Simple Decay: Radioactive Parent  Stable Daughter

1000 ingrowth of daughter

900
D* = N0 (1 - e-lt)
800

700

600

500

400

300

200

100
N = N0 e-lt
D0 decay of parent
0
0 1 2 3 4 5 6 7 8 9 10

Half-lives

1
 Decay Series: Radioactive Parent  Radioactive Daughter

200

N1 (T
100 1/ = 10
2
hr)
80
60
Decay of parent
40

N 20

N2 (T1/ = 1 h
2 r)
10
8
6
Ingrowth from parent
4
and decay of daugther
2

1
0 1 2 3 4 5 6 7 8 9 10 11 12

Time in hours
Image by MIT OpenCourseWare. After Figure 4.4 in Faure.

2
 Consider the decay series N1  N2  N3
Remember:

1) -dN1/dt = l1 N1
Now we consider N2, that is produced by decay of N1 and itself decays to N3:

2) dN2/dt = l1 N1 – l2 N2
Remember:

3) N1 = N1,0 e –l1t
Substitute 3) into 2):

4) dN2/dt = l1 N1,0 e –l1t – l2 N2

Rearrange:

5) dN2/dt + l2 N2 – l1 N1,0 e –l1t = 0

Solving this first order differential equation for N2 yields:

6) N2 = l1/(l2 – l1) N1,0 (e –l1t - e –l2t) + N2,0 e –l2t

The solution, as well as equivalent solutions for three nuclides and the general case, are known as Bateman
(1910) equations/solutions.

The first term in equation 6) is the number of N2 atoms decayed from N1 not yet decayed to N3
The second term in equation 6) is number of N2 atoms that remain from the initial N2,0

3
The classic Bateman
paper on the famous
“Bateman equations”

Bateman, Harry. "The solution of a

system of differential equations occurring
in the theory of radioactive
transformations." In Proc. Cambridge
Philos. Soc, vol. 15, no. pt V, pp. 423-
427. 1910.

4
 continue…

If there are no atoms of the original daughter N2,0, then 6) simplifies to:

7) N2 = l1/(l2 – l1) N1,0 (e –l1t – e –l2t)

Example: 238U  234U  230Th  …  206Pb

8) (230Th) = (230Th)x + (230Th)s x = excess, not supported, s = supported from 238U

Let’s first consider the excess activity only, at some time, t:

9) (230Th)x = (230Th)x,0 e –l230 t

Normalize by a “stable” isotope. Relative to the short-lived daughters, 232Th is “stable”

10) (230Th/232Th)x = (230Th/232Th)x,0 e –l230 t

Application!
Now let’s consider the 238U-supported (230Th) – see equation 7)

11) (230Th)s = l234/(l230 – l234) 234U

0 (e –l234t – e –l230t)

At secular equilibrium (234U) = (238U) then 234U l234 = (238U)

Also l230 - l234 ≅ l230 as l234 is small: e –l234 t ≅ 1

5
 238U Decay Series

22.3 y 19.9 m

Peucker-Ehrenbrink, 2012 6
 238U Decay Series

± constant supply
from decay of 238U

Size of spout
equals λ

Fill level in each

tank equals N

Flux equals (A)

Courtesy of Mineralogical Society of America. Used with permission.

7
Application in determining chronologies of sediments
Basic decay equation: N = N0 e -l t assuming no U-supported activity
Replace time (t) with depth in sediment column (d) divided by sedimentation rate (sr)
t = d / sr
Decay equation: N = N0 e -l d/sr t = d / sr
ln N = ln N0 - ld/sr

In a diagram of ln N (y axis) and d (x axis)

the slope (m) is
Figure of log(230Th/232Th)A versus
m = - l / sr
Core Depth, cm, has been removed
and
due to copyright restrictions.
sr = - l / m
Faure, Gunter. “Principles of
Isotope Geology.” (John Wiley & This method is also known as the ionium
Sons, 1986): 367. (230Th) method of dating.

8
 Complications…

a) b)
log (230Th/232Th)

c) d)

Depth in the core

9
 Complications…

a) b)
log (230Th/232Th)

a) Constant sedimentation rate

b) Change in sedimentation rate

c) Mixing at the top

d) 238U-supported 230Th dominates

c) d)

Depth in the core

10
 continue…
If there are no atoms of the original daughter N2,0, then 6) simplifies to:

7) N2 = l1/(l1 – l2) N1,0 (e –l1t – e –l2t)

Example: 238U  234U  230Th …  206Pb

8) (230Th) = (230Th)x + (230Th)s x = excess, not supported, s = supported from 238U

Let’s first consider the excess activity only, at some time, t:

9) (230Th)x = (230Th)x,0 e –l230 t

Normalize by a “stable” isotope. Relative to the short-lived daughters, 232Th is “stable”

10) (230Th/232Th)x = (230Th/232Th)x,0 e –l230 t Application!

Now let’s consider the 238U-supported (230Th) – see equation 7)

11) (230Th)s = l234/(l230 – l234) 234U

0 (e –l234t – e –l230t)

At secular equilibrium, (234U) = (238U) then 234U l234 = (238U)

Also l230 - l234 ≅ l230 as l234 is small: e –l234 t ≅ 1

11
 continue…

11) 230Th
s = l234/(l230 - l234) 234U
0 (e –l234t – e –l230t)

l230 230Ths = l234 234U

0 (1 – e –l230t)

12) (230Th)s = 238U

0 (1 – e –l230t)

From equation 9) (230Th)x = (230Th)x,0 e –l230 t

(230Th) = (230Th)x,0 + (230Th)s

Total 230Th activity = initial excess 230Th activity + 238U-supported activity

13) (230Th) = (230Th)x,0 e –l230t + 238U (1 – e –l230t)

Normalize to 232Th

14) (230Th/232Th) = (230Th/232Th)x,0 e –l230t + (238U/232Th) (1 – e –l230t)

If (230Th/232Th) is plotted against (238U/232Th), equation 14) is a linear equation, the so-called

230Th-238U isochron diagram

12
 230Th-238U isochron diagram
(230Th/232Th)

t=0

Equipoint

(238U/232Th) Modified after figure 21.7 of

© John Wiley & Sons. All rights reserved. This content is excluded from our Creative Faure, Gunter. “Principles of
Commons license. For more information, see http://ocw.mit.edu/fairuse. Isotope Geology.” (John Wiley &
13 Sons, 1986): 379.
 238U-series 235U-series 232Th-series

238 235
U 234
U U
4.47 by 245,000 y 0.704 by

234 231
Pa Pa
6.69 h 32,800 y

234 230 231 227 232 228

Th Th Th Th Th Th
21.4 d 75,000 y 1.06 d 18.7 d 14.1 by 1.91 y

227 228
Ac Ac
21.8 y 6.15 h

226 223 228 224

Ra Ra Ra Ra
1600 y 11.4 d 5.75 y 3.63 d

222 219 220

Rn Rn Rn
3.823 d 3.96 s 55.6 s

222 214 210 215 216 212

Po Po Po Po Po Po
-5
3.04 m 1.6 10 s 138.4 d 0.0018 s 0.15 s 3 10-7 s

214 210 211 212

Bi Bi Bi Bi
19.7 m 5.01 d 2.14 m 1.01 h

214 210 208 211 207 212 208

Pb Pb Pb Pb Pb Pb Pb
26.9 m 22.6 y stable 36.1 m stable 10.6 h stable
207 208
Tl Tl
4.77 m 3.05 m

Peucker-Ehrenbrink, 2012 14
 238U-series 235U-series 232Th-series

238 235
U 234
U U
4.47 by 245,000 y 0.704 by

234 231
Pa Pa
6.69 h 32,800 y

234 230 231 227 232 228

Th Th Th Th Th Th
21.4 d 75,000 y 1.06 d 18.7 d 14.1 by 1.91 y

227 228
Ac Ac
21.8 y 6.15 h

226 223 228 224

Ra Ra Ra Ra
1600 y 11.4 d 5.75 y 3.63 d

222 219 220

Rn Rn Rn
3.823 d 3.96 s 55.6 s

222 214 210 215 216 212

Po Po Po Po Po Po
-5
3.04 m 1.6 10 s 138.4 d 0.0018 s 0.15 s 3 10-7 s

214 210 211 212

Bi Bi Bi Bi
19.7 m 5.01 d 2.14 m 1.01 h

214 210 208 211 207 212 208

Pb Pb Pb Pb Pb Pb Pb
26.9 m 22.6 y stable 36.1 m stable 10.6 h stable
207 208
Tl Tl
4.77 m 3.05 m

Peucker-Ehrenbrink, 2012 15
226Ra - 230Th disequilibrium diagram

Figure of radioactive disequilibria

between 226Ra-230Th and 238U-230Th in
lavas from austral and southern
volcanic zones removed due to
copyright restriction.

After Figure 1 in Sigmarsson, O., J.

Chmeleff, J. Morris, and L. Lopez-
Escobar. "Origin of 226 Ra–230Th
disequilibria in arc lavas from southern
Chile and implications for magma
transfer time." Earth and Planetary
Science Letters 196, no. 3 (2002):
189-196.

16
 230Th-234U-238U activity ratio diagram

Courtesy of Mineralogical Society of America. Used with permission.

From: Chabaux, Riotte and Dequincey, U-Th-Ra Fractionation during weathering and river transport. In:
Bourdon et al. (Eds), Uranium-series geochemistry, Rev. Mineral. Geochem., vol. 52, chapter 13, 533-576.
17
 238U-series 235U-series 232Th-series

238 235
U 234
U U
4.47 by 245,000 y 0.704 by

234 231
Pa Pa
6.69 h 32,800 y

234 230 231 227 232 228

Th Th Th Th Th Th
21.4 d 75,000 y 1.06 d 18.7 d 14.1 by 1.91 y

227 228
Ac Ac
21.8 y 6.15 h

226 223 228 224

Ra Ra Ra Ra
1600 y 11.4 d 5.75 y 3.63 d

222 219 220

Rn Rn Rn
3.823 d 3.96 s 55.6 s

222 214 210 215 216 212

Po Po Po Po Po Po
-5
3.04 m 1.6 10 s 138.4 d 0.0018 s 0.15 s 3 10-7 s

214 210 211 212

Bi Bi Bi Bi
19.7 m 5.01 d 2.14 m 1.01 h

214 210 208 211 207 212 208

Pb Pb Pb Pb Pb Pb Pb
26.9 m 22.6 y stable 36.1 m stable 10.6 h stable
207 208
Tl Tl
4.77 m 3.05 m

Peucker-Ehrenbrink, 2012 18
 Further Reading…
•Bourdon, B. et al. (Ed.) Uranium-Series Geochemistry, Rev. Mineral. &
Geochem., vol. 52, p. 20-21 (general solution to U-series equations).

•Bourdon, B. et al. (Ed.) Uranium-Series Geochemistry, Rev. Mineral. &

Geochem., vol. 52, p. 2-7 (U-series introduction).

•DecaySeries toy (simple Excel file).

19
 Activity = (l N)
A = 1 Ci, 3.7 106 bq
1.E+18
1.E+16
N
1.E+14
1.E+12
1.E+10
1.E+08
1.E+06
1.E+04
1.E+02
1.E+00
1.E-02
1.E-04
1.E-06

l
1.E-08
1.E-10
1.E-12
1.E-04 1.E-02 1.E+00 1.E+02 1.E+04 1.E+06 1.E+08 1.E+10

Half-life (years)

20
 Measurement Uncertainties
All measurements are afflicted with uncertainties. For large number of events, binomial distributions
asymptotically approach Gaussian (or normal) distributions. The spread in events (here numerical values of
isotope ratios, count rates or ion currents) is equal to N. According to Gaussian statistics about 2/3 of the
results lie within the range N ± N (one standard deviation), about 95% lie within the range N ± 2N (two
standard deviations), and ~99% lie within the range N ± 3N. The fractional uncertainty is thus N/N, or
1/N. If you measure twice as long (N*) you get twice as many events

N* = 2N

the fractional uncertainty is (2N)/2N = 1/(2N)

i.e. = 1/2 * 1/N

reducing the fractional uncertainty only by ~30%. The fractional uncertainty improves only as the square
root of time (or ion current, or count rate). If you attempt to improve the uncertainty by a factor of two, you
need to measure four times as long, or measure a four-times stronger ion current.
In order to evaluate if uncertainties associated with small ion beam intensities significantly affect the
measured ratios it is often helpful to assume that all uncertainties are associated with uncertainties in the
smallest ion current (least abundant isotope). By assuming an arbitrary uncertainty in the measurement of
this ion current you can plot an error trend on plots of isotope ratio versus another isotope ratio (same
isotope in the denominator, i.e. m2 = m4, if m1 and m3 are isotopes in the numerator). This trend is often
distinct from a instrumental fractionation trend and helps to assess what process dominates the uncertainty
of your analysis.

21
 Measurement Uncertainty
1.E+03

1.E+02

1.E+01
Counting
1.E+00 f(lN)
1.E-01

1.E-02

1.E-03

1.E-04
Mass spectrometry
1.E-05 0.01% transmission f(N)
1.E-06
1.E-04 1.E-02 1.E+00 1.E+02 1.E+04 1.E+06 1.E+08 1.E+10
~20
Half-life (years)

22
The Reporting of Data & Uncertainties

Text removed due to copyright restrictions.

See page 70 of Warren, Warren S. The physical

basis of chemistry. Academic Press, 2000.

23
MIT OpenCourseWare
http://ocw.mit.edu

12.744 Marine Isotope Chemistry

Fall 2012

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