Notation for Expressing Isotopic

Compositions (abundances)
Delta Value ()
Ratios reported relative to a standard in the delta notation
expressed as parts per thousand or permil ()
10.0, = 1.0%

R = absolute isotope ratios (heavy/light)

13C/12C
18O/16O

R samp - R std
# 1000
R std
R samp
d ] 0 00 g = c R - 1 m # 1000
std
d ] 0 00 g =

Notation for Expressing Oxygen Isotopic

Composition (abundances)
18

d18 O ] 0 00 g =

16

O samp - 18O
18
O 16O std

16

O std

# 1000

For example;!
Rsamp= 18O/16Osamp= 0.0020931!
Rstd= 18O/16Osamp= 0.0020052!
2009.31 # 10-6 - 2005.20 # 10-6
# 1000
2005.20 # 10-6
d18 O ] 0 00 g = 2.05
d18 O ] 0 00 g =

Notation for Expressing Isotopic (cont.)

If Ra > Rstd, a positive or heavier

If 18Oa = 15.5,
18O/16O is 1.55% > 18O/16O
a
std
If Ra < Rstd, a negative or lighter

If Da = -60,
D/Ha is 6.0% < D/H std

Isotope Fractionation!
Redistribution of isotopes of an element among
various species or compounds!
Fractionation factor ( ) - defines the fractionation
associated w/ equilibrium exchange reaction
between two substances.
A-B =
1/
3

RA
RB

CaC16O3 + H218O 1/3CaC18O3 + H216O

For water-calcite
103 ln CaCO3-H20 = 2.78x106/T2 - 2.79
at 25C,
CaCO3-H20 = 1.02878

Conversion of to delta:
R

A= A 1 x 103 ()
RSTD

and

B= B 1 x 103 ()
RSTD

Express Ra & Rb in terms of and substitute into;

A-B =

A-B =

Ra
Rb

A + 1000
B + 1000

If the 18Ol of the ocean is -1.0, and the water temperature is 25C,
assuming equilibrium, what is the 18Oc of calcite that precipitates from
this water? c-l = 1.028 at 25C
18Oc = (-1.0+103) - 103
18Oc = 27.7

Oxygen Isotopes!
16O

- 99.763%
- 0.0375
18O - 0.1995
17O

A()= (

RAsamp
RSTD

-1) x 103

Standard - Mean Ocean Water (SMOW)

PDB = 0.97002 SMOW - 29.98
SMOW = 1.03086 PDB + 30.86

Equilibrium Fractionation: During condensation, heavier isotope is

concentrated in the liquid phase, lighter isotope in the vapor phase
vapor pressure- H218O (20) < H216O (18)

at 25C
l-v = 1.0092
if 18Ol = 0.0, 18Ov = -9.2

Oxygen Isotope Ratios!

28!

Precipitation!

Oxygen Isotope Fractionation in

Marine Carbonates!
Isotope Exchange reaction between H2O and HCO3,
CaCO3 enriches calcite in 18O. !
Ca + HCO3 CaCO3 + H2O + CO2!
CaCO163 + H2O18 CaCO183 + H2O16!
CO3-H2O = Rc/Rw = 1.028 at 25C

Calcite Shells - roughly 28 higher (enriched)

than seawater!
May deviate from equilibrium!
Vital effects - inclusion of metabolic CO2!
Reaction rates - faster-decreases fractionation!

Temperature dependence!
fractionation increases w/ lower T!
103 ln CaCO3-H20 = 2.78x106/T2 - 2.79

(Erez and Luz, 1983).

Pelagic Planktonic Foraminifera!

Calibration of Oxygen Isotope

Fractionation: Planktonic Foraminifera!

Lab culturing experiments

Orb-H2O = 3.19-0.208T
Plankton Tows & Box Cores, Indian Ocean (20N-30S)
Orb-H2O = 3.50-0.214T

Pelagic Benthic Foraminifera!

Scale bar
(100-250 m)

Calibration of Oxygen Isotope

Fractionation : Benthic Foraminifera!
C. wullerstorfi

Oridorsalis

Pyrgo

Box Cores
Rio Grande Rise, Norwegian Greenland Sea, E. PacificRise
(Belanger et al.,1981, Palaeo3, v.33, p.205-220)

So how are oxygen isotopes

used for stratigraphic
correlation?!
Seawater 18O frequently
changes!!

Liquid-Vapor Fractionation & 18O of

precipitation!

18Ov = -9.2

During H2O evaporation, 16O concentrated in vapor phase

vapor pressure- H216O (18) > H218O (20)
at 25C, l-v = 1.0092
if 18Ol = 0.0, 18Ov = -9.2

Condensation/Precipitation
18Ov decreases toward high latitudes!
Ice-sheet 18O= -30 to -50!

Oxygen Isotope Ratios!

Glacial Ice-volume and Ocean 18O!

Ice-sheets (18 kya, present day)!

Sea-level Change, 150 kya to present!

10

120
meters

Pleistocene Glacial-Interglacial 18O/s.l.

calibration?!
1.2/120 m = 0.1/10 m!

Isotope stages - Odd/Even!

780 k.y.

Orbital/Astronomically Tuned!

11

Plio-Pleistocene Glacial Cycles?!

Northern Hemisphere Ice-sheets
2.6 to 1.2 Ma: low amplitude cycles
40,000 yr frequency
1.2 to 0.6 Ma:
low amplitude cycles
100,000 yr frequency
0.6 to 0 Ma: large amplitude cycles
100,000 yr frequency

Orbital cycles (ETP)!

Eccentricity 100, 413 ky (2.3 m.y.)!

Earth - sun distance 0.0 to 0.06!
Effect on insolation: ca. 0.7 W/m2
uniform across latitudes!
Tilt 41 ky (1.25 m.y.)!
angle ~ 22-24.3!
hotter summers / colder winters in both
hemispheres
Effect on insolation: up to 17 W/m2 at
high latitudes!
Precession 19, 23 ky!
wobble!
hot summers/cold winters in one
hemisphere, and cold summers/hot
winters on the other.
Effect on insolation: up to 40 W/m2

12

Orbital Computations: !
Eccentricity 0-1 Ma!
Lask2001
0.07

0.06

0.05

0.04

0.03

0.02

0.01

-200

-400

-600

-800

-1000

kyr

13

 Cibicidoides!
Globogerina
bulloides!

Cibicidoides!

14

Orbitally Tuned to Specmap!

Building a Global Oxygen Isotope Record !

Challenges:!
1. vital effects:!
kinetic effects - respiration, etc.!
solution: monospecific, fixed size!
2. Temperature vs. ice-volume:!
solutions: !
assume constant temperatures - <2C!
Where? Deep ocean and W. equat. tropics!
Benthic foraminifera vs. tropical planktonic foraminifera!
Independent temperature proxies!
Mg/Ca!
Alkenones!

3. Regional Runoff/Salinity effects!

solutions: !
Hydrogen Isotopes-aquatic plants!

15

Deep-sea Oxygen Isotope Record!

Benthic
Foraminifera!
Minimal variations
in T & S!

An indirect record
of ice-volume!

Cenozoic Glaciomarine Sediments:!

Southern Ocean / Antarctic !

Zachos et al. (1993)

16

Increased physical weathering of Antarctica ~ 37 Ma!

3.5

689 (Stott et al.,

1990)

3.0

744 (Zachos et al.

1996)
748 (Zachos et al.,
1992)

2.5
2.0

18O PDB 1.5

()
1.0
Increased
Ice-volume

0.5
0.0
-0.5

690
689
738
744

70
60

(Ehrmann &
Mackensen , 1992)

50

% Illite

40
30
20
10
0

Increased Physical
Weathering
25

30

35

40

45

AGE (Ma)
Zachos et. al. (1999)

17

Carbon Isotopes: !
Stratigraphic Applications!
Cambrian marine sections

Carbon Isotopes!
C12 - 98.89%!
C13 - 1.11%!
13C()=

13 C 12 C samp

1 x 103
13 12
C C sta

Fractionation of carbon isotopes

1. CO2 hydration
CO2 - HCO3 = 7.7 (25C)
2. Photosynthesis
CO2 - CH2O = -10 to -25

18

C fractionation w/ respect to HCO3!

Modern Benthic
Foraminifera 13C !

DIC 13C

Grossman, 1984, GCA, v.48, p. 1505-1512

19

Marine Carbonates & C-isotope ratios!

Calcite/Aragonite Secreting Organisms: !
Coccolithophorids, planktonic & benthic foraminifera!
Ca + 2HCO3 CaCO3 + CO2 + H2O !
13C CaCO3 - 13C DIC = SHELL-DIC ~ -1 to 2.0!
Factors influencing shell C-isotope composition!
1. 13C DIC!
2. Vital Effects deviation from equilibrium isotope values!
DIC-CaCO3 fractionation (calcification rates) ~0.5!
metabolic carbon (respired CO2)!
symbionts (planktonic foraminifera) (increases 13CHCO3 )~
1.0!
These effects can be quantified via Laboratory and Field
experiments assumed to be constant with time in each
species!

Vertical Carbon isotope gradient!

1 to 2 13CTDC gradient !
1. Biological pump!
Export production
(10-20% of PP)!
Corg ~ -20!

2.Density stratification!

20

What drives changes in the mean ratio of

the oceans?!

13C/12C

in

1.# Reservoirs: temporary repositories for material that

flows through them.!
steady-state for mass- neither growing nor
decreasing.!
Sinks - output!
Sources input!

C isotopes: burial of organic vs. inorganic carbon

13CCO 2/plant = 16
marine algae
modern 13C = -23

13CCO 2/calcite = -9

dissolved CO 2
modern 13C = -7

protist calcite
modern 13C = +2

Fluxin (Gt/yr) = Fluxout(Gt/yr)

forg

Fluxout = Fluxorg + Fluxcarb

Fluxin = volcanoes and weathering (??)

Assume steady state flux

1 = fcarb + forg
Add a tracer
13Cin = fcarb 13Ccarb + forg 13Corg
13Cin = -5

forg = 1 - fcarb

0.32
0.3
0.28

forg 0.26

forg = (13Cin - 13Ccarb )/( 13Corg - 13Ccarb )

forg = (13Ccarb + 5)/13Corg/carb

forg

0.24
0.22
0.2
0

13C

carb

21

Cambrian Carbon Isotope Maxima!

Cambrian marine sections

Cenozoic 13C & 18O!

Zachos et al. (2008)

22

Paleocene-Eocene Carbon Isotope

Excursions and Thermal Maxima
(Hyperthermals)!
Global warming/Carbon Injections Events!
PETM or ETM-1 (~55.5 Mya)!
ELMO or ETM-2 (~53.7 Mya)!
X or ETM-3!

Paleocene-Eocene Geography
Bighorn 550
1051

Contessa
577

1262

~55 M.y.a.

690

23

Lourens et al., 2005!

Walvis Ridge (ODP Leg 208)!

Spiess et al., 2003

24

Site 1262!
Late Cretaceous,
Cenozoic carbonate
ooze/clay!
3 APC holes
Composite (spliced)
section!

Zachos, Kroon et al., 2005

1262A,B,C!
PaleoceneEocene!
Stratigraphically
complete!
SR ~ 12-14 m/
m.y.!
Distinct lithologic
cycles (%CaCO3)!

Zachos, Kroon et al., 2005

25

Site 1262
Magnetostratigraphy!
(Bowles, 2006)!

Pass through core

(grey)!
Discrete samples
(blue)!

Upper Cretaceousearly Eocene!

C23n-C30n!

Meters composite depth (mcd)

Inclination for holes

A,B,C (80-222 mcd)!

26

Site 1262!
PETM

ETM-2

Carbonate dissolution horizons!

PETM, ETM-2 (ELMO)!

Site 1262!
ETM-2

PETM
18-19 cycles

Fe /color (*a) cycles !

Eccentricity!
405 (~4.5) !
100 k.y.(~18 to 19) !

Precession (86-89 cycles)!

Basis for an oribitally tuned age model!

27

SITE 1262, Walvis Ridge I!

Site 1262 13C & Fe (53-58 Mya) !

Zachos et al, in review

28

Site 1262 Bulk 13C / Eccentricity!

53 to 58 Ma!
53.0

54.0

55.0

56.0

57.0

58.0
0.20

400 kyr

13C

PETM!

0.0

Ecc.*

13C

-0.20

Laskar 04

4.0

0.20

3.0

*CIE removed
13C 2.0

0.0

13C
400ky

1.0
J
0.0

3.0

H
2.0

1.0
0.0
Age (Myr PEB)

C
-1.0

-0.20
-2.0

29