Chapter 6: Isotopes

Chart of the Nuclides

Stable versus
Radioactive Isotopes

Note the very narrow band

of isotopic stability. Once a
nucleus leaves this band,
usually because of the
addition of neutrons, it
becomes radioactive.
Types of Radioactive Decay
 Radioactive Decay and Growth
The decay of a radioactive isotope is a first-order reaction and can be
written:
dN/dt =-N

Where N is the number of unchanged atoms at the time t and  is

the radioactive decay constant.
This equation can be rewritten as:
N = Noe-t
Where No is the number of atoms present at t = 0. This is the basic
form of the radioactive decay equation.
Half-life: the length of time that it takes for half of the atoms to
spontaneously decay.
t½ = ln2 /  = 0.693 / 

The radioactive decay equation can also be written in terms of

activity.
A = Aoe-t

Where A is the activity at some time t, and Ao is the activity at t = 0.

Rearranging this equation and solving for t yields:

t = 1/ ln (Ao/A)
In practice, it is often easier to consider radioactive decay in
terms of a radioactive parent and radioactive progeny (daughter).
**For any closed system, the number of progeny atoms plus the
number of parent atoms remaining must equal the total number
of parent atoms at the start. Solving for time yields the
following equation:
t = 1/ ln[1 + (P/N)]
Where N = the number of parent atoms and P = the number of
progeny atoms produced.
The number of radioactive
progeny can be determined from
the following formula:
P = No(1 – e-t)
With the passing of time, the
radioactive parent atoms will
decline and the radioactive progeny
will increase.
 Measurement of Radioactivity

Becquerel (Bq) is the basic measurement of radioactivity. 1Bq =

1.000 disintegrations per second.
Curie (Ci) another commonly used measurement of radioactivity. 1Ci
= 3.700 x 1010 disintegrations per second. A picocurie is 1 x 10-12
curies.
Gray (Gy): the unit used in the study of the chemical and biological
effects of radiation. A dose of 1Gy deposits 1 joule of energy per
kilogram of material.
Rad: another often-used unit where 1Gy = 100 rad.
The biological effects of radiation are due to changes in the chemistry of the
cells. These changes are caused by ionization, excitation, dissociation and
atomic displacement due to the passage of the radiation through the cells.
The sievert (Sy) is the unit of radiation dosage used to measure the biological
effects of radiation.
In the past, the rem (roentgen equivalent man) was the commonly used unit,
where 1 Sy = 100rem.
The relative biological effectiveness (RBE) is a measure of the ability of various
types of radiation to cause ionization in biological materials. The dosage in
sieverts is equal to the dosage in grays multiplied by the RBE.
Table 6–3 RBE Values for Various Types of Radiation*

Radiation RBE
X and γ rays 1
Beta rays and electrons 1
Thermal neutrons 2
Fast neutrons 10
Protons 10
Alpha particles 20
Heavy ions 20
 Tritium dating
There are three isotopes of hydrogen: 1H, 2H (deuterium), and 3H
(tritium), with average terrestrial abundances (in atomic %) of
99.985, 0.015 and <10-14 respectively.
Tritium is radioactive and has a half-life of t½ = 12.43 years. This means it is
used to date sample that are less than 50 years old.
Tritium is produced in the upper atmosphere by the bombardment of nitrogen
with cosmic-ray produced neutrons.
14
7𝑁 + 𝑛 → 3 42𝐻𝑒 + 31𝐻
The production rate is 0.5 ± 0.3 atoms cm-2 sec-1

Tritium abundances are measured in several ways:

tritium unit (TU) = 1 tritium atom per 1018 hydrogen atoms

dpm L-1 = disintegrations per minute per liter

pCi L-1 picocuries per liter (of water.)

1TU = 7.1 dpm L-1 = 3.25 pCi L-1

From the onset of of atmospheric testing of fusion bombs in 1952, until
the signing of the Atmospheric Test Ban Treaty in 1963, bomb- produced
tritium was the major source of tritium. Prior to the testing of fusion
devices, the tritium content of precipitation was probably between 2 and
8TU. A peak of several thousand TU was recorded in the northern
hemisphere precipitation in 1963.
Event dating describes the
marking of a specific period
where the abundances of an
isotope are uncharacteristically
elevated or diminished. For
example, groundwaters that
were recharged between 1952
and 1963 will have a distinctive
signature indicating an increase
in 3H production.
Tritium decays through - emission. This means that the parent material
is 3H and the progeny material is 3He.

Given T = 5.575 x 10-2 y-1, if through sampling ground water you find 3H
= 25TU and 3He = 0.8TU, what time has passed since that groundwater
was recharged (at the surface)?
Recall: t = 1/·ln[1 + (P/N)]
t = 17.937·ln[1 + (0.8/25)] = 0.6 y
 Carbon – 14 Dating
14C has been used for dating samples
that are roughly 50,000 years old or
younger (accelerator mass
spectrometry ups the usage to 100,000
years). There are 3 isotopes of carbon:
12C, 13C, & 14C, with average terrestrial

abundances of 98.90, 1.10, and <10-10,

respectively. 14C is the only radioactive
carbon isotope with a half-life of 5,730
years.
14
7𝑁 + 𝑛 → 11𝐻 + 146𝐶

14 14
6𝐶 → 7𝑁 + β- + 𝜈 + Q

1 𝐴𝑜
t= _ ln( )
1.209 𝑥 10 4 𝐴
In order to use 14C for geochronology, it is assumed that the atmosphere is
in secular equilibrium with respect to 14C. Meaning that the rate at which
14C is produced by cosmic ray flux is equal to the rate of decay of 14C, so

the abundance of 14C in the atmosphere remains constant. However, for a

variety of reasons, the abundance of 14C has not remained constant over
time. These variations need to be accounted for when using this dating
method.
In order to calibrate the C-14 time
scale one must use carbon-
containing materials of known age.
A popular choice is the bristlecone
pine, the oldest of which has an
age of almost 5,000 years.
 U-Series Disequilibrium Methods of Dating

For a system that has been closed for a sufficiently long time, secular
equilibrium will be achieved and the relative abundance of each isotope
will be constant.
When the system enters disequilibrium due to separation of either
parent or progeny, or subsequent decay, the reestablishment of
equilibrium can be used as a dating method.
For example, when 234U decays to 230Th in sea water, the 230Th is rapidly
removed from sea water because, unlike uranium, thorium is very
insoluble (reactive). In this case, the 230Th that accumulates in the
sediments is said to be unsupported, as it is now separated from its
parent isotope.
 Ta ble 6-1. Uranium decay series*

Uranium 238 Uraniu m 235

Emitted Emitted
Isotope particle Half-life Isotope particle Half-life
238 235
92 U α 4.47 x 10 9 yrs 92 U α 7.038 x 10 8 yrs
234 231
90 Th β- 24.1 d ays 90 Th β- 1.063 days
234 231
91 Pa β- 1.17 min 91 Pa α 3.248 x 10 4 yrs
234 227
92 U α 2.48 x 10 5 yrs 89 Ac β- 21.77 yrs
230 227
90 Th α 7.52 x 10 4 yrs 90 Th α 18.72 days
226 223
88 Ra α 1.60 x 10 3 yrs 88 Ra α 11.435 d ays
222 219
86 Rn α 3.8235 days 86 Rn α 3.96 sec
218 215
84 Po α 3.10 min 84 Po α 1.78 x 10 -3 sec
214 211
82 Pb β- 27 min 82 Pb β- 36.1 min
214 211
83 Bi β- 19.9 min 83 Bi α 2.14 min
214 207
84 Po α 1.64 x 10 -4 sec 81 Tl β- 4.77 min
210 207
82 Pb β- 22.3 yrs 82 Pb Stable
210
83 Bi β- 5.01 d ays
210
84 Po α 138.38 days
206
82 Pb Stable
*Data source: Chart of the Nu clides (1989).
 Ta ble 6-2. Thorium decay series*

Emitted Emitted
Isotope particle Half-life Isoto pe particle Half-life
232 216
90 Th α 1.40 x 10 10 yrs 84 Po α 0.14 5 sec
228 212
88 Ra β- 5.76 yrs 82 Pb β- 10.6 4 hr
212
228 83 Bi α (3 3.7%) 1.00 9 hr
89 Ac β- 6.15 hr
β - (66.3%)
228 208
90 Th α 1.913 yrs 81 Tl β- 3.05 3 min
224 212
88 Ra α 3.66 days 84 Po α 2.98 x 10 -7 sec
220 208
86 Rn α 55.6 sec 82 Pb Stable
*Data source: Chart of the Nu clides (1989).
230Th Dating of Marine Sediments:
As we saw in the last example, 230Th is reactive in the marine
environment (i.e., it is rapidly removed from seawater by particles).
In fact it has a mean residence time of about 300 years.
Given that the addition and removal of U (230Th’s parent) to the
ocean is in balance (U has a residence time in seawater of about 1
million years), 230Th is produced at a constant rate. This means
that as long as there has been no disruption to the sediment layers
on the sea floor, the uppermost layer will represent present-day
230Th deposition to the sediments.

230Th = 9.217 x 10-6 y-1.

t = 108,495 ln(230Thinitial / 230Thmeasured)
Example 6-4
The 230Th activity is measured for a marine sediment core. The top
layer of the core has a 230Th activity of 62 dpm. At a depth of 1m, the
230Th activity is 28 dpm. Calculate the age of the sediment at a depth of

1m.
t = 108,495 ln(62/28) = 86,246 y
Rate = (sediment thickness / time) = 1m / 86,246 y = 1.16 cm /1000 y.
230Th / 232Th Sediment Dating
This method uses the ratio of these two radioisotopes instead of
just 230Th. In this case the age equation is
t = 1/ln (R0 / R) = 108,495 ln (R0 / R)
Where……
R = 230Th / 232Th measured
R0 = 230Th / 232Th initial

R is also = (230Th / 232Th)0 e-t

So far the examples have been for ‘unsupported’ activity. We have

assumed that parent and progeny are separated.
Supported activity – case where a parent or grandparent was originally
present in the sediment. Decay of this parent and/or grandparent contributes
to the total activity of the progeny.

particle 230Th

238U 234U 230Th

230Th
= Thorium scavenged from the water column = unsupported acitvity

230Th = Thorium produced from 238U in the particle = supported activity

230Th 230Th
Total activity = +
230Th / 231Pa Sediment Dating
Very similar to the 230Th / 232Th except the half life is shorter, so you
can use it for somewhat faster accumulation rates.

Activity and Sediment-Rate Relationships

Radioactive decay is a first-order process (i.e. exponential decay)

If sedimentation is constant then the sedimentation rate (a) = ( /-2.303m)

m is the slope
Deterministic system is a system in which no randomness is involved in the
development of future states of the system. Can accurately predict future
states.
Stochastic system has a random probability distribution or pattern that may
be analyzed statistically but may not be predicted precisely.
U-Th-Pb isotopic systems

 206 Pb   206 Pb   238 U  238t

 204    204    204  (e  1)
 Pb meas  Pb initial  Pb 

 207 Pb   207 Pb   235 U  235t

 204    204    204  (e  1)
 Pb meas  Pb initial  Pb 

 208 Pb   208 Pb   232 U  232t

 204    204    204  (e  1)
 Pb meas  Pb initial  Pb 
 Stable Isotopes
Do not spontaneously breakdown to form other isotopes

Table 6-6. Average terrestrial abun dances of stable isotopes

used in en viron mental stu dies*
Average Terrestrial
Ele ment Isotope Abundance (atom %)
1
Hydrogen 1
H 99.985
2
1
H 0.015
12
Carbon 6
C 98.9
13
6
C 1.1
14
Nitrogen 7
N 99.63
15
7
N 0.37
16
O xygen 8
O 99.762
17
8
O 0.038
18
8
O 0.2
32
Sulfur 16
S 95.02
33
S 0.75
16
34
S 4.21
16

16 subp36 S
0.014
*Data source: IUPAC (1992).
Isotopic Fractionation – partitioning of isotopes during phase change
or reactions. Partitioning is proportional to the masses of the isotopes.

Equilibrium Fractionation: forward and backward reaction rates are

equal for each isotope.
Bi-directional reactions at equilibrium (like water vapor over water)
Lighter isotopes in the gas phase (lighter isotopes = more kinetic
energy).
Example: evaporation of water in a closed space

Kinetic Fractionation: unidirectional reactions in which reaction rates

are dependent on the masses of the isotopes and their vibrational
energies.
Example: breakdown of calcite in an acid solution to produce Ca2+ and
CO2 (g) . The gas escapes and therefore doesn’t equilibrate with the
calcite.
 Fractionation Factor
Describes the partitioning of stable isotopes between two substances, A and B
 = RA / RB
where R is the ratio of the heavy to light isotope of the element for each
substance and α is the fractionation factor

The fractionation factor

varies as a function of
temperature and at high
temperature it
approaches unity.
 The  (delta notation)

 = [(Rsamp – Rstd) / Rstd] x 1000

same as Units are per mil “‰”
 = [(Rsamp / Rstd) -1] x 1000

R is the ratio of the heavy to light isotope. Various standards are used
depending on the element.

Table 6–7 Stable Isotope Ratios for Standards (Data from Kyser (1987)).
Element Standard Ratio

Hydrogen V-SMOW 2H/1H = 155.76 × 10−6

Carbon PDB 13C/12C = 1123.75 × 10−5

Oxygen V-SMOW 18O/16O = 2005.2 × 10−6

PDB 18O/16O = 2067.2 × 10−6

Nitrogen NBS-14 15N/14N = 367.6 × 10−5

Sulfur CDT 34S/32S = 449.94 × 10−4

 18
EXAMPLE 6–5 The isotopic ratio of O/16O in V-SMOW is 0.0020052. A rainwater sample
collected in Boston, Massachusetts, has an 18O/16O ratio of 0.0019750. Calculate the delta value
for this rainwater sample.

 Ratiosample  Ratiostandard   0.0019750  0.0020052 

    1000    1000
 Ratio standard   0.0020052 
 15.1‰

The delta value is reported in parts-per-thousand (‰), and the negative value means that the
sample is isotopically lighter than the standard.
Rearranging the delta-notation equation and combining it with the
fractionation factor () equation allows for calculation of the delta value of
one compartment if you know the delta value for the other compartment.

 = RA/RB = (A + 1000) / (B + 1000)

 Oxygen and Hydrogen Isotopes in Water
Used for ‘sourcing’ water
For hydrogen we use 1H and 2H (deuterium, D)
For oxygen we use 16O and 18O

 values for O and H in water are zero for seawater.

For water vapor in equilibrium with seawater at 25ºC - D = -69 ‰

and 180 = -9.1 ‰
For water vapor in equilibrium with seawater at 10ºC - D = -84 ‰
and 180 = -10.1 ‰

Temperature effects the fractionation from liquid to vapor phase

for H and O. The temperature effect comes into play both for
latitude and altitude. This temperature effect on fractionation is
what gives rise to different isotopic values In H and O for different
areas of precipitation.
The process of fractionation during condensation
Start with water vapor that is isotopically light in H and O relative to
seawater

As the vapor begins to condense out into clouds

Initial droplets are rich in 18O and D
Vapor becomes more depleted in 18O and D

As condensation continues-
Vapor becomes more depleted
Droplets in turn reflect lower 18O
and D coming from source vapor

The change in isotopic value of both

the vapor and liquid is a function of
how much of the original vapor is
left.

Described by a Rayleigh Distillation function

Rayleigh Distillation (or fractionation)

18Ov = [18O0 + 1000] f (-1)

fraction
vapor remaining
starting
vapor

To relate the condensing liquid to the vapor

18Ol = (18Ov + 1000) - 1000

Isotope fractionation of H and O in water (during condensation)

This process results in:

-rain early in a precip event is isotopically heavier than at the

end of the event
-delta values of rain decreases from coastal to inland areas
-rain is isotopically lighter at the poles

The H and O isotopes in precipitation are related:

D = 8 18O + 10 (excess of D relative to 18O; d)

or
D = 8 18O + d , where d is the D excess
 D = 8 18O + 10

Is the equation for the

Global Meteoric Water Line

This has nothing to do with

meteors

Figure 6-6. Plot of D versus 18O illustrating the mean global meteoric water line and
local meteoric water lines. Other processes that affect the isotopic ratios - e.g., low-
temperature water-rock exchange, geothermal exchange, and evaporation - are also
illustrated. A and B are two water masses and the dashed line represents the possible
isotopic compositions of water produced by mixing of these two end members. The
diagram is modified from “Uses of Environmental Isotopes” by T. B. Coplen in
REGIONAL GROUND WATER QUALITY edited by W. M. Alley, pp. 227-254.
Copyright © 1993. This material is used by permission of John Wiley & Sons, Inc.
Different areas influenced by evaporation, water-rock
interaction, etc. will cause a deviation in the D excess ()
relative to 18O in water.

It is the different D values relative to the GMWL that allows

you to ‘tag’ water masses.

With this tag you can examine contributions of different water sources
to ground and surface waters.
Example 6-7: River flow below a dam is a mixture of water coming from the
reservoir behind the dam and from a groundwater source.

River…..18O = -3.6‰ , D = -44.6 ‰

Res….. 18O = -4.5‰ , D = -38 ‰
GW…. 18O = -3.0‰ , D = -49 ‰
What's the percentage contribution of each source?

This is a two-endmember mixing problem.

2 equations, 2 unknowns,
For D…….fGW DGW + fres Dres = Driv Redefine fGW in terms of fres,
Substitute and solve sequentially
For 18O… fGW 18OGW + fres 18Ores = 18Oriv

Also fGW + fRES = 1

f1 = 0.40 GW supplies 40% of the water in the river

f2 = 0.60 Reservoir supplies 60% of the water in the river
Climate Change
Because the fractionation of H and O in water changes with temp, isotopic
measurements of ice-cores are used to estimate paleoclimate.

1) Isotopic composition of snow reflects air temp.

2) Colder air = more negative D and 18O

3) Warmer air = less negative D and 18O

4) Works the same in both hemispheres

5) Once snow is packed into glacier, ice stratigraphy not disturbed,

paleothermometer locked into place

Ice ages can confound this approach to some extent because by locking up
a bunch of ocean water into glaciers, the overall D and 18O of all water
gets less negative. This effect is small relative to the temp effect.
 Antarctic

Arctic Antarctic
When records from both hemispheres agree, it is
a global climate change

When the disagree, it is a local climate change

 Carbon -7‰

We can use 13C to detect

fossil fuel contributions to
atmospheric CO2. The
Suess effect.
DIC in aqueous systems
There are isotopic fractionations associated with each step of the carbonate buffering
system. Recall from Chapter 3 that the dominant carbonate species is pH
dependent.

CO2 gas ~ CO2 aq

CO2 aq  H2CO3

H2CO3  HCO3-

HCO3-  CO32-

CO32-  CaCO3
 Figure 6-10. Isotopic fractionation factors, relative to CO2 gas, for
carbonate species as a function of temperature. Deines et al. (1974).

Ta ble 6-8. Fractionation factors for

carbonate species relative to gaseous CO2 *

H 2CO 3 1000 ln α = -0.91 + 0.0063 10 6 /T2

HCO 3 - 1000 ln α = -4.54 + 1.099 10 6 /T2
2
CO 3 1000 ln α = -3.4 + 0.87 106 /T2
Ca CO3 (s) 1000 ln α = -3.63 + 1.194 10 6 /T2
*From Deines et al. (1974).

Isotopic composition of DIC also

depends on open vs closed
system.
Using Equations in Table 6-8

Example 6-8: CaCO3 is ppt in water in equilibrium with the atm. What is the 13C
for the carbonate at 25ºC.

CaCO3 relative to CO2g: 1000ln = -3.63 + 1.194 x 106/T2

= 9.8….calcite is 9.8‰ heavier than CO2g

CO2g = -7‰, so calcite is 2.8‰

Example 6-9: Bicarb in ocean dominate DIC. What is the 13C

for DIC in the ocean at 10ºC.

HCO3- relative to CO2g: 1000ln = -4.54 + 1.099 x 106/T2

= 9.18..bicarb is 9.18‰ heavier than CO2 g

Bicarb dominates DIC so …

CO2g = -7‰, therefore ocean 13 DIC = 2.8‰

Methane
Figure 6-11. 13C and deuterium isotopic values
for methane from various sources and reservoirs.
M
- abiogenic (from the mantle), P - petroleum, A -
atmosphere, G - geothermal (pyrolitic from
interaction with magmatic heat), T - thermogenic
(from kerogen at elevated temperatures), F -
acetate fermentation (bacterial), and R - CO2
reduction (bacterial). After Schoell (1984, 1988).

This technique, at least

the carbon part, has
been used to determine
whether some deep-sea
methane-based
communities are fueled
by thermogenic or
biogenic methane
deposits.

Methane hydrates, biogenic in origin

13C average of about -65 ‰ (range -40 to -
100‰)
Carbon isotopes – food webs, paleo or otherwise.

C3 plants (deciduous trees) – 13C = -15‰

C4 plants (grasses, marsh, corn…) – 13C = -30‰

plankton – 13C = -22‰

Small trophic fractionation …about 1 ‰

carnivores
15N

herbivores

13C
Nitrogen
Stable isotopes of N and O used to trace sources of nitrogen pollution
usually in the form of NO3- or NH3
15N can be substantially altered by biological processes

Nitrates in surface and groundwater

Fertilizer 15N = 0 ‰
In theory you can use 15N to distinguish
Manure 15N = 15 ‰ ± 10‰ sources. In practice, it’s difficult……

Nitrate is reactive in surface and groundwaters undergoing denitrificaiton.

As denitrification converts nitrate to N2, the residual nitrate becomes isotopically

heavier. So a fertilizer source of nitrate that has undergone some denitrification
will start to look isotopically like the manure nitrate.

A way to constrain this problem is to also measure 18O in nitrate

Fertilizer 18O = +23 ‰ (oxygen in nitrate comes from air)
Manure 18O = -10‰ (oxygen in nitrate comes mostly from water)
During denitrificaiton, both O and N are fractionated but their fractionations
relative to each other are predictable

Red circles = measurements

Draw the predicted fractionation lines

for each end-member (blue lines).
Note they have the same slope

Draw a line through the measured

GW sample (the mixture) that is
perpendicular to the fractionation slopes
(dashed line)

Now you can either do a mixing calc

Figure 6-12. Determination of the relative importance of
to determine fraction of each source, or nitrate sources to a groundwater system. Two sources for
Amount of A = C-B / A-C nitrates are fertilizer and manure. Both are undergoing
denitrification. A and B represent each source at a particular
The ‘lever law’…just like torque in physics stage in the denitrification process. C is the isotopic
composition of the nitrate in the groundwater due to simple
mixing. In this example, approximately 60% of the nitrate is
contributed by the fertilizer.
NH4+ and NO3- in rain

Sources of NOx = 65% from fossil fuel

Sources of NH4+ = bacterial breakdown of organic matter and animal/human waste

Volatilized NH4+ is extremely isotopically light (30-40‰ lighter than waste)

Global NO2 pollution

Sulfur

Big isotopic difference between

sulfides and sulfates

Sulfate reduction (microbial) has

a big fractionation, as does microbial
sulfide oxidation

Is the sulfide produced during sulfate

reduction isotopically lighter or heavier
than the sulfate?

What’s the major source of sulfate on

the planet?

Burning fossil fuels…

Mixing

Binary mixing

mix = AfA + B(1-fA)

If the two sources have unequal concentrations of the element of interest, the
mixing equation must be weighted to reflect that:

mix = AfA(A/M) + B(1-fA)(B/M)

…..where A,B, and M are the concentrations

of source A, B, and the mixture with respect to the element of interest.
Mixing with more than two end members

Figure 6-14. Plot of PO43- versus NO3- in water

samples from feedlot runoff (M), cultivated fields (F),
uncontaminated groundwater (G), and contaminated
well water (W). The sample of contaminated well water
falls within the triangle defined by compositions M, G,
and F, indicating that this sample is a mixture of these
three compositions. The relative proportions of each
end member can be determined by applying the lever
rule (see Example 6-11).
Paleothermometry – using carbonates

18O in carbonate

Fractionation factor governing water (oxygen) equilibration with CaCO3

is
temperature dependent

t (ºC) = 16.9 – 4.14(18Ocalcite – 18Owater) + 0.13(18Ocalcite – 18Owater)2

Due to large and seasonal variations in freshwater oxygen isotopes,

only oceanic carbonate organisms work.

Lots of other assumptions and corrections so the tool is used as a

relative indicator of paleotemperature.