1. GEOCHRONOLOGY HONOURS 2006 Lecture 01 Introduction to Radioactive Decay and Dating of Geological Materials

2. Revision – What is an Isotope?

3. Protons, Neutrons and Nuclides  The mass of any element is determined by the protons plus the neutrons.  Where the element has different numbers of neutrons these are called isotopes  Any element can have isotopes that have the same proton number but different numbers of neutrons and hence a different mass number.  The mass of any element is made up of the sum of the mass of each isotope of that element multiplied by its atomic abundance.  Various combinations of N and Z are possible, although all combinations with the same Z number are the same element.

4. Stable versus Unstable Nuclides  Not all combinations of N and Z result in stable nuclides.  Some combinations result in stable configurations –Relatively few combinations –Generally N ≈ Z –However, as A becomes larger, N > Z  For some combinations of N+Z a nucleus forms but is unstable with half lives of > 10 5 yrs to < 10 -12 sec  These unstable nuclides transform to stable nuclides through radioactive decay

6. Radioactive Decay  Nuclear decay takes place at a rate that follows the law of radioactive decay  Radioactive decay has three important features 1.The decay rate is dependent only on the energy state of the nuclide 2.The decay rate is independent of the history of the nucleus 3.The decay rate is independent of pressure, temperature and chemical composition  The timing of radioactive decay is impossible to predict but we can predict the probability of its decay in a given time interval

7. Radioactive Decay  The probability of decay in some infinitesimally small time interval, dt, is dt, where is the decay constant for the particular isotope  The rate of decay among some number, N, of nuclides is therefore dN / dt = - N[eq. 1]  The minus sign indicates that N decreases over time.  Essentially all significant equations of radiogenic isotope geochronology can be derived from this expression.

8. Types of Radioactive Decay  Beta Decay  Positron Decay  Electron Capture Decay  Branched Decay  Alpha Decay

9. Beta Decay  Beta decay is essentially the transformation of a neutron into a proton and an electron and the subsequent expulsion of the electron from the nucleus as a negative beta particle.  Beta decay can be written as an equation of the form 19 K 40 -> 20 Ca 40 +  - + + Q Where  - is the beta particle, is the antineutrino and Q stands for the maximum decay energy. _ _

10. Positron Decay  Similar to Beta decay except that now a proton in the nucleus is transformed into a neutron, positron and neutrino.  Only possible when the mass of the parent is greater than that of the daughter by at least two electron masses.  Positron decay can be written as an equation of the form 9 F 18 -> 8 O 18 +  + + + Q Where  + is the positron, is the neutrino and Q stands for the maximum decay energy.

11. Positron VS Beta Decay The atomic number of the daughter isotope is decreased by 1 while the neutron number is increased by 1. The atomic number of the daughter isotope is increased by 1 while the neutron number is decreased by 1. Therefore in both cases the parent and daughter isotopes have the same mass number and therefore sit on an isobar.

13. Electron Capture Decay  Electron capture decay occurs when a nucleus captures one of its extranuclear electrons and in the process decreases its proton number by one and increases its neutron number by one.  This results in the same relationship between the parent and the daughter isotope as in positron decay whereby they both occupy the same isobar.

14. Alpha Emission  Represents the spontaneous emission of alpha particles from the nuclei of radionuclides.  Only available to nuclides of atomic number of 58 (Cerium) or greater as well as a few of low atomic number including He, Li and Be.  Alpha emission can be written as: 92 U 238 -> 90 Th 234 + 2 He 4 + Q Where 2 He 4 is the alpha particle and Q is the total alpha decay energy

15. Alpha Emission A daughter isotope produced by alpha emission will not necessarily be stable and can itself decay by either alpha emission, or beta emission or both.

16. Branched Decay  The difference in the atomic number of two stable isobars is greater than one, ie two adjacent isobars cannot both be stable.  Implication is that two stable isobars must be separated by a radioactive isobar that can decay by different mechanisms to produce either stable isobar.  Example 71 Lu 176 decays to 72 Hf 176 via negative beta decay 72 Hf 176 decays to 70 Yb 176 by positron decay or electron capture.

17. Branched decay scheme for A=38 isobar

18. Branched decay scheme for A=132 isobar

19. Decay of 238U to 206Pb

20. Radiogenic Isotope Geochemistry  Can be used in two important ways 1. Tracer Studies  Makes use of the differences in the ratio of the radiogenic daughter isotope to other isotopes of the element  Can make use of the differences in radiogenic isotopes to look at Earth Evolution and the interaction and differentiation of different reservoirs

21. Radiogenic Isotope Geochemistry 2. Geochronology  Makes use of the constancy of the rate of radioactive decay  Since a radioactive nuclide decays to its daughter at a rate independent of everything, it is possible to determine time simply by determining how much of the nuclide has decayed.

22. Radiogenic Isotope Systems  The radiogenic isotope systems that are of interest in geology include the following K-Ar Ar-Ar Fission Track Cosmogenic Isotopes Rb-Sr Sm-Nd Re-Os U-Th-Pb Lu-Hf

23. Table of the elements

24. Radiogenic Isotope Systems  The radiogenic isotope systems that are of interest in geology include the following K-Ar Ar-Ar Fission Track Cosmogenic Isotopes Rb-Sr Sm-Nd Re-Os U-Th-Pb Lu-Hf

25. Geochronology and Tracer Studies Isotopic variations between rocks and minerals due to 1.Daughters produced in varying proportions resulting from previous event of chemical fractionation 40 K  40 Ar by radioactive decay Basalt  rhyolite by FX (a chemical fractionation process) Rhyolite has more K than basalt 40 K  more 40 Ar over time in rhyolite than in basalt 40 Ar/ 39 Ar ratio will be different in each 2.Time: the longer 40 K  40 Ar decay takes place, the greater the difference between the basalt and rhyolite will be

26. The Decay Constant  Over time the amount of the daughter (radiogenic) isotope in a system increases and the amount of the parent (radioactive) isotope decreases as it decays away. If the rate of radioactive decay is known we can use the increase in the amount of radiogenic isotopes to measure time.  The rate of decay of a radioactive (parent) isotope is directly proportional to the number of atoms of that isotope that are present in a system, ie Equation 1 that we have seen previously. –dN/dt = - N,[eq. 1] –where N = the number of parent atoms and is the decay constant –The -ve sign means that the rate decreases over time

27. The Half Life  The half life of a radioactive isotope is the time it takes for the number of parent isotopes to decay away to half their original value. It is related to the decay constant by the expression –T 1 / 2 = ln2/  For 87 Rb, the decay constant is 1.42 x 10 -11 y -1, hence, t 1/2 87 Rb = 4.88 x 10 10 years. In other words after 4.88 x 10 10 years a system will contain half as many atoms of 87 Rb as it started off with.

28. Geologically Important Isotopes and their Decay Constants

29. Using the Decay Constant The number of radiogenic daughter atoms (D*) produced from the decay of the parent since date of formation of the sample is given by D* = N o - N [eq. 2] Where D* is the number of daughter atoms produced by decay of the parent atom and N o is the number of original parent atoms Therefore the total number of daughter atoms, D, in a sample is given by D = D o + D* [eq. 3]

30. Using the Decay Constant The two equations can be combined to give D = D o + N o – N[eq. 4] Generally, when rocks or minerals first form they contain a greater or lesser amount of the daughter atoms of a particular isotope system, i.e., not all the daughter atoms that we measure in a sample today were formed by decay of the parent isotope since the rock first formed.

31. Dating of Rocks from Radioactive Decay Recalling that -dN/dt = N[eq. 1] Integration of the above yields N=N o e - t [eq. 5] We can substitute this into equation 4 to get D=D o + Ne t – N [eq. 6] which simplifies to D=D o + N(e t – 1) [eq. 7]

32. The Radiogenic Decay Equation  Equation 7 is the basic decay equation and is used extensively in radiogenic isotope geochemistry.  In principle, D and N are measurable quantities, while D o is a constant whose value can be either assumed or calculated from data for cogenetic samples of the same age.  If these three variables are known then the above equation can be solved for t to give an “age” for the rock or mineral in question.

33. Plotting Geochron Data  There are two methods for graphically illustrating geochron data  1. The Isochron Technique –Used when the decay scheme has one parent isotope decaying to a daughter isotope. –Results in a straight line plot  2. The Concordia Diagram –Used when more than one decay scheme results in the formation of the daughter isotopes –Results in a curved diagram (we’ll talk more about this later when we look at U-Th-Pb)

34. The Isochron Technique  The Isochron Technique –Requires 3 or more cogenetic samples with a range of Rb/Sr 3 cogenetic rocks derived from a single source by partial melting, FX, etc. 3 coexisting minerals with different K/Ca ratios in a single rock  Let’s look at an example in the Rb/Sr system

35. The Rb-Sr system  Strontium has four naturally occurring isotopes all of which are stable – 38 Sr 88, 38 Sr 87, 38 Sr 86, 38 Sr 84  Their isotopic abundances are approximately –82.53%, 7.04%, 9.87%, and 0.56%  However the isotopic abundances of strontium isotopes varies because of the formation of radiogenic Sr 87 from the decay of naturally occurring Rb 87  Therefore the precise isotopic composition of strontium in a rock or mineral depends on the age and Rb/Sr ratio of that rock or mineral.

36. Rb-Sr Isochrons  If we are trying to date a rock using the Rb/Sr system then the basic decay equation we derived earlier has the form Sr 87 = Sr 87 i + Rb 87 (e t –1)  In practice, it is a lot easier to measure the ratio of isotopes in a sample of rock or a mineral, rather than their absolute abundances. Therefore we can divide the above equation through by the number of Sr 86 atoms which is constant because this isotope is stable and not produced by decay of a naturally occurring isotope of another element.

37. Rb-Sr Isochrons  This gives us the equation 87 Sr/ 86 Sr = ( 87 Sr/ 86 Sr)i + 87 Rb/ 86 Sr(e t – 1)  To solve this equation, the concentrations of Rb and Sr and the 87 Sr/ 86 Sr ratio must be measured.  The Sr isotope ratio is measured on a mass spectrometer whilst the concentrations of Rb and Sr are normally determined by XRF or ICPMS.

38. Rb-Sr Isochrons  The concentrations of Rb and Sr are converted to the 87 Rb/ 86 Sr ratio by the following equation. 87 Rb/ 86 Sr = (Rb/Sr) x (Ab 87 Rb x WSr)/(Ab 86 Sr x WRb), where Ab is the isotopic abundance and W is the atomic weight.  The abundance of 86 Sr (Ab 86 Sr) and the atomic weight of Sr (WSr) depend on the abundance of 87 Sr and therefore must be calculated for each sample.

44. What can we learn from this? 1.After each period of time, the 87 Rb in each rock decays to 87 Sr producing a new line 2.This line is still linear but is steeper than the previous line. 3.We can use this to tell us two important things The age of the rock The initial 87 Sr/ 86 Sr isotope ratio

45. Determining the Age of a Rock

47. Let’s look now at the initial ratio

48. The Fitting of Isochrons  After the 87Sr/86Sr and 87Rb/86Sr ratios of the samples or minerals have been determined and have been plotted on an isochron, the problem arises of fitting the ‘best’ straight line to the data points.  The fit of data points to a straight line is complicated by the errors that are associated with each of the analyses

49. The Fitting of Isochrons

50. Equations for Calculating the Best Slope and Intercepts of a Straight Line

51. The initial ratio  How do we know if a series of rocks are co- genetic?  For rocks to be co-genetic, implies that they are derived from the same parent material.  This parent material would have had a single 87 Sr/ 86 Sr isotope value, ie the initial isotope ratio  Therefore, all samples derived from the same parent magma should all have the same 87 Sr/ 86 Sr isotope ratio  If they don’t, it implies that they are derived from a different parent source.

57. Errorchrons and MSWD Values  A line fitted to a set of data that display a scatter about this line in excess of the experimental error is not an isochron.  The sum of the squares of miss-fits of each point to the regression line, may be divided by the number of degrees of freedom (number of data points minus two) to yield the Mean Squared Weighted Deviates (MSWD).  MSWD values give an indication of scatter and can therefore be used to indicate whether an errorchron or isochron is indicated by the data.  MSWD values should be near unity to be indicative of an isochron. Values over 2.5 are definitely errochrons.

58. Sm-Nd Isotope System  Sm has seven naturally occurring isotopes  Of these 147 Sm, 148 Sm and 149 Sm are radioactive but only 147 Sm has a half life that impacts on the abundance of 143 Nd.  The decay equation for Sm/Nd is – 143 Nd/ 144 Nd = ( 143 Nd/ 144 Nd)i + 147 Sm/ 144 Nd(e t – 1)

59. Epsilon Notation  Archean plutons have initial 143 Nd/ 144 Nd ratios that are very similar to that of the Chondritic Uniform Reservoir (CHUR) predicted from meterorites.  Because of the similar chemical behaviour of Sm and Nd, departures in 143 Nd/ 144 Nd isotopic ratios from the CHUR evolution line are very small in comparison to the slope of the line.  Therefore Epsilon notation for Sm/Nd system is: –  Nd(t) = (( 143 Nd/ 144 Nd) sample (t)/( 143 Nd/ 144 Nd) CHUR (t) – 1) x 10 4

60. Behaviour of Rb and Sr in Rocks and Minerals  Rb behaves like K  micas and alkali feldspar  Sr behaves like Ca  plagioclase and apatite (but not clinopyroxene) Rock TypeRb ppmK ppmSr ppmCa ppm Ultrabasic0.240125,000 Basaltic308,30046576,000 High Ca granite11025,20044025,300 Low Ca granite17042,0001005,100 Syenite11048,00020018,000 Shale14026,60030022,100 Sandstone6010,7002039,100 Carbonate32,700610302,300 Deep sea carbonate102,9002000312,400 Deep sea clay11025,00018029,000

61. Behaviour of Sm and Nd in Rocks and Minerals  Both Sm and Nd are LREE  Because Sm and Nd have very similar chemical properties that are not fractionated very much by igneous processes such as fractional crystallisation.  Useful for looking at metamorphic processes not igneous processes Rock / MinSm ppmNd ppmSm/Nd Olivine0.070.360.19 Garnet1.172.170.539 Apatite2237180.311 Monazite15,00088,0000.17 MORB Thol3.3010.30.320 Rhyolite4.6521.60.215 Eclogite2.618.640.302 Granulite4.9631.80.156 Sandstone8.9339.40.227 Chondrites0.1990.6200.320

62. Rb-Sr vs Sm-Nd  Sm-Nd –Mafic and Ultramafic igneous rocks –Metamorphic Events –Rocks that have lost Rb-Sr  Rb-Sr –Acidic and Intermediate igneous rocks –Rocks enriched in rubidium and depleted in strontiu,

63. Model Ages  The isotopic evolution of Nd in the Earth is described in terms of a model called CHUR, which stands for “Chondritic Uniform Reservoir”.  CHUR was defined by DePaolo and Wasserburg in 1976.  The initial (or primordial) 143 Nd/ 144 Nd ratio and present 147 Sm/ 144 Nd ratio and the age of the Earth have been determined by dating achondrite and chondrite meteorites  The model assumes that terrestrial Nd has evolved in a uniform reservoir whose Sm/Nd ratio is equal to that of chondritic meteorites.

64. CHUR and the Isotopic Evolution of Nd  We can calculate the value of CHUR at any time, t, in the past using the following equation and values

65. Implications  Partial melting of CHUR gives rise to magmas having lower Sm/Nd ratios than CHUR  Igneous rocks that form from such a melt therefore have lower present day 143 Nd/ 144 Nd ratios than CHUR  The residual solids that remain behind therefore have higher Sm/Nd ratios than CHUR  Consequently, these regions (referred to as “depleted regions” of the reservoir) have higher 143 Nd/ 144 Nd ratios than CHUR at the present time

66. Nd-Isotope Evolution of Earth

67. Model Dates  CHUR can be used to calculate the date at which the Nd in a crustal rock separated from the chondritic reservoir.  This is done by determining the time in the past when the 143 Nd/ 144 Nd ratio of the rock equaled that of CHUR  Skipping lots of in between steps the equation becomes

68. Model Dates  Dates calculated in the above manner make one very big assumption –The Sm/Nd ratio of the rock has not changed since the time of separation of Nd from the Chondritic Reservoir  If there was a disturbance in the Sm/Nd ratio then the date calculated would not have any geological meaning.  This criteria is better met by Sm/Nd than by Rb/Sr because of the similar behaviour of Sm/Nd.

69. Model Dates and Sr-Isotope Evolution  The isotopic evolution of Nd and Sr in the mantle are strongly correlated.  This correlation gives rise to the “mantle array”  The mantle array (defined from uncontaminated basalts in oceanic basins) arises through the negative correlation of 143 Nd/ 144 Nd and 87 Sr/ 86 Sr ratios  This indicates that oceanic basalts are derived from rocks whose Rb/Sr ratios were lowered but whose Sm/Nd ratios were increased in the past

71. Sr-Isotope Evolution of Earth

72. Epsilon Sr Calculations