
content of surface water. Per unit of PO 4 upwelled the more CaCO 3 which rain% the
smaller the reduction in CO 2 partial pressure caused by plant growth. The above
calculation was made assuming the ratio of CaCO 3 to P rain for the glacial ocean as for
the interglacial ocean (as shown in Appendix A, in today's ocean about l mole CaCO 3 rains
per 4 moles of organic carbon rained). As there is no way to determine the extent to which
this ratio changed during glacial time, it must remain an uncertainty in the reconstruction
attempted here. As shown in Table 3, the resulting glacial PCO is moderately sensitive to
changes in this ecologically controlled parameter. If the ratio o3 CaCO 3 rained to P rained
during glacial time were on the average roughly the same as in today's oceanp then a change
in the mean phosphorus content from 2.2 to 3.2 iJm/kg would be adequate to produce the
PCO change inferred from the ice core record.
2Fortunately we do not have to rely on an estimate of the C/P ratio in the organic
material deposited on the shelves at the close of glacial time to get at the change in the
mean phosphorus content of sea water. There is a more direct approach. A phosphorus
content change would be recorded in the ocean as a change in the difference between the
613C for warm surface water carbon (i.e., POt~ free water) and the 613C for mean deep
water carbon. This difference is in turn recorded by planktonic and benthic forams found in
deep sea sediments.
 Glacial to interglacial changes in ocean chemistry 161

TABLE 3. Influence of temperature, salinity, ~CO~, PO 4 in upwelled water and the

ratio of organic carbon to CaCO 3 carbon on the CO 2 partial pressure in
surface water. +

Temp Sal Alk Y.CO2 AIk-ECO 2 CO 3 P_c6O

°C °/oo vg/kg ]~m/kg vm/kg vm/kg 10- a~m

Change Temperature
23 34.7 2276 1961 315 222 332
22 34.7 2276 1961 315 222 319
21 34.7 2276 1961 315 221 305
20 34.7 2276 1961 315 220 292
Change Salinity
23 34.7 2276 1961 315 222 332
23 35.0 2296 1978 318 22# 336
23 35.3 2315 1995 320 226 342
23 35.6 2335 2012 323 228 346
Change ECO 2 (Hold Alkalinity Constant)
23 34.7 2276 1961 315 222 332
23 34.7 2276 2001 275 196 404
23 34.7 2276 2041 235 171 498
23 34.7 2276 2081 195 146 622
Change ~CO 2 (Hold Alk- CO 2 Constant)
23 34.7 2276 1961 315 222 332
23 34.7 2316 2001 315 224 34#
23 34.7 2356 2041 315 225 357
23 34.7 2396 2081 315 227 370
Change AOrg/ACaCO 3 ( i . e . , AAIk = 2 A~CO2)*
23 34.7 2216 1931 285 200 364
23 3#.7 2246 1946 300 211 347
23 34.7 2276 1961 315 222 332
23 34.7 2306 1976 330 233 318
23 34.7 2336 1991 345 244 305
Change PO 4 in upwelled water hold AOrg/ A C a C O 3 Equal to 4
(i.e., A~CO 2 = 2.5AAIk)**
23 34.7 223# 1856 378 262 237
23 3#.7 2255 1909 346 242 281
23 34.7 2276 1961 315 222 332
23 34.7 2297 2013 284 203 393
23 34.7 2318 2066 252 183 471
! !
These calculations were carried out using the I<i and K~ apparent dissociation
constants of carbonic acid in sea water determinedby MehrBack et al. (1973), and
the CO o solubility of Weiss (1974) following the procedures outlined by Broecker and
Takahas~i (1978).
The organic carbon to CaCO 3 carbon ratios are respectively 2.6, 3.2, 4.0, 5.4 and 8.2
* *
The PO a contents in the upwelled water are respectively 3.2, 2°7, 2.2, 1.7 and
1.2 pmlk'g.
162 W.S. Broecker

The reason is that the difference between the 613C value for warm surface water
(wsw) and for mean ocean water (mow) is a measure of the mean phosphorus content of the
sea. To a close approximation this relationship is as follows:
[ po~]
(6 13C)wsw _(613C)mow _- - ~(C)_ org x [ CO~ mow
mow

For today's sea [POtt]mo w is close to 2.2 um/kg and [zCO2]mo w is close to 2250 um/kg.
The C / P ratio in marine organic m a t t e r averages 105. The isotope fractionation during
photosynthesis (4) is about 20 per rail. Thus in today's ocean

(613C)ws w _ ( 813C)mo w _- 2.050/00 .

The dependence of the ~3C for a given water sample on its PO 4 content is given by the
relationship

613C = 613Cwsw - . 9 3 [P04]

As can be seen in Fig. 3, this relationship holds in today's ocean for all except Antarctic
waters.
Taking the ZCO 2 and PO 4 contents of the glacial ocean to be 20.55 (i.e., ~-~
336 x 1
974
x 2250) and 3.2 um/kg, the corresponding equations become

( 6C 13)wsw _ (8 C 13)mow = 2.74O/oo

and

6 1 3 c G = (613CG)wsw 0.86 [PO 4 ]

The change in the value of the PO 4 = 613C trend coefficient from 0.93 to 0.86 is the result
of the increased oceanic r CO 2 content. The values of (C/P)org and Aare assumed to have
been the same during glacial and interglacial time.
The difference between the glacial and interglacial 13C/12C ratio for warm surface
water, n 13C, is given by the relationship

(46 13cG-I)wsw = (2.74 + (613CG)mo w) - (2.05 + (813CI)mo w)

= 0.7 + (6 13CG)mo w - (613CI)mo w

As outlined above, Shackleton (1977) has shown that the 613C for mean ocean water was
about 0.7 per rail lower during glacial time than during interglacial time. Thus

( n813C)ws w .,~ 0.0O/oo

 Glacial to interglacial changes in ocean chemistry 163

3 I I I I I I

WARM SURFACE
WATERS (FOSSIL
FUEL CO2 CORRECTED)
2

SLOPE
- 0.9 %o//~.m/kg
A
o

F
rO
CIRCUMPOLAR
DEEP
WAT E R -
ATLANTIC
DEEP
WAT E R
0 PACIFIC " ~ ~
DEEP
WAT E R
I I I I I
0 I 2 5 4
PO 4 (~m/kg)
Fig. 3. 6 13C-PO# relationships for major water types in the world ocean based on
the measurements at Scripps (Kroopnick et a l . , 1970; Kroopnick
et a l . , 1972; Kroopnickp 1974a; Kroopnick, 1974b; Kroopnick et a l . , 1976)
and at the University of Hawaii (Kroopnick~ 1980).

The reason for this near zero value is that for surface ocean water the ocean-wide shift of
0.7 per mil would be almost exactly compensated by an increase in the surface to deep
ocean 613C difference related to the higher glacial P O j ~ C O 2 ratio for mean sea water.
This compensation can be shown to occur as long as the C and P removed as organic debris
are in the Redfield ratio.
Estimating the glacial to interglacial change in 613C for surface waters from data on
planktonic forams has proven more difficult than estimating the 613C change for deep
water (and hence for mean ocean water) from data on benthic forams. Although thousands
of such analyses have been mad% relatively few have been published. The reason given by
164 W,S. Broecker

most investigators is the lack of regularity between 613C and climate (as determined by
6180 measurement on the same shells). Also, workers in the field are aware of the
following complications in the interpretation of ~13C data on planktonic foraminifera:
(1) Large and small tests of the same species show as much as 1°/oo difference in ~13C.
(2) As the 613C value in the ocean changes very rapidly with depth in the thermocline
(see Fig. 4)9 vertical migration of forams will lead to $13C vaJues more negative than
those expected for growth in the surface mixed layer.
(3) To date, most measurements have been made on spinous species which have symbiotic
algae growing on them. Because of photosynthetic fractionation by the algae the
CO3 = from which the shells form may not have the same 613C as that in the
surrounding water.
8C13 (%°)
0 I 2
o I I ~ I • t0
O0 0

I _lg
QO
I

E2 oo
oo

I-
w 3 O0
Q

Oo
4

7-~BOTTOM

I I I I I

Fig. 4. 13C values on CO 2 as a function of water depth at GEOSECS station 347

in the Pacific Ocean off Baja, California. The analyses were made by
Kroopnick et al. (1970).

Van Donk (1970) was one of the first to investigate the 613C record in planktonic
foraminifera. His measurements on G. ruber from Caribbean core V12-122 are summarized
in Fig. 5. As can be seen, there is no consistent relationship between 613C and c l i m a t e (as
indicated by 6180 m e a s u r e m e n t s on the same samples). In Fig. 6 the 613C values for both
 Glacial to interglacial changes in ocean chemistry 165

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166 W.S. Broecker

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 Glacial to interglacial changes in ocean chemistry 167

G. ruber and G. sacculifera are plotted against the 6180 values for the same samples.
Although the scatter is large, no significant difference is seen between the interglacial and
glacial averages for G. tuber. For G. sacculifera the scatter of the glacial ~ 13C values is
even larger than the ruber. Again, however, there is only a small difference between the
average for glacial and interglacial samples. Shackleton (1977) gives 613C values for the
same two species from a South Atlantic core (V22-17#). He finds an 0.#°/oo lower value
for G. ruber during glacial than during interglacial times and an 0.2O/oo lower value for G.
sacculifera. The 613C results from two equatorial Pacific cores studied by Berger and
Killingley (1977) are shown in Fig. 7. They show very little glacial to interglacial change.
Finally, the results for a third equatorial Pacific core (V17-177) are given in Fig. 8
(Shackleton, personal communication). Even though Shackleton worked with samples from
a narrow size range the scatter remains large. In this core glacial samples average 0.I°/oo
lower in 613C than the interglacial samples. The results from these cores are summarized
in Table 4 and Fig. 9. They are consistent with a near-zero estimate for the glacial to
interglacial 613C difference for surface water expected if the PO4 content of peak glacial
mean sea water were 3.2 ~m/kg (as opposed to today's value of 2.2 pm/kg).
Having shown how the 613C and PO# paleorecords are coupled I will now turn the
argument around and use the 613C record to calculate the PO# content of mean glacial sea
water. The equation is as follows

I
[ PO4] mow
(Z~13cG-I)ws w + (~613cG-I)mo w + 20 x 105
I
[ Z C02] mow
[ POt4 ] Gmow
20 x 105
[ZC02] G
mow

If the glacial to post-glacial planktonic shift is taken to be +0.1 and the mean benthic shift
to be +0.7, then

2.2
[ PO4 ]Gmow = -.1 + .7 + 20 x 105 2250 3.1 pm/kg
20 x 105
168 W.S. Broecker

Thus we see that the change in surface water ~13C and deep water 813C are consistent
with the transfer of carbon (as organic m a t t e r ) and phosphorus from the sea to some other
reservoir in nearly the Redfield proportions.

Dissolved Oxygen in the Deep Sea as a Possible Crosscheck

A possible crosscheck on this hypothesis could be obtained if the change in the mean
0 2 c o n t e n t of deep water from glacial to interglacial time could be assessed. The 0 2
c o n t e n t of deep sea water depends on the ratio of the atmospheric 0 2 pressure to the mean
oceanic POq c o n t e n t . If the PO# c o n t e n t of the ocean was higher during glacial time then
the 0 2 c o n t e n t of the deep sea must have been lower. For each additional I ~m/kg of PO t,
the 0 2 c o n t e n t would drop by about 135 ~m/kg. Thus, if as estimated above the PO t of
average sea water was about 0.9 ~m/kg higher then the 0 2 c o n t e n t of deep water was about
120 lJm/kg lower.

Peter Weyl (pers. comm.) proposed to me an alternate explanation for the 13C data
presented in this paper. He postulates that i f for some reason the organic material
that fell from the surface ocean to the deep ocean during glacial times carried 3096
morel~ari~/a relative to phosphorus than that falling during interglacial times) then
the C/ C ratio difference between surface and deep water would have been
larger, as suggested by the analyses of planktonic and benthic forams summarized
here. He would be forced, as was Shackleton (1977), to call upon in clr~ased forest and
soil storage during interglacial time to explain the whole ocean 8 C shift. If one
rethinks the evidence presented here in terms of Weyl's hypothesis, one realizes that
the two scenarios would produce identical records of all the properties discussed. In
fact the more I think about his hypothesis, the more I realize that i t is equally
plausible to my own.
There is one way in which more detailed studies of deep sea records might
differentiate between the two explanations, i/~s mentioned in the text) my
explanation does not permit any spike in the 6"~C record for planktonic forams
during transitions from glacial to interglacial time, as the phosphorus and organic
carbon removals from the oceans are simultaneo~ t Weyl's hypothesis) on the other
hand, decouples the cause for the whole ocean 8 C change (forlejst growth plus soil
development) from that for the change in the surface to deep 8 C difference (i.e.,
the changes in the mean C/P ratio in falling particulates). If, as is likel~[~a fo~e2st
growth lagged the change in C/P ratio in raining organic particles then the ~"C/ C
ratio record for planktonic forams would show a change toward lower values during
the time interval between these two events. While such a spike is not seen in the
data presented here, i t might show up in higher sedimentation rate cores (i.e., cores
in which events of 1,000 years duration were not blurred by bioturbation).
In Weyl's estimation the C/P ratio in the debris which falls to the deep sea may differ
from the biochemically controlled value of about 105 for plant matter because P (and
N) are preferentially consumed by herbivores (and higher members of the food chain),
leading to fecal pellets enriched in C relative to P (and N). Thus his hypothesis would
call on a change in the "food web" between glacial and interglacial time. Evidence
with regard to the current C/P ratio in organic matter respired within the deep sea is
given in Appendix C,
 Glacial to interglacial changes in ocean chemistry 169

A
I I I
• • ERDC B x 9 2 + 1 2 8
• • 0 0 0
2.0 -- qlO •0 0 O
"<-~0--1.95 - - ~ o
0 •o;
• o o

r• o•
m O O • O
O 0
t,O
00
1.5 0
WARM COLD
• G. S ~ C C U L I F E R A - I
-2.0 -I.5 -I.0 -0.5
SOl8 (%0)
B
I I I
ERDC Bx 9 2 + 1 2 8
P. OBLIQUILOCULATA
1.5 R m

0 °
O O O ®

ro °~e e e

e• @ °o ee
I.O
o 000% o~
WARM o • COLD •
I • I I
-1.5 -I.0 -0.5 -0.0
SOl8 (%0)

Fig. 7. 13C and 180 results for G. sacculifera (A) and for P. obliquiloculata (B) from
two western equatorial Pacific cores analyzed by o Berger and
KiIlingley(1977). The solid dots are for core Bx92 taken 2 south of the
equator and the open circles are for core Bx128 taken on the equator.
170 W.S. Broecker

I I I
RCI7-177
2 . 0 -- ® G. S A C C U L I F E R
ond G . R U B E R
®
E)

®
o % o
(9
O
- i s
or)
m

O
1.5 -- 8 e ®
ao
® ® ®(9
®
®
WARM COLD
I
1.0
-2!o .,!5 -I.0
8o18 (%0)

Fig. 8. 613C and 6180 results for G. ruber and G. sacculifera from equatorial
Pacific core RC17-177. As these analyses are based on tests from a
restricted size range (355-425 microns for G. sacc. and 425-500 microns for
G. ruber), they should be less subject to systematic error than other such
records. The analyses were carried out by Shackleton, who allowed me to
present them here.

Based on studies of the ecology of benthic Iorams Streeter and Shackleton (1979)
provide evidence for a lower glacial 0 2 content in the deep A t l a n t i c Ocean. Unfortunately,
as similar estimates have yet to be made for the Pacific and Indian Oceans) no oxygen
crosscheck on the hypothesis presented here can yet be made.

Why PO# and Not NO 3 as the Basis for These Calculations?

N i t r a t e rather than phosphate is considered by some marine biologists to be a rate-
l i m i t i n g ingredient for l i f e in the sea. While the arguments presented here could easily be
recast in terms of NO3, I f i r m l y believe that phosphate rather than nitrate is the ultimate
l i m i t i n g ingredient for life in the sea. The reason is that the ecology of marine organisms
 Glacial to interglacial changes in ocean chemistry 171

~CJ3(%o)
I 0 I 2

~
i
,~ ,-, 2.6 %,,

| BENTHICS
40
f/)
ILLS')/ (I.E. DEEP
IO
r v WATER)

O 80 - L
D
2.0 °/oo
ILl
(.9
<Z
120
- I PLANKTONICS
(I.E. SURF. WATER)
160

Fig. 9. Possible time histories of 613C in the surface and deep seas. The small
change for surface water represents a balance between the carbon and
phosphorus effects (see text).

can shift in order to fix the amount of atmospheric nitrogen needed to maintain the
biochemical N to P ratio (i.e., ~'15). There is no corresponding way to generate PO#. The
rate of supply to the sea of phosphorus is set by the continental weathering rate.

The Glacial to Interglacial Change in Surface Water CO2 Partial Presure

Based on the above temperature change~ volume change, ZCO 2 change, deep water
CO 3 change and PO 4 change, a rigorous calculation of the change in surface water Pco2
between glacial and interglacial time can be made.
Table 5 gives the PCO for a glacial surface ocean where the temperature was 2.5 C
2
lower, the mean oceanic salinity was 1.027 times higher, the mean oceanic £CO 2
concentration was 185um/kg higher, the CO3 = ion concentration of deep water was
3 ~m/kg higher, and the mean oceanic PO o concentration was 0.9 ]Jm/kg higher. The ratio
of organic carbon to CaCO 3 carbon rain is assumed to have been the same as today's (i.e, $
to 1). In order to achieve the required CO3 = ion content for deep water, an alkalinity
increase of 181 ~m/kg is required. Since the ZCO2 change is 185 iJm/kg the ratio of CaCO 3
precipitated to organic carbon removed to the shelves is close to unity. This is consistent
with the estimate made above that "compensation" was nearly complete. The resulting
glacial PCO is 225 x 10-6 atm.
The d~pendence of this result on the assumed changes in oceanic parameters is as
follows (based on the calculations given in Table 2):
172 W.S. Broecker

1) For each degree change in the glacial to interglacial change in the surface ocean AT
(assumed here to be 2.5 C), the PCO would change by about 13 x 10-6 atm (the lower
the glacial temperature, the lower t~e glacial PCO )"
2) For each 30-meter change in the glacial to interglacial sea level change (assumed
here to be 100 meters), the PCO would change by about 4 x 10-6 arm (the lower the
glacial sea level, the higher the g~acial PCO )"
3) For each 3 ~m/kg change in the CO3 = ion c~ncentration of deep water ( CO 2 content
held constant), the PCO of the atmosphere would change by about 9 x 10-6 arm (the
higher the CO3 = ion content the lower the glacial PCO )"
4) For each 0.1 ]Jm/kg change in the glacial PO 4 concentration the PCO would change
by about 10 x 10-6 atm (the higher the glacial PO 4 content, the lo2er the glacial

PCO2)"

TABLE 5. Interglacial to glacial changes in ocean chemistry. +

p 0 S ALK Z CO 2 CO 3 PO 4 NO 3 Pco2
Atm C °/oo 1Jg/kg !Jm/kg 10-6atm

Today's Average Deep Water (IADW)

400 1.0 34.7 2365 2250 86 2.2 33 -

IADW Brought to the Surface and Isochemically Heated to 21 C

21.0 34.7 2365 2250 101 2,2 33 1000

IADW Brought to Surface a f t e r Loss of PO 4 (and NO 3) to Plants

21,0 34.7 2271 1961 217 0.0 0 311

Glacial Average Deep Water (GADW)

390 1.0 35.6 2546 2435 89 3.1 46

GADW Brought to Surface and Isochemically Heated to 18.5 C

18.5 35.6 2546 2435 103 3.1 46 1050

GADW Brought to Surface after Loss of PO 4 (and NO 3) to Plants

18.5 35.6 2415 2029 270 0.0 0 231

Glacial surface ocean averages 2. C lower than today's,
Volume of glacial ocean .974 that of today's (sea level - 100 meters).
+ C a l c u l a t e d by the same procedures as outlined in Table 3.
 Glacial to interglacial changes in ocean chemistry ].73

5) For each 15% change in the ratio of organic-C to CaCO3-C rain, the PCO changes
-6 2
by about 9 x I0 arm (the more CaCO 3 rained per unit of organic C rained during
glacial time, the higher the glacial PCO )"
6) For each I% change in the ZCO 2 con~ent of sea water (CO3 = held constant), the
PCO^ would change by about 3 x 10-6 atm (the higher the glacial ~CO2, the higher
the g~acial PCO2).
Taking the glacial surface ocean temperature uncertainty to be I C, the glacial sea
=
level uncertainty to be 30 meters, the glacial CO 3 uncertainty to be 3 pm/kg, the glacial
PO 4 uncertainty to be + 0.I pm/kg, the glacial ZCO 2 uncertainty to be I% and the glacial
CaCO3-C to organic-C ratio uncertainty to be 15%, the aggregate error on the glacial
P c o 2 estimate is about 25 x I0 - 6 arm.

Chronology of Ocean Chemistry Chan~es

Other than stating that the change in CO2/N 2 ratio observed by Delmas et al. (1980)
and Berner et al. (19g0) in ice cores occurred over a period of a few thousand years9 I have
not discussed the chronology of the proposed ocean chemistry changes. Clearly another
check on the authenticity of the hypothesis outlined above is to determine whether the
chronologies of ice volume (from 6180 measurements on benthic forams), of continental
and shelf organic carbon storage (from 613C measurements on benthic forams), and of
atmospheric CO 2 content (from ice core studies) are internally consistent.
The relationship between the 613C and 6180 records is most easily studied because
these two records are kept by the same shell samples. Thus no questions regarding
correlation exist. Shackleton provides four sets of benthic foram data across glacial to
interglacial transitions. The pertinent results are listed in Table 6. To the first
approximation the 6180 and 613C changes are synchronous. Across one of the transitions
(termination II in M 12392) no case for a lead or lag can be made. Across the three
termination I transitions, there is a suggestion that the 613C change lags the 61gO change.
Such a lag is to be expected both from Shackleton's forest-soil hypothesis and from the
Niitisuma shelf sediment hypothesis. Detailed studies in high deposition rate cores will
have to be carried out before the existence of this lag can be pinned down.
Berner et al (lgg0) have shown that the change in CO2/N 2 ratio and the change in
6 180 both for the Camp Century (Greenland) and Byrd Station (Antarctica) ice cores are
broadly coincident. Thus i t appears that both the CO2/N 2 and the 613C changes occurred
during or very shortly after termination I (the rapid demise of the Wisconsin age ice
sheets).
Another consideration with regard to the chronology of the glacial to interglacial
transition is the 6 13C record for warm surface water (i.e., the planktonic forams record).
As mentioned above, the whole ocean 613C shift was largely nulled in the surface ocean by
174 W.S. Broecker

a compensation presumably due to the PO 4 effect. If the shelf hypothesis is correct) then
the two effects would have the same chronology and the nulling should persist through the
transition as well. On the other hand, were one of the causes to have lagged the other,
then a spike in 613C should be seen across the transition. As shown in Table 7, there is no
evidence for a ~13C spike associated with either the termination I or termination II
transitions.

TABLE 6. The phase relationship between the glacial to interglacial 6180 and 813C
changes as recorded by benthic forams. T~$ solid lines designate where the
glacial termination (as recorded by the 6 "O change) occurred. The data
are from Shackleton, 1977.

NORTH ATLANTIC SOUTH ATLANTIC SOUTH PACIFIC

M12392 UVIG, PEREG. V22-174 AUBERIANA Y71-6-12MG UVIG, PEREG

Depth 6180 613C Depth ~ 180 613C Depth 6180 ~ 13C

cm °Ioo °Ioo cm °/oo °Ioo cm °/oo °Ioo

8 3.34 0.19 0 3.07 0.Q8 1 3.51 -0,74

23 3.16 0.26 10 3.23 0.56 + 6 3.58 -0.92
31 3.05 0,10 20 3.09 0.28 12 4,55 -1.04
I 51 3.82 -0.91 I 30 3.44 0.03 18 4.68 -1.09
61 4.28 -0.77 40 3.99 0.09 24 4.73 -1.30
71 4.43 -0.95 47 4.74 0.11 30 4.57 -1.30
50 4.73 0.14 36 4.80 -1.39
824 3.17 -0.38
II 844 4.12 -0.51
856 4,54 -1.03
864 4.52 -1.27

Refers to the last termination (J" 1 I)000 years ago)

Refers to the previous termination (J" 125)000 years ago)

It would of course be of considerable interest to study the nature of the interglacial

to glacial transition. The ice core studies of Delmas et al. (1980) and of Berner et al.
(1980) do not extend back far enough in time to cover this transition. The benthic aI3c
record covers this interval only in core M 12392. As can be seen in Fig. I, the ~13C
transition in this core) although not well defined for this time interval) does give the
appearance of following the 6180 record. If so) then the main 613C change occurred at
about 70,000 years ago (the end of Emiliani's stage 5). It may turn out that like the 6J80
record the 613C record will show a more gradual transition from interglacial to glacial
than from glacial to interglacial. Detailed studies of the 6180-~ 13C relationship for both
 Glacial to interglacial changes in ocean chemistry 175

planktonic and benthic forams from Emiliani's stage 6 to his stage 4 will prove most
interesting in this connection,
The Role of Chemical Gradients within the Deep Sea
The deep A t l a n t i c is now fed primarily by water produced adjacent to Iceland. Its
proximity to this primary deep water source gives the central A t l a n t i c a higher 0 2 content
and higher 613C value than the other deep waters in the ocean. It has been suggested by a
number of authors that this northern A t l a n t i c source did not function during glacial time
and that waters forming round the perimeter of Antarctica were the main source of deep
water during glacial time. Were this the case, then changes in the benthic ~13C record in
the Atlantic would be influenced by both the global changes mentioned above and the
history of the northern Atlantic source.
There are three ways by which such a change in the deep water ventilation pattern
might be detected. One is through a comparison of the ~13C record for Atlantic and
Pacific benthics. As can be seen from Table I, the glacial to interglacial dI3c change for
four A t l a n t i c cores averaged 0.8O/o0 while that for two Pacific cores averaged 0.6°/oo.
Were the two oceans to have had the same source and ventilation time during glacials, the
Atlantic 613C change should have been 1.0°/oo larger than the Pacific change. Thus the
few data in hand do not support the Antarctic source hypothesis.
Another potential source of evidence in this record is the O 2 c o n t e n t of deep water.
Streeter and Shackleton (1979) use the ecology of benthic foraminifera to show that the O 2
c o n t e n t of deep A t l a n t i c water was lower during glacial time than during peak interglacial
time. This observation could reflect either the general lowering of global deep water 0 2
suggested here or the demise of the northern Atlantic source water. Until similar studies
have been carried out in the Pacific and Indian Oceans no firm conclusion can be drawn.
The third source of evidence lies in the lysocline and compensation depth record. In
today's ocean these horizons lie l to 2 kilometers deeper in the Atlantic than in the Pacific.
This difference is directly a t t r i b u t a b l e to the rapid flushing of the Atlantic by waters from
its northern source region. Were the waters in the Atlnatic to have had the same source
and ventilation time as those in the Pacific and Indian Oceans during glacial time, then the
lysocline depths should have b e e n more nearly equal. Sediment evidence shows that the
lysocline in the Pacific and Indian Oceans were slightly deeper than today's, while that in
the Atlantic was perhaps somewhat shallower. The Pacific lysocline was, however, still
considerably shallower than that in the Atlantic during glacial time. Thus, while the
evidence in hand favors a less divergent distribution of chemical properties between the
Atlantic and Pacific during glacial time than today, it suggests that substantial differences
of the type now seen persisted during glacial time.
176 W.S. Broecker

A Calcium C a r b o n a t e Preservation Event in Early Holocene Time?

As mentioned above compensation for the 10 x 1016 moles of carbon which appear to
have been removed from the sea as organic carbon a t the end of glacial t i m e would require
the deposition of 10 x 1016 moles of C a C O ~ (beyond the normal deposition rate). Spread
over the e n t i r e deep sea floor (area 3.3 x 10"4m 2) this would produce a layer of c a r b o n a t e
sediment 3 cm thick (3 gm/cm 2 with bulk dry density of 1.0 gm/cm3). As realized by
Shackleton (1977) such an event should not go unnoticed in the s e d i m e n t a r y record. Were
the organic m a t t e r formed instantaneously the CO3 = ion content of the entire ocean would
rise by about 50 ~m/kg. This would cause the entire deep ocean to become s u p e r s a t u r a t e d
with r e s p e c t to c a l c i t e and a fair fraction of it to become s u p e r s a t u r a t e d with r e s p e c t to
aragonite. This would lead to the preservation in deep sea sediments of CaCO 3 normally
destined for dissolution.
In order to understand why such events might not be quite so evident in deep sea
sediments as it might at first appear, it is necessary to consider s e p a r a t e l y three s e p a r a t e
major subdivisions of the sea floor:
1) the c a l c i t e rich sediment lying above the lysocline in which l i t t l e c a l c i t e dissolution
occurs today;
2) the c a l c i t e bearing sediments lying between the lysocline and the compensation depth
which today a r e being subject to appreciable c a l c i t e dissolution;
3) the red clay sediments from beneath the compensation depth which have lost nearly
all their c a l c i t e to dissolution.
The following c h a r a c t e r i s t i c s of deep sea sediments must also be kept in mind:
1) the a v e r a g e accumulation r a t e of the non CaCO 3 in the deep sea lies largely in the
range of 0.3 to 1.0 gm/cm 2 per 103 yrs (i.e., assuming a dry density of 0.5 gm/cm 3 for
such sediment~ only 5 to 16 cm have a c c u m u l a t e d during all of Holocene time);
2) the a v e r a g e rain r a t e of c a l c i t e toward the deep sea floor largely lies in the range 1.0
to 2.5 g m / c m 3 per 103 yrs (i.e., assuming a dry density of 1.0 gm/cm 3 for such
s e d i m e n t 10 to 25 cm a c c u m u l a t e d during Holocene time);
3) the e f f e c t i v e depth of bioturbation in Holocene deep sea sediments averages about
9 cm;
4) almost all l a t e Holocene sediments and all glacial age sediments a r e nearly free of
aragonite;
5) s e d i m e n t a t i o n r a t e s , and the e x t e n t of c a l c i t e dissolution changed almost everywhere
a t the close of glacial t i m e .
Without giving the reasons, these boundary conditions lead me to the conclusion that
the o c c u r r e n c e of an early Holocene CaCO 3 preservation event would only be readily
a p p a r e n t in the following two situations:
l) a brief episode of a r a g o n i t e preservation in early Holocene t i m e in sediments from
beneath (but not too far below) the present day lysocline for aragonite;
 Glacial to interglacial changes in ocean chemistry 177

2) a 10 or so centimeter thick zone of moderate calcite content sediment at the top of

red clay cores from beneath (but not too far below) the calcite compensation depth.
One would expect a core top zone of moderate calcite content rather than a layer of
calcite beneath a late Holocene red clay layer because the few centimeters of red
clay deposited above the calcite layer would have been rather thoroughly mixed into
the underlying calcite by bioturbation.
Evidence for both types of preservation event exists. Shackleton (1977) pointed to an
episode of aragonite (i.e., pteropod) preservation associated with termination I in Caribbean
core V12-122, as evidence for an ocean response to the removal of carbon as organic
material (see Fig. 10). Berger (1977) provides further evidence for this aragonite
preservation spike.

8018 Fig, 10, Relationship between pteropod

oO.O-O.S-LO-L5-2D-2.5 (arago~i~e shells) preservation and
the ~'~O record in Caribbean
..... -"-X
core V12-122 (Broecker, 1871).
The dashed line shows the
pteropod abundance (as measured
b ~ C h e n ) and the solid line the
6~°O values for G. ruber (as
JOOi measured by Van Donk9 1970).

150-

,oo-
250-

300 --
0 4000 8000
NO. P T E R O P O D S
gm COARSE FRAC.

Sundquist et al. (1977) show that on the west flank of the East Pacific Rise from 5°N
to 30°S there is a zone covering a depth range of a few hundred meters where red clay
seidment is capped by a calcite-bearing layer a few tens of centimeters thick. Sediments
from shallower depths are rich in CaCO 3 throughout; those from deeper depths are entirely
free of CaCO 3. The calcite-bearing layer at the top of the transition zone cores could
have been laid down during the preservation event required by the hypothesis presented
here. Radiocarbon ages on CaCO 3 from this layer lie mainly in the range 9,000 to 16,000
years. Although the average age (oo I%000) is a few thousand years too great, the dating is
178 W.S. Broecker

TABLE 7. 613C and 6"180 data for planktonic forams across terminations (i.e., glacial
to interglacial transitions). The solid ~oes show where the terminations
occurred (as recorded by the change in ~ °O).

Depth 6180 613C Depth 8180 613C

cm °/oo °/oo cm °/oo °/oo
V22-174 ERDC Bx 92
•.I- q¢#

G. RUBER G. SACC.

0 -1.23 1.62 1 -1.98 1.95

10 -1.21 1.25 2 -2.10 2.00
20 -1.01 1.30 4 -2.11 2.06
I 30 -0,73 1.16 7 -1.86 2.18
40 -0.22 0.98 8 -1.98 2.13
43 -0.18 1.09 10 -1.99 2.15
47 0.01 1.00 12 -2.07 2.01
50 0.12 0.89 13 -1.94 2.07
53 0.28 1.09 17 -1.83 2.00
18 -1.87 1.84
V22-174 . I 22 -1.56 1.96
G. SACC. 23 -1.58 2.16
24 -0.95 1.79
0 -0.92 2.18 27 -1.12 1.68
10 -0.74 2.03 28 -0.85 1.56
20 -0.59 1.90 29 -0.75 1.81
30 -0.14 1.73 32 -1.01 1.91
40 +0,22 1.65 33 -0.94 1.88
43 +0.41 1.74
47 +0.53 1.90 ERDC Bx 1.2.8
50 0.64 1.69 G. SACC.
53 0.49 1.90
5 -1.83 1.59
ERDC Bx 9 ~ . 7 -1.79 1.99
P. OBLIQU. 9 -1.71 1.53
10 -1.69 1.78
1 -1.19 1.15 II -1.63 1.78
2 -1.32 1.11 12 -1.65 1.81
4 -1.35 1.12 13 -1.65 2.02
7 -1.11 1.03 14 -1.09 2.10
8 -1.14 1.19 15 - 1 .5 5 1.91
10 -1.18 1.20 16 -1.60 1.83
12 -1.03 1.12 17 -i.86 1.81
13 -1.19 0.94 18 -1.32 2.00
15 -1.22 0.94 19 -1.29 1.75
17 -0.95 1.08 20 -1.54 1.75
18 -0.94 0.79 21 -1.32 1.85
20 -0.79 1.07 22 -1.31 1.74
22 -0.72 0.88 23 -1.11 1.76
I
23 -0.77 0.95 25 -1.09 1.81
24 -0.43 1.01 26 -1.19 1.89
25 -0.18 1.02 27 -1.53 1.65
27 -0.21 1.11 28 -1.09 1.77
28 -0.21 1.12 30 -0.94 1.95
29 -0.11 1.17 32 -1.00 1.67
 Glacial to interglacial changes in ocean chemistry 179

TABLE 7. CONTINUED.

Depth 6180 613C Depth 6180 613C

cm °/oo °/oo cm °/oo 0/00

32 -1.00 1.67
30 -0.16 1.19 33 -1.20 1.50
32 +0.05 0.88

ERDC Bx 12.8. RC17-177

P. OBLIQU. O. SACC. + G. RUB. +

1 -1.21 1.26 5 -2.08 1.98

2 -1.19 1.29 15 -1.87 1.85
3 -1.24 1.16 I 25 -I.00 1.68++
4 -1.06 1.19 35 -0.89 1.76
5 -1.15 1.25 45 -1.15 1.71
6 -1.20 1.17 55 -1.19 1.74
8 -1.24 1.27 65 -1.30 1.69
9 -1.26 1.01
10 -1.30 1.04 160 -2.06 1.49
12 -1.21 1.04 165 -2.06 1.50
13 -1.09 0.95 170 -1.95 1.22
14 -1.15 1.11 175 -1.79 1.50
15 -0.95 0.95 II 180 -1.52 1.31++
16 -0.88 0.86 185 -1.16 1.37
17 -0.74 0.93 190 -1.00 1.38
18 -0.80 1.01 ++ 195 -0.98 1.57
19 -0.75 1.00 200 -0.93 1.35
20 -0.80 1.00
21 -0.85 0.96
22 -0.55 1.04
23 -0.56 1.03
24 -0.73 1.04
26 -0.47 1.09
27 -0.45 0.96
30 -0.43 1.07

Shackleton (1977)
Berger and Killingley (1977)
+ Shackleton (pers. comm.)
++ I refers to the last t e r m i n a t i o n (.e 11,000 years ago), and II to the previous
t e r m i n a t i o n (J" 125,000 years ago).
180 W.S. Broecker

consistent with the preservation event hypothesis. As similar preservation events should
have occurred during e a r l i e r glacial to i n t e r g l a c i a l transitions) the hypothesis would have to
be made t h a t these layers largely dissolved during the 100)000-year t i m e periods separating
t e r m i n a t i o n s . Indeed Sundquist e t al. (1977) present evidence t h a t the c a l c i t e in the core
top layer in the transition zone cores is a l r e a d y undergoing dissolution. This is evidenced
both by the f a c t t h a t they have lower CaCO 3 contents than the tops of cores taken above
the transition zone) and that they have higher ratios of solution=resistent to solution=
sensitive planktonic species than do the tops of cores taken above the transition zone.
Remnant m a t e r i a l from previous interglacials may make up part of the layer and account
for the somewhat higher than e x p e c t e d average 14C age.

Implications t o C l i m a t i c Theory
Were the PCO in the a t m o s p h e r e during glacial times on the order 100 x 10- 6 atm
2
lower than today) then c l i m a t i c modeling tells us t h a t the mean global t e m p e r a t u r e would
have been 1.0 to 2.0 C cooler than now. The albedo d i f f e r e n c e between the glacial and
i n t e r g l a c i a l e a r t h may well have been large enough to produce a I to 2 C cooling.
A c c e p t i n g the CLIMAP (1976) e s t i m a t e of a 5 C global t e m p e r a t u r e d i f f e r e n c e between
18,000 years ago (peak glaciation) and today) the combined albedo plus CO 2 e f f e c t would
c o n t r i b u t e significantly to the cooling during glacials. As both the CO 2 and albedo change
appear the consequence of the c l i m a t e changes they cannot then be called upon to induce
them. Some other driving mechanism must be involved. The CO 2 changes discussed here
m e r e l y amplified this cause.
Many s c i e n t i s t s believe that the primary cause for glacial cycles is the changes in
seasonal c o n t r a s t produced by periodic changes in the earthts orbital e l e m e n t s (i.e., the
Milankovich hypothesis). One problem with this hypothesis is that) whereas the chronology
of the seasonal c o n t r a s t changes is quite d i f f e r e n t at high northern than a t high southern
l a t i t u d e s , the c l i m a t i c records for these two regions a r e very similar. As the CO 2 change
discussed here is induced by the growth and r e t r e a t of the northern hemisphere ice sheets
(there is no evidence for significant changes in ice volume for the southern hemisphere),
the CO 2 change provides a means of t r a n s m i t t i n g the northern hemisphere c l i m a t i c e f f e c t s
to the southern hemisphere.

Conclusions
The 13C record in deep sea cores is consistent with an oceanic PO 4 induced reduction
in the a t m o s p h e r i c CO 2 c o n t e n t during glacial t i m e . One means of achieving the rapid
reduction in oceanic PO 4 c o n t e n t necessary to produce the CO 2 pressure rise observed in
ice cores is to deposit organic-rich shelf sediments during the early phases of the
i n t e r g l a c i a l sea level transgression.
 Glacial to interglacial changes in ocean chemistry 181

Like glacially=induced albedo changes, the glacially-induced atmospheric CO 2 c o n t e n t

changes must have served as an amplifier for some primary cause of climatic change. The
CO 2 change may prove, however, to be a boon to those who favor the Milankovitch
hypothesis in that it provides a way to transmit a northern hemisphere climatic change to
the southern hemisphere.

Acknowledgments
Taro Takahashi was kind enough to carry out the Pco2 calculations given in this
paper. Because the final answers were obtained only after many iterations, this proved to
be a considerable task. Discussions with Garry Brass, who put me on to shelf sediments,
with Rick Fairbanks, Nick Shackleton, Bob Matthews and Claude Duplessy, who brought me
up to date on the 13C results for deep sea cores and with Taro Takahashi on ocean carbon
chemistry, are much appreciated. Flip Froelich somehow sensed my struggle to decide how
best to move phosphorus in and out of the oceans on a glacial to interglacial time scale and
sent, unsolicited, at just the critical moment, a summary of his phosphorus budget for
today's ocean. As his budget verifies the long suspected but heretofore very shaky 100,000-
year oceanic residence time for phosphorus, my temptations to turn to continental
weathering rate, oceanic mixing rate changes . . . were squelched and I was in a receptive
mood for Brass's suggestion of the formation and destruction of a small reservoir of shelf
sediment. I also thank Mike Bender who over the years has shared my interest in nutrient
element-driven changes in ocean chemistry. Several discussions with him rekindled my
interest in one of my earlier scientific loves and led me to "pounce" on the ice core results.
He also was kind enough to give the paper a thorough review. I also thank Hans Oeschger
and his colleagues at Bern for giving me early access to their ice core results and for taking
the time to explain to me the strengths and weaknesses of their data set.
A f t e r reading a draft of this paper Peter Weyl came to see me at Lamont and
convinced me of the logic of his alternative explanation for the evidence presented here
(i.e., that the ratio of C/P in the organic matter raining to the deep sea was higher during
glacial than during interglacial times).
Finally, I acknowledge Eric Kraus, whose invitation to speak at the CIMAS Symposium
in Miami gave me a deadline to work against. [ must apologize to him and to the readers of
this volume for my failure to provide the review of temporal variations in ocean chemistry,
which was my assigned task.
This is a Lamont-Doherty Geological Laboratory contribution.
182 W.S. Broecker

APPENDIX A
CaCO 3 to Organic Carbon Rain Rate Ratio
The e s t i m a t e of the ratio of carbon leaving the surface ocean as organic carbon to
that leaving as CaCO 3 was made as follows. The compositions of surface water samples
from various parts of the ocean were normalized to the salinity of circumpolar deep water
(34.71°/oo). Circumpolar deep water was chosen for the normalization because its
composition lies close to that /or mean deep water. The normalized PO#, NO3, ECO 2 and
ALK concentrations for the surface water were then subtracted from those for circumpolar
water. The alkalinity difference was then corrected for the n i t r a t e effect (i.e., the NO 3
change is added to the alkalinity change). The amount of CaCO 3 produced from this
surface water is then taken to be half the corrected alkalinity difference. The amount of
organic carbon produced can then be obtained in two ways. first, by the difference
between the ~.CO2 difference and the amount of CaCO 3 proproduced, and second, by the
Redfield ratio of carbon to phosphorus in marine plant tissue (i.e., 0.05) times the
difference in phosphate content. An example is shown in Table A - I . The results for 20
stations (occupied during the GEOSECS program) are summarized in Table A-2. The ratio
of organic to CaCO 3 utilization ranges from 3.5 to 7.2 and averages #.5.

TABLE A - l . Example of method used to calculate the ratio of organic carbon to CaCO 3
carbon produced in surface waters.

PO# NO 3 CO 2 ALK

Circumpolar 2.22 32. l 22#5 2354

Deep water

Norm alized 0.06 0.1 1951 2318

Stn 31 Surf H20

Difference 2.16 32 294 36

ACaCO3 = 36 2+ 32 = 34 ~m/kg

aCorg = 294 - 34 = 260 ~ m / k g (Method #1)

~C = 105 x 2.16 = 227 ~m/kg (Method #2)

org

AC
org 244
= = 7.2
8ZaCO 3 "34

To salinity of circumpolar deep water.

 Glacial to interglacial changes in ocean chemistry 183

TABLE A-2. Organic to CaCO 3 carbon utilization ratio for 20 GEOSECS surface waters
(circumpolar deep w a t e r was used at the base for normalization).

METHOD #1 METHOD #2
Station T ACaCO 3 ACorg A Corg ACorg
Number C ACaCO 3
vmlkg

ATLANTIC

31 27 34 260 227 7.2

37 28 38 298 231 7.0
42 27 59 263 224 4.1
54 26 61 277 222 4.1
61 17 56 229 217 4 .0
105 25 56 243 210 4 .0
115 19 55 234 230 4.2
120 18 65 240 226 3.6

PACIFIC
214 28 60 259 226 40
201 18 37 133 190 44
227 27 66 232 228 35
244 26 48 220 174 4 1
260 29 47 291 208 5 1
269 27 49 275 225 5 1

INDIAN

438 27 66 239 222 3.5

442 30 65 254 221 3.7
446 28 38 242 226 6.2
417 27 59 240 183 3.6
420 27 54 227 209 4.0
427 26 56 245 217 4.1

Mean 4.5

This approach might be c r i t i c i z e d because of the selection of a single deep water as

the base for the calculation. As shown in Table A-3, the calculated ratio of carbon
re m o v ed as organic m a t e r i a l to carbon removed as CaCO 3 is smaller using North Atlantic
Deep Water (NADW) as the base for normalization and larger using North Pacific waters.
This is because much of the CaCO 3 raining to the deep Atlantic is preserved in sediments,
while most all of that raining into the deep Pacific dissolves. As roughly 15% of the
CaCO 3 and I% of the organic carbon failing from surface waters is preserved in sediment,
the e s t i m a t e s made here are biased by about 15%. Thus the global mean ratio of organic to
CaCO 3 removal from surface water (4.5) should be decreased by 15%. Based on these
considerations, I conclude that the best e s t i m a t e of Co r g / CaCO 3 is 4 + I.
184 W.S. Broecker

TABLE A-3. Dependence of ACor~/&CaCO ~ e s t i m a t e s for station 31 surface water (deep

w a t e r s e l e c t e d for n~t'malizati~n).

METHOD #1 METHOD #2

ACorg IxCorl ~
lXCaCO 3 IXCorg ACaCO3 ACorg aCaCO3

NADW (Stn #2
3000 m e t e r s ) 26 233 8.6 132 5.1

CPDW (Stn 76
0,000 m e t e r s ) 3# 260 7.6 227 6.7

NPBW (Stn 217

5000 m e t e r s ) 85 337 #.0 2## 2.9

NPIW (Stn 21#

1100 m e t e r s ) 103 376 3.7 318 3.1
Mean 6.0 #. 5

APPENDIX B
The 613C - PO# Relationship
Two major processes control the distribution of 13C/12C ratios of the oceants
dissolved inorganic carbon.
(1) The f o r m a t i o n (through photosynthesis) and destruction (through respiration) of
organic tissue. The carbon fixed during photosynthesis is depleted in 13 C by about 200/00.
The isotope s e p a r a t i o n during respiration is quite small. The mean dissolved inorganic
carbon content of sea w a t e r is 2250 ]Jm/kg. Thus for each 100 lam/kg of organic m a t t e r
formed in s u r f a c e water or r e l e a s e d in the deep sea the isotopic ratio of the dissolved
inorganic carbon will change by about 0.9o/00 (becoming richer in 13C as a result of
photosynthesis and poorer in 13C as a result of respiration).
(2) Because of the t e m p e r a t u r e dependence of the CO 2 ( g a s ) - E CO 2 (aqueous)
equilibrium carbon f r a c t i o n a t i o n (~ - 0 . 1 ° / o o / C ) and because of the possibility of a kinetic
s e p a r a t i o n during net uptake or release of CO 2 from the surface sea, the i n t e r a c t i o n
between local s u r f a c e s e a w a t e r and the a t m o s p h e r e will lead to departures in the 13C/t2C
r a t i o in local surface w a t e r from the ECO 2 -13C/12C relationship mentioned above. This
situation is complex because the response t i m e for carbon isotope equilibration between
m i x e d - l a y e r w a t e r and the a t m o s p h e r e (~ 10 years) is comparable to or longer than the
residence t i m e of surface w a t e r in a given region. As shown in Fig. B-l, isotopic
equilibrium has not in general been achieved between carbon in surface water and that in
the overlying air. On the other hand, the time for chemical equilibration between the CO 2
 Glacial to interglacial changes in ocean chemistry 185

partial pressure in mixed-layer water and air (J" I year) is more nearly comparable to the
residence time of water in a given region of the surface ocean. Because of this the kinetic
effects resulting from net invasion or evasion of CO 2 from the surface ocean could play an
important role in the 13( distribution for surface waters.
\I I I

EQUILIBRIUM
"" WITH ATM 813C=-7.2
MOOK ET AL.(1974)

•• [] [] O •O
-2 "; ®,%'x
[ DW° \ : 0o
I LSW ~ osw
I I .o.T.E.. CE.TRAL A"TA"CT.CI \
I I A~L'"~'c • O ® I \
/ [PACIFIC I [] [] [
|

O/I I I
O IO 20 30
TEMPERATURE (°C)

Fig. B - I . Plot of ~13C versus water temperature for surface waters from various
re~ons of the ocean. Also given are the preformed ( i . e , A.O.U. corrected)
8 " ' C values for three key deep waters, Weddell Sea Bottom Water (WSBW),
mixtures of Labrador Sea Deep Water (LSW) and Denmark Straits Overflow
Water (DSW) and Two-Degree Discontinuity Water (TDDW). The trend
expected, i f isotopic equilibrium with the atmosphere existed, is shown by
the solid line. Clearly, while the surface ocean as a whole is at steady state
with the atmosphere local equilibrium has not been achieved.

To save confusion in the discussions which follow, it must be stressed at the onset
that the average 13C/12C ratio in the surface ocean must be maintained at a dynamic
steady state with the global deep water. The ~13C in the atmosphere in turn reflects some
mean of the 6 13C distribution in surface waters. As the atmosphere contains only 2% as
much carbon as the ocean, its 13C/12C ratio is slave to the carbon cycles occurring within
the sea.
186 W.S. Broecker

13C in Deep Sea Carbon

The distribution of ~13C values in deep A t l a n t i c and deep Pacific waters follows
quite well the trend expected from photosynthesis and respiration (Kroopnick, 1971 and
197¢a). This is best seen using plots of ~13C versus POe rather than dl3c versus CO 2.
The reason is that the concentration of ZCO 2 is altered by CaCO 3 formation and
dissolution as well as by the formation and respiration of organic residues. L i t t l e carbon
isotope separation occurs during the CaCO 3 cycle. Also, the total CO 2 content of the
surface sea differs from region to region, depending on the alkalinity of the water and on
the degree of equilibration with the atmosphere. The POe content of seawater is a much
better index of the extent to which carbon was gained during photosynthesis and lost
through respiration than is the £CO 2 content. As can be seen in Fig. 3 in the main part of
the paper the 613C values for surface and deep waters in the temperate and equatorial
ocean form an approximately linear trend. The details of this trend are discussed in a
separate paper (Broecker and Wanninkhof, in press). The trend is roughly that which would
be expected from the relationship

C
a6 13C- A 13Cphot ° -~or8

A[PO# ] [z
CO2]- mean ocean

200/00 x 105
2250 ]Jm/kg

0.93~

The 13C/12C ratios and phosphate contents for deep waters at the time they left
contact with the atmosphere (i.e. their preformed POe and 613C values) can be
reconstructed using the 0 2 content of the water. The relationships are as follows:

= _ A.O.U.
POe ° POe 130

and
613cO = ~13C _ ~.93 A.O.U.

This reconstruction has been carried out for a number of the oceans' major water types (see
Table B-I). These waters have nearly the same preformed 613C value (I.3 + 0.1) but show
a range of preformed PO 4 contents (from 0.7 to 1.4 !Jm/kg).
 Glacial to interglacial changes in ocean chemistry 187

TABLE B-I. Preformed phosphate and ~13C for s e v e r a l i m p o r t a n t deep water types.

Water Sat Obs Obs Preformed Obs Preformed

AOU
Type 0 02 02 PO 4 PO 4 813C 613C

C ~m/kg ~m/kg °/oo °/oo

NSBW =1.3 358 321 37 0.92 0.65 1.1 1.4

NADW 2.0 331 269 62 1.38 0.92 0.9 1.4

AABW 0.0 3q? 225 122 2.29 1.39 0.45 1.3

CPDW 0.7 301 207 13# 2.20 1.20 0.$ 1.4

NPBW i.0 339 162 177 2,40 1.08 -0.I 1.2

NPOMW 34 320 20 300 3.10 0.88 -0,8 1,3

NSBW Norwegian Sea Bottom Water

NADW North A t l a n t i c Deep Water
AABW A n t a r c t i c Bottom Water
CPDW Circumpolar Deep Water
NPBW North Pacific Bottom Water
NPOMW North Pacific Oxygen Minimum Water

13C in Surface Water Carbon

6 13C results for Atlantic surface waters and Pacific surface waters cover in the
range 1.3 to 2.4O/oo (see Figs. B-2 and B-3). The low 613C values (i.e., < l.S°/oo) come
from the polar regions where the surface waters contain appreciable phosphate.
The influx of fossil fuel CO 2 has reduced the ~13C in both the atmosphere and
surface water over the last 100 years. Broecker and Wanninkhof (in press) e s t i m a t e this
reduction to be about 0.3°/oo.
It is possible that a kinetic isotope fractionation associated with the with the net
transfer of CO 2 to or from the surface ocean causes some of this variability. The possible
reason for this kinetic e f f e c t is shown in Fig. B-q. Its implication to the ocean 13C cycle is
shown in Table B-2. Seasonal cycles in t e m p e r a t u r e should produce seasonal cycles in the
13C for the surface mixed layer.
There is, however, a controversy with regard to the magnitude of the kinetic
fractionation. Keeling (1977) estimates it to be l q ° / o o for invading CO 2. He cites
experiments involving CO 2 uptake in KOH solutions. Sigenthaler and Munnich (in press)
challenge this conclusion, claiming that the large kinetic fractionation seen for KOH is the
result of the reaction between CO 2 and O H - ions in the boundary film, While this reaction
dominates for KOH solutions it is of minor importance for the sea. In the absence of the
OH reaction, Sigenthaler and Munnich (in press) e s t i m a t e that the kinetic fractionation
188 W.S. Broecker

2.5 I I I I I I

O0
0 0 0
0
0 0 0
2.0 0 0 0 O0 0
0

v 0
0 0 0 0 0 %0 °
0
0 oo
0o 1.5 %8 ° m
0
0
0
ATLANTIC o o
#
I.O m I I I I I
60 ° 40 ° 20 ° 0 ° 20 ° 40 ° 60 ° 8 0 '='
$ LATITUDE N

2.5 I I I I I I
• 0
0
O 0 •
%" 2 . 0 B • • O0
• • •
&'o • 0 •
(J q~ • m • 0
mi =ram" • •
co 1.5 • II I
• 80 ,,,• •

PACIFIC

I I I i I I I
I.C
60 ° 40 ° 20 ° 0° 20 ° 40 ° 60 ° 80 °
S LATITUDE N
25 I 0 I I I I I
0 0
A
0
%0 o o
O O O O
2.0
° -

o )
PACI F IC
1.5
150°W 8I
I I I I I I
60°40 ° 20 ° 0 ° 20°40°60 o
S LATITUDE N

Fig. B-2. 613C values for surface w a t e r s from the A t l a n t i c and Pacific Oceans. In
the upper pannel are the GEOSECS A t l a n t i c d a t a (Kroopnick) 1980). In the
middle panel a r e the pre=GEOSECS m e a s u r e m e n t s on Pacific surface water
samples made in the La 3olla l a b o r a t o r y (Kroop~ick, 1974a, I97#b) and the
GEOSECS m e a s u r e m e n t s on the CO 2 used for C analyses (Ostlund) 1980).
In the lower panel all the anlayses made in the La 3olla l a b o r a t o r y on Hudson
70 samples (Kroopnick et al.9 1977)o
 Glacial to interglacial changes in ocean chemistry 189

32-

28 SURFACE
WATER
--MEAN 1.9%o
24

A
A
20 A
P A
<50 ° P A
UD A P A
W 16 A P A
J A P P
O_ A P P
P P P
12- P P P
P P P
P P P A
b_ m
P P P A
0 P P P P
P P P
d P
P
P
P
P
P
P
P
A
P
Z 4- P P P P P
P P P P P
IHR, P P P P P
m
P P P P P I P
M EAN 1.6% o

!f
> ~"~0 NP NA NP
OU NP NA NA
NA ANT NA
ANT ANT ANT ANT
ANT ANT ANT ANT
ANT ~,NT ANT NA 'ANT ANNATI
ANT ANT ANT ANT;ANT NA

= ) = = = t i = = = = i =
1.00 1.25 1.50 1.75 2.oo 2.25 2.50
813C (%0)

Fig. B=3. Histogram of 613C values for surface water samples. The upper panel gives
the results for samples collected between 50°N and 50°S in the Atlantic (A)
and Pacific (P). The lower panel summarizes the results on high latitude
samples from the Antarctic (ANT), northern Atlantic (NA) and Northern
Pacific (NP).
190 W.S. Broecker

~ CISAIR~-7 %0
ESCAPING CO2

INVADING CO2
8 C I 3 ~ - 2 1 °/oo
l c,3 = - 2 , o/oo

8ClSsw 2 %o

A 8CI31NVASION = - 14 %o

A 8 CI3 EVASION = - 2 3 % 0
EQUIL FRAC= 9%0

Fig. B-4. The equilibrium isotope fractionation between atmosphere and ocean carbon
is about 9 /oo (at 18 C). Experiments involving the u~take of atmospheric
CO 2 by KOH solutions yield 8 C values of about -21 /oo for the captured
CO~. This suggests (but does not prove) that a kinetic fractionation occurs
duri'hg CO~ uptake by or loss from the surface ocean. Sigenthaler and
Munnich (i~ press) dispute the applicabilit~y of the KOH results to sea water.
Their calculations suggest that the -21VlOO value shown in this figure be
reduced to -2O/oo.

would be only 20/00. If so, then the seasonal changes alluded to above would be only about
half as great as shown in Table B-2. (The invading CO 2 would be I I°/oo rather than 23°/oo
lighter than that in ambient sea water.)
 Glacial to interglacial changes in ocean chemistry 191

TABLE B-2. Hypothetical experiment in which surface ocean water at equilibrium with
the CO 2 in the atmosphere at 25 C (both chemically and isotopically) is
cooled by 15 C. The cooling would lower the PCO^ in the water by about
I00 x 10-6arm. Were the water contained in an 86 m deep tank, the half
time for the reestablishment of chemical equilibrium would be about 0.7
sw -6
years (invasion r a t e 16 moles m - 2 y r - 1 , evasion r a t e PCO /330 x 10 ) x (16
moles m - 2 y r -1 and Revelle l a c t o r 10). The half t i m e for2reestablishment of
isotopic equilibrium would be about 7 years. Thus, as shown in the table,
chemical equilibrium would have been largely reestablished a f t e r 2 years,
while isotopic equilibrium would have proceeded only a fraction of the way
toward equilibrium. If the 60 ~m/kg of excess CO~ required to reestablish
c h e m i c a l equilibrium e n t e r e d from the air with a ~3C of - 2 1 ° / o o , then the
613C of the w a t e r would shift from 2.0 to 1.q% o as the result of chemical
equilibration. Subsequent isotopic equilibration would t a k e the 813C back to
the initial +2.0 value and beyond to 3.0°/oo.

Initial After 2 Years 20 Years

Equil Cooling Later Later

Temp 25 15 15 15
C

PCO 2 330 230 330 330

10-6atm

E CO 2 s . w . 2000 2000 2060 2060

6 13C s . w . .
O/o ° 2.0 2.0 1.4 3.0

The a c t u a l value would be several tenths per rail higher because of partial isotopic
equilibrium with air during this t i m e interval,

APPENDIX C
Carbon to Phosphorus Ratio in Organic Debris Being Oxidized
Within the Deep Sea
Although it is well established that the ratio of carbon to phosphorus in
microorganisms a v e r a g e s close to 105, an additional assumption is required if this ratio is
to be applied to the relationship between ~13C and POrt in the deep ocean. This assumption
is t h a t carbon and phosphorus a r e respired in this 105 to 1 ratio. If for example, phosphorus
were r e c y c l e d more e f f i c i e n t l y within the sea than carbon, the ratio of C / P in respiration
192 W.S. Broecker

~ o I I I' J I '"
270 ATLANTIC OCEAN
0"4= 4 5 . 8 0 %0
260

250
°-,26 ~ .

24(

25(
1.2 1.3 1.4 1.5
PO 4 ( / x M / k g )

200 ! I I I

180

~L ~6o
dO2 I
?
(M
0 140 &~-COzOaG = -158 _ 106 ~'~
A P04 - #30

120 I I I , I I
2.0 2.2 2.4 2.6
PO 4 (FM/kg)
160
!~--~R9 I I i I " ,
1 2 CiF5 COCEAN --
140

120

I00

80 _ T °~ ~ ~\- o

~-T~.- -~To -'~

60 I i I I I I\
2.4 2.6 2.8 3.0
PO 4 (p.M/kg)

Fig. C-1. Plots of dissolved oxygen against dissolved phosphate along the #5.gO°/oo
isopycnal horizon (depth 2300 to 2600 meters) in the three major oceans.
 Glacial to interglacial changes in ocean chemistry 193

TABLE C-I, Relationship between dissolved 0 2 and PO 4 along the 45.800/00 isopycnal
horizon.

Standard Latitude Longitude O~ PO/i

Num bet IJm/kg lam/~g

ATLANTIC OCEAN

27 42°00'N 42°02'W 273 1,19

28 39°00'N 43°59'W 269 1,20
29 35°58'N 47°00'W 269 1,19
30 31°48'N 50°46'W 259 1,27
31 27°00'N 53°32'W 255 1,32
32 23°50'N 54°00'W 254 1,31
33 21°00'N 54°00'W 255 1,31
34 18°01'N 53°59'W 259 1,28
36 15°00'N 53°56'W 257 1,26
37 12°02'N 51°00'W 263 1,22
39 07°58'N 43°51'W 263 1,25
40 03°57'N 38°31'W 258 1,28
42 00°58'N 37°04'W 261 1,24
46 00°59'5 34°02'W 258 1,25
48 04°00'5 29°00'W 253 1.29
106 16°00'5 01°58'E 232 1.50
107 12°00'S 02°00'E 233 1,50
109 02°00'5 04°30'W 248 1,38
110 00°01'S 09°ll'W 251 1,33
111 02°00'N 14°01'W 250 1,37
112 06°20'N 17°16'W 242 1,40
113 10°59'N 20°32'W 243 1,42
114 21°II'N 21°46'W 237 1.43
115 28°01'N 26°00'W 251 1,34
116 29°56'N 30°24'W 254 1,32
117 30°40'N 38°58'W 261 1,27
118 31°18'N 45°39'W 260 1,27
119 31°49'N 50°53'W 264 1,24
120 33°16'N 56°33'W 267 1,22
121 35°59'N 67°59'W 270 1,19

INDIAN OCEAN

435 39°57'S 109°58'E 185 2.16

it36 29° 15'S 109°58'E 160 2.37
4/.38 19°29'S 101o 17'E 157 2,37
440 09°21'S 95°46'E 149 2,44
441 05o0 I'S 91°46'E 145 2,46
442 01o 12'S 90° ~-5'E 141 2,50
445 08°3 I'N 86°02'E 127 2,57
446 12°29'N 84°29'E 124 2,59
194 W.S. Broecker

PACIFIC OCEAN
218 50°26,N 176°35'W 86 2.71
220 53°06,N 177° 17'W 70 2.90
221 45° 13'N 169°25,W 94 2.69
222 40° 10'N 160°30'E 94 2.64
223 34°58,N 151°50,E 106 2.70
224 34° 15'N 141°58,E 97 2.72
225 32°37,N 161°55,E 95 2.73
226 30°34,N 170°36'E 92 2.71
201 34° 10'N 127°53'W 92 2.90
202 33°06,N 139° 34'W 90 2.83
204 31°22,N 150°02'N 85 2.87
212 30°00,N 159°50'W 96 2.77
213 31°00,N 168°27,W 92 2.7~
214 32°01,N 176°59'W 92 2.78
215 37°28,N 177° 19'W 87 2.75
217 44°40'N 177°03'W 82 2.75
227 25°00'N 170°05'E 110 2.58
228 19°0I'N 169°21,E 116 2.55
229 12°53'N 173°20'E 116 2.55
230 12°29'N 177°26'E i14 2.62
231 14°07'N 178°34'W 110 2.57
232 15°24'N 176° 13'W 113 2.62
233 18°14'N 169°08,W 110 2.67
234 19°52'N 163° 14'W 109 2.59
235 16°45'N 161°23,W 110 2.65
236 13°16'N 163°58,W 112 2.65
237 12°30'N 165°25,W 110 2.53
238 08°II'N 167°04'W 113 2.64
239 05°53'N 172°00'W 114 2.64
240 03°22'N 177° 13'W 119 2.55
241 04°33'N 179°00'E li7 2.68
242 03°04'N 178°55'E 122 2.65
243 02°00'N 178°56'E 121 2.67
244 01°01'N 178°55,E 121+ 2.62
245 00°31'N 178°59'E 123 2.54
246 00°00, 178°59'E 123 2.56
247 00°28'S 17~°59'E 124 2.58
248 01°02'S 179°02'E 121 2.58
249 02001% 179°01,E 12q 2.59
250 02°59'S 178°59'E 131 2.53
251 04°34'S 178°57'E 131 2.58
252 08°29'S 178°05'W 140 2.58
253 12°40'S 175°03'%!/ lqq 2.5/+
254 13°14,S 173°48'W 145 2.51
255 12°1 l'S 169°54'W 149 2.39
256 09( ll'S 169°00,W 142 2.42
257 IC IO'S i 69°58'W 142 2.47
259 15 03'S 170°22'W 148 2.46
260 15 )16'S 169°54,W 149 2.44
261 15 46'S 169°1 l'W 151 2.38
262 16 OI'S 168°28,W 150 2.38
263 16( 39'S 167°04'W 152 2.43
264 17<)16'S 166°00,W 152 2.44
265 1 7 ( '48'S 164°56'W 152 2.39
267 19°15'S 171°25,W 148 2.46
268 20°30'S 172°48'W 146 2.46
 Glacial to interglacial changes in ocean chemistry 195

269 23'559'S 1714°26'W 1147 2.143

270 23'558'S 175°15'W 1147 2.148
272 214()02'S 175°143'W 1148 2.143
273 29'537'5 175°142'W 150 2.142
275 30' )0 I'S 176°50'W 130 2,143
277 30' )07'S 179°314'W 151 2.142
278 36531'S 179°36'W 157 2.39
30,7 2g' )30'N 121°29'W 99 2.714
3145 22 ( 31'N 122°12'W 101 2.72
3143 16°31'N 123°01'W IOQ 2.69

would increase down the water column (i.e.) i t would be less than I05 in shallow water and
greater than 105 in deep water). To check this I have looked at the slopes of the
relationship between dissolved oxygen and phosphorus along the 145,80°/oo 014-horizons in
the deep Atlantic) Indian and Pacific Oceans. The data used is given in Table C-! and
plotted in Fig. C - I . The slopes of the lines in these plots can be converted to organic
carbon to phosphorus ratios by dividing by -1.30 (the ratio of 0 2 molecules consumed per C
atom oxidized). As can be seen from the figure the ratio is 1096 lower than the "expected"
vlaue of 105 in the deep Atlantic Ocean) very close to the expected value in the deep Indian
Ocean and 3096 higher than the expected ratio in the deep Pacific Ocean.

References
Berger, W.H. (1977): Deep=sea carbonate and the deglaciation preservation spike in
pteropods and foraminifera. Nature 265: 301=304.
Berger) W.H. and J.S. Killingley (19775: Glacial-Holocene transition in deep=sea
carbonates: Selective dissolution and the stable isotope signal. Science 157: 563=566.
Berner, W.) H. Oeschger and B. Stauffer (19805: Information on the CO 2 cycle from ice
core studies. Radiocarbon 22: 227=235.
Broecker) W.S. (19715: Calcite accumulation rates and glacial to interglacial changes in
ocean mixing. I__n: K.K. Turekian (Ed.), The Late Cenozoic Glacial Ages. Yale
University Press) pp. 235=265.
Broecker, W.S. (19745: Chemical Oceanography. Harcourt Brace 3ovanovitch, New York)
214 pp.
Broecker) W.S. and T. Takahashi (1978): The relationship between lysocline depth and in
situ carbonate in concentration. Deep=Sea Res. 23: 65-95.
Broecker) W.S. and R.K. Wanninkhof (in press): 13C as an oceanic tracer.
CLIMAP (19765: The s u r f a c e o f ice=age Earth. Science 191: I131=I137.
196 W.S. Broecker

Delmas, R.3., J.-M Ascencio and M. Legrand (1980): Polar ice evidence that atmospheric
CO 2 20,000 yr. B.P. was 5996 of present. Nature 284: 155-157.
Duplessy, 3.-C. (1978): Isotope Studies. I_.n: 3ohn Gribbin (Ed.), Climatic Change.
Cambridge Press, pp. 46-47.
Froelich, P.N., M.L. Bender, N.A. Luedtke, G.R. Heath and T. DeVries (in press): The
marine phosphorus cycle. American Journal of Science.
Gardner, J.V. (1975): Late Pleistocene carbonate dissolution cycles in eastern equatorial
Atlantic. Cushman Foundation Foraminileral Research Special Publication 13: 129-
141.
Keeling, C.D. (1973): The carbon dioxide cycle: Reservoir models to depict the exchange
of atmospheric carbon dioxide with the ocean and land plants. In: S.I. Rasool (Ed.),
C h e m i s t r y of the Lower A t m o s p h e r e , pp. 251-329.

Kroopnick, P.M. (1971): Oxygen and Carbon in the Oceans and the Atmosphere: Stable
Isotopes as Tracers for Consumption, Production and Circulation Models. Ph.D.
Dissertation, University of California, San Diego, 230 pp.
Kroopnick, P.M. (1974a): The dissolved O2-CO2-13C system in the eastern equatorial
Pacific. Deep-Sea Research 21:211-217.
Kroopnick, P.M. (1974b): Correlations between 13C and ECO 2 in surface waters and
atmospheric CO 2. Earth and Planetary Science Letters 22: 397-403.
Kroopnick, P.M. (1980): The distribution of 13C in the Atlantic Ocean. Earth
and Planetary Science Letters 49: 469-484.
Kroopnick, P.M., W.G. Denser and H. Craig (1970): Carbon-13 measurements on dissolved
inorganic carbon at the North Pacific (1969) GEOSECS Station. 3ournal
of Geological Research 75: 7668=7671.
Kroopnick, P.M., R.F. Weiss and H. Craig (1972): Total CO2, 13C and dissolved oxygen -
180 at GEOSECS II in the North Atlantic. Earth and Planetary Science Letters 16:
I03-ii0.
Kroopnick, P.M., S.V. Margolis and C.S. Wong (1976): 613C variations in marine carbonate
sediments as indicators of the CO 2 balance between the atmosphere and the oceans.
In: N.R. Anderson and A. Malahofi (Eds.), The F a t e of Fossil Fuel CO 2 in the Oceans.
Plenum Press, New York.
Luz, B. and N.3. Shackleton (1975): CaCO 3 solution in the tropical East Pacific during the
past 130,000 years. Dissolution of Deep=Sea Carbonates, Cushman
Foundation F o r a m i n i f e r a l R e s e a r c h , Special Publication 13.
Mehrbach, C., C.H. Culberson, 3.E. Hawley and R.M. Pytkowicz (1973): Measurement of
the a p p a r e n t dissociation constants of carbonic acid in s e a w a t e r at atmospheric
pressure. Limnology and Oceanography 18: 897=907.
 Glacial to interglacial changes in ocean chemistry 197

Mook, W.G., ~.C. Bommerson and W.H. Stoverman (197$): Carbon isotope fractionation
between dissolved bicarbonate and gaseous carbon dioxide. Earth
and Planetary Science Letters 22: 169-176.
Niitsuma, N. and T.-L. Ku (1977): What happened at the time of the Earth's Magnetic
Field Reversals? Kagaku 46(II): 671-678.
Ostlund, H.G. (1980)" GEOSECS Atlantic and Pacific 13C measurements on radiocarbon
samples, (Miami) Tritium Laboratory Data Release #80-09.
Shackleton, N.3. (1977): Tropical rainforest history and the equatorial Pacific carbonate
dissolution cycles. In. N.R. Anderson and A. Malahoff (Eds.), The Fate of Fossil
Fuel CO2 in the Oceans. Plenum Press, New York, pp. Q01-428.
Sigenthaler, U. and K.O. Munnich (in press): 13C fractionation during CO2 transfer from
air to sea.
Streeter, S.S. and N.3. Shackleton (1979)" Paleocirculation of the deep North Atlantic: A
150,000 year record of benthic foraminifera and 180. Science 203- 168-171.
Sundquist, E., D.K. Richardson, W.S. Broecker and T.-H. Peng (1977): Sediment mixing and
carbonate dissolution in the Southeast Pacific Ocean. In: N.R. Anderson and A.
Malahoff (Eds.), The Fate of Fossil Fuel CO 2 in the Oceans. Plenum Press, New
York, pp. ~29-451.
Van Donk, 3. (1970): The Oxygen Isotope Record in Deep Sea Sediments. Ph.D. Thesis.
Columbia University.
Weiss, R.F. (1974): Carbon dioxide in water and sea water: The solubility of a non-ideal
gas. Marine Chemistry 2: 203-215.