STABLE ISOTOPES

➢ Stable isotopes are non-radioactive forms of atoms.

➢ Although they do not emit radiation, their unique properties enable them to be
used in a broad variety of applications, including water and soil management,
environmental studies, nutrition assessment studies and forensics.
Hydrogen and oxygen

➢ Hydrogen has two stable isotopes.

➢ Oxygen has three stable isotopes.

➢ 11𝐻 and 168𝑂 are the most abundant isotopes

of these elements.

➢ The difference in the masses of the isotopes affects

the strength of covalent bonds these isotopes
form with atoms of other elements.
➢ The strength of the covalent bond arises from the reduction of energy
of a diatomic molecule that occurs when two atoms that a
infinite distance approach each other
to form a molecule.

➢ According to the theory of quantum mechanics, the energy of a diatomic molecule (E)
at absolute zero is—

1
E = hv
2

Where,
h = Planck’s constant = 6.626176 X 10-34J/Hz
Ʋ = vibrational frequency
When light isotope element is vibrational frequency decrease the en
replaced by heavier isotopes of molecules decreases of the molecule

Decrease of energy increase in the strength Heavy isotope

of covalent bond formed molecules are more
by heavy element stable than lighter ones

Therefore, molecules containing heavy isotope are less reactive than the lighter isotopes.
➢ The masses of isotopes play a role in
determining the velocities of molecules
in a gas at a particular temperature.

➢ All molecules of an ideal gas have the

same KE at a specified temperature—

1
KE = 2 mv2
Velocity of molecules of light isotope is greater than the velocity of molecules of heavy isotopes
➢ The existence of two stable isotopes of H and three isotopes of O makes nine different
isotopic varieties of water molecule.

H216O
H217O
H218O
HD16O Where H = 11𝐻 and
HD17O D = 21𝐻
HD18O
D216O Masses range from 18.010565 amu (H216O)
D217O to 22.02716 amu (D218O)
D218O

➢ This mass difference is the basis for the fractionation of the isotopes of H and O
in water molecules that take place during evaporation of water to form vapor and
during condensation of vapor to form liquid water (Gat 1984).
Mathematical relations

➢ Isotope fractionation is represented by—

18O 0.200
R = 16 = = 0.002004
O 99.762

➢ The isotope ratios of H and O are measured by mass spectrometry.

➢ The values are expressed relative to standard mean ocean water (SMOW) (Hoefs, 1997).
Standard mean ocean water (SMOW)

➢ Standard mean ocean water (SMOW) is a standard sample of pure water of accurately
known isotopic composition which is maintained by the International Atomic Energy Agency.

➢ It is used for precise calibration of density and isotopic composition measurements.

➢ The use of standard reduces systematic errors in measurements

made on different spectrometers
•The original standard was proposed by Harmon Craig in 1961
• SMOW ("Standard Mean Ocean Water") which never existed but was calibrated relative to
a sample from the Potomac River (STD NBS-1)
• (18O/16O) SMOW = 1.008 (18O/16O) NBS-1 = (1993.4 ± 2.5) * 10-6
• (2H/1H) SMOW = 1.008 (2H/1H) NBS-1 = (158 ± 2) * 10-6

•subsequently the IAEA (International Atomic Energy Agency) prepared a standard water from
distilled seawater that was modified to have an isotopic composition close to SMOW
• (18O/16O) VSMOW = (2005.2 ± 0.45) * 10-6
• (2H/1H) VSMOW = (155.76 ± 0.05) * 10-6

•for isotopically very depleted samples another standard, SLAP

("Standard light Antarctic Precipitation")
• d18OSLAP = -55.50 ‰ VSMOW
• d2HSLAP = -428.0 ‰ VSMOW

•the VSMOW is the currently accepted since ~ 3 decades

➢ The use of standard permits R values to be expressed in terms of a parameter called delta (δ

Rspl −Rstd
δ18O = X 103 %
Rs𝑡𝑑

Where Rspl = 18O/ 16O of sample

Rstd = 18O/ 16O of standard (SMOW)

➢ δ18O is the difference between the R values of sample and standard

expressed in terms of permille (i.e. parts per thousand) relative to R value of standard.
➢ Similary, the R value of H is defined as D/H—

Rspl −Rstd
δD = R X 103 %
s𝑡𝑑

➢ The δ parameters of O and H may be positive, negative, or zero.

Positive δ18O sample has higher 18O/ 16O ratio than standard
(i.e. sample is enriched in 18O relative to seawater standard)

Negative δ18O sample has lower 18O/ 16O ratio than the standard
(i.e. sample is depleted in 18O relative to seawater standard)

➢ Isotope composition of O in sample is always expressed in terms of

enrichment or depletion of the heavy isotope relative to SMOW.
➢ When liquid water undergoes a change in state by evaporating to form water vapor
under equilibrium conditions at a constant temperature, the D/H and 18O/ 16O
of the vapor differs from the remaining liquid water.

➢ That means isotope fractionation takes place during evaporation of

liquid water to water vapor.

➢ Expressed quantitatively by isotope fractionation factor α defined by—

R𝑙
αlv =
R𝑣

Where, R𝑙 = isotope ratio of liquid

Rv = isotope ratio of vapor
➢ Isotope fractionation factors decrease with increasing temperature
and approaches value of 1.

➢ It means that mass-dependent isotope fractionation virtually ceases

as the T approaches high values.
Q. Calculate the δ18O values of an ice core recovered from Greenland having oxygen isotope (18O/ 16O) ratios of
1934.3 X 10-6, 1945.67 X 10-6, and 2015.7 X 10-6 at 200 Ma, 150 Ma and 130 Ma,s respectively. Interpret the past
climatic conditions from the derived δ 18O values at the given years. [The 18O/ 16OVSMOW ratio is 2005.2 X 10-6].

Q. An ice core recovered from East Antarctica exhibit the following oxygen isotopic ratios (18O/ 16O):
2037.2 X 10-6, 1920.07 X 10-6 , 1967.3 X 10-6 , 1915.04 X 10-6 at 10 Ma, 50 Ma, 130 Ma and 180 Ma, respectively.
Calculate the δ18O values at the given geological time and interpret on the past climatic conditions.
 METEORIC PRECIPITATION

➢ The lightest molecule (H216O) evaporates preferentially

relative to the heaviest water molecule (D218O)

➢ Conversely, the heaviest molecule in water vapor

condenses preferentially relative to the
lightest molecule.

Water vapor depleted in D and 18O

relative to seawater

Liquid condensate enriched in D and 18O

that forms from the WV relative to vapor
The resulting fractionation of isotopic water molecules is a direct
consequence of the effect of masses of isotopic molecules on their
velocities expressed by the equation—
Temperature dependence of fractionation

l
➢ 103 ln αv vs T ( ֯ C)diagram for H and O isotopes.

➢ Figure illustrates the point that both fractionation factors

decrease with increasing temperature.
➢ The results demonstrate that water vapor
forming by evaporation at the surface of the ocean
at 20 ֯ C is depleted in 18O and D relative
to SMOW (Craig 1961).

➢ The effect of this process on

the isotope composition of water
remaining in the
ocean is negligible because the
ocean is virtually an infinite
reservoir of water.
Meteoric water line

➢ Craig (1961) observed that the δ18O and δD

values of precipitation that has not been evaporated
are linearly related by:

δD = 8 δ18O + 10
➢ This equation, known as the "Global Meteoric Water
Line”(GMWL)

➢ The isotopic delta values of meteoric water

(rain, snow, or hail) from site all over the earth form
a linear array represented in Figure by a straight line
whose equation (Rozanski et al. 1993) is—

δD = (7.96±0.02) δ18O + 8.86±0.17

➢ The intercept of the meteoric water line with the
vertical axis is at D= 8.86±0.17.

➢ The numerical value of the intercept is called

deuterium excess (DE).

➢ DE may originate during evaporation of seawater

in the source region of certain air masses.

DE = δD- 7.96 δ18O

➢ The δD and δ18O values of meteoric
precipitation become more negative
with increasing latitude north and south.

➢ The greater the distance between

the ocean and inland storm event
are, the more likely that rain will be
lighter due to rain out of heavier
isotopes

➢ This phenomenon arises from the

combined effects of decreasing T and
number of rainout events.
➢ Therefore, the δD and δ18O values of
meteoric precipitation reflect the latitude
of the site where the water was collected.

➢ Both of which cause the remaining

vapor in air masses to become depleted
in D and 18O.

➢ Lighter isotopes preferentially

evaporate while heavier isotopes
condense to form precipitation
preferentially to light isotopes.
For example,

➢ The δ18O values of ice in the east Antartic

icesheet approach -60% because of
low-T isotope fractionation and the long distance
between the source of air masses and site of
deposition in the interior of Antartica.

δD = (7.96±0.02) δ18O + 8.86±0.17

= 7.96 (-60) + 8.86
= -469%
Climate records in Ice cores

➢ The temperature dependence of δD and δ18O

values of snow precipitated in the polar
regions is used to interpret the isotope
composition of ice cores recovered from
icesheets in Greenland and Antartica.

➢ Ice cores have also been recovered from

high mountains in the Andes (Peru), Tibet,
and Mt Kilimajaro (E.Africa).

➢ These ice cores contain a record climatic

conditions during and subsequent to the
Wisconsin glaciation.
➢ Long ice cores have been covered from—

Camp century (Greenland)

Summit (Greenland)

Byrd Station (West Antartica)

Dome C and Vostok (East Antartica)

➢ All these cores exhibit a pronounced increase

of δ18O values of ice deposited at the end of
Wisconsin glaciation about 10k-12k years ago.
For example,

➢ The δ18O value of ice at Camp Century increased from -40 to -32%
during the transition from Lt. Pleistocene to Holocene Epoch
(Johnsen et al. 1972).

➢ The increase in δ18O values is attributed to the increase in annual average T

in Greenland and Antartica.

➢ The δ18O profiles demonstrate that the core at Summit (Greenland) and
Vostok (E.Antartica) are closely correlated for up to 250k years in the past.

➢ This confirms the hypothesis that the continental glaciations of Pleistocene

Epoch were global in scale
Vostok ice core

➢ Vostok core was recovered by teams of Russian and French

investigators at the Russian research station named Vostok.

➢ Located at East Antartic ice sheet .

➢ Elevation of this site at 3488m asl.

➢ Average annual temperature is -55.5 ֯ C.

➢ Ice sheet nearly 4000m thick and is

underlain by Lake Vostok.
➢ The profile of δ18O values in the Figure provides a detailed
climate record upto 250k years.

➢ There is an increase in the δ18O values in the interglacial

periods when the climatic conditions are warmer.
➢ The Eem interglacial lasted only about 20k years.

➢ The preceding Saale glacial age which existed for 80k years.

➢ Prior Holstein interglacial existed for 15k to 20k.

➢ If this pattern continues in the future, the present Holocene

interglacial is already half over.
O in silicate minerals

➢ The isotope composition of O in silicate minerals is expressed by δ18O

on the SMOW scale as defined by equation—

Rspl −Rstd
δ18O = R X 103 %
s𝑡𝑑

➢ The O of silicate is liberated by fluorination of powdered samples using

F2, BrF5 (Bromine pentafluoride) or ClF3 (Chlorine trifluoride).

➢ The reaction is carried out in Ni tubes at 500-600 ֯ C in well-ventilated fume hoods

because fluorine gas is highly toxic.

➢ The O released by fluorination is reacted with hot graphite to form CO2, which is
analyzed by mass spectrometry (Hoefs 1997).
Basalt and mantle

➢ Silicate minerals are enriched in 18O and have

positive δ18O that range from—

Quartz +20%
Ferromagnesian +5 and +6%
minerals

➢ Basalts erupted along MORs and OIBs have

comparatively low δ18O values (+5.73 and +5.48 av)

➢ The average δ18O values of these basalts are

representative of O in the lithospheric mantle from
which basaltic magma originate by decompression
melting (Faure 2001).
➢ Volcanic rocks in oceanic and continental subduction
zones and alkai-rich basalts in Italy have distinctly
higher δ18O values than MORBs, OIBs, and CFBs

➢ Because volcanic rocks in SZ contain O derived

from marine sediments.

➢ While, the alkali-rick rocks of Italy formed in part by

partial melting of subducted K-rich oceanic crust.
➢ The basalts of Iceland have a wide range of δ18O values
ranging from +2.9 to +6.2% (Harmon and Hoefs 1995).

➢ The low δ18O values are attributed to contamination of

basalt magmas by assimilation of hydrothermally altered
volcanic rocks at depth within the volcanic edifice.
➢ The high δ18O values of Society Island basalts (+6 to+6.7%)
correlate with the high 87Sr/86Sr and low 144Nd/143Nd
indicating that the basalt magmas originated from mixed
sources containing a crustal component (high δ18O ).

➢ The δ18O values of marine sediment and upper oceanic

crust in Table 26.5 range from +7 to +42%,
indicating that they are enriched in 18O relative
to MORBs and OIBs.

Partial melting of lower oceanic crust, or their assimilation

by mantle-derived magmas causes the resulting basalts
to have anomalously low δ18O values as exemplified
by some Iceland basalts.