Indirect Dating Methods:

1. Dating Alteration Assemblages Dating hydrothermal mineral assemblages (e.g, sericite; biotite) in altered wall rocks adjacent to a mineral deposit is probably the most common way to indirectly date mineralization. In relatively simple cases this should be straightforward.

2. Dating Host Rocks for Mineralization This approach is obviously only applicable in situations where the mineralization can be tied temporally and genetically to the host rocks, and is therefore highly model-dependent. This method is probably reasonably accurate for VMS and SEDEX type deposits and for porphyry deposits, if the causative pluton can be conclusively identified.

3. Bracketing the Age of Mineralization Obtaining precise and accurate crystallization ages for pre- and post-ore intrusions is the only fool-proof method of dating mineralization. This is particularly valuable when used in conjunction with some of the other dating methods.

Common methods of indirect dating

K-Ar and 40Ar/39Ar

U-Pb Pb isotopes

K-Ar and 40Ar/39Ar Geochronology

The conventional K-Ar dating method and the derivative 40Ar/39Ar method are two of the most widely used geochronological tools for a wide range of geological applications Potassium is one of the most abundant elements and a major constituent of the Earths crust; however the radioactive K isotope (40K) comprises only a small fraction (0.017%) of the total K present in rock-forming minerals The relative proportion of naturally occurring K isotopes is fixed: 39 K 93.2581%
40 41 40

K 0.0167% K 6.7302%

K decays to 40Ar with a half-life of 1250 m.y.

K in a rock or mineral undergoes branching decay a small proportion (~11.0%) decays to 40Ar by electron capture and the remainder decays to 40 Ca by beta decay.
40

Basis of K-Ar Dating Method K is contained in the mineral lattice (or within volcanic glass) Ar is inert, so is not present in rocks or minerals (or is present in very small quantities) With time, 40K decays to 40Ar*, which is trapped in the crystal lattice The age is proportional to the relative abundances of 40K and 40Ar* To calculate an age, amounts of 40K and 40Ar* must be determined Age calculation: T = 1/ (40Ar*/40K(/) + 1 Where = total decay constant of 40K (= +) = decay constant of 40K to 40Ar*

Conventional K-Ar Extraction Line and Mass Spectrometer

Mass spectrometer Extraction line

Conventional K-Ar Dating Method:

40

Ar* and 40K contents are measured on separate sample aliquots

K determination: Total K is measured and 40K content is calculated using the constant ratio of K isotopes Ar determination: Isotopic ratios are measured using a 38Ar tracer (38Ar is the least abundant naturally occurring Ar isotope)

Calculating a K-Ar age: Age is proportional to 40K/40Ar* Determination of 40Ar* requires corrections for other sources of 40 Ar Ar in a sample is not all 40Ar*; but also includes some nonradiogenic 40Ar, usually of atmospheric origin
40 40

Ar* = 40Ar(m) 36Ar(m) [295.5] (m = measured)

Sources of analytical uncertainty: 1. Homogeneous monomineralic sample? Sample preparation or single mineral phase 2. Atmospheric Ar correction Inherent in samples, but also lab 3. Precision of analysis Laboratory care

K-Ar Isochrons K-Ar data can also be portrayed and interpreted using an isochron approach The age of the sample should be proportional to the slope of the isochron The lower intercept should correspond to the 40Ar/36Ar ratio of the atmosphere (295.5)

The problem is that the non-radiogenic component of Ar present in the different minerals (or whole rock samples) commonly does not have exactly the same isotopic composition; thus one of the basic premises of the isochron method is invalid

K-Ar and 40Ar/39Ar Geochronology

40

Ar/39Ar method is a variation on the conventional K-Ar method.

It is analytically more difficult and time-consuming A great deal more information can be obtained from an analysis ability to recognize thermal disturbance, mixed mineral phases, the presence of excess Ar, complex thermal history sample impurities etc.

40

Ar/39Ar Method

Based on measuring K and Ar in the same sample aliquot K content is determined indirectly from conversion of 39K to 39Ar by bombardment with fast neutrons in the core of a nuclear reactor

Ar isotopic measurement is similar to that used in the conventional K-Ar method, but uses a more sensitive and more accurate mass spectrometer, and a more precise sample heating method (to permit incremental heating). Resistance furnace
Extraction line

Mass spectrometer

Laser

A typical Ar-Ar extraction line and mass spectrometer

Irradiation of a K-bearing mineral or whole rock sample by fast neutrons in the core of a reactor converts a small proportion of 39K to 39Ar Ar is unstable and decays back to 39K with a half-life of 269 yrs (fortunately this is slow enough that the delay between sample irradiation and analysis is not a problem)
39

Several other interfering isotopes of Ar are also produced by the irradiation process. This is especially a problem with phases such as hornblende or plagioclase that contain significant amounts of Ca in addition to K. The relevant reactions are:
40 40 42

Ca 36Ar Ca 37Ar Ca 39Ar

Ar does not occur naturally; therefore we can measure the amount of 37Ar in the irradiated sample and use this conversion factor to estimate how much reactor-induced 36Ar and 39Ar are present, and subtract these
37

We must accurately estimate the efficiency of conversion of 39K to 39Ar in the reactor. This will vary depending on the particular reactor that is used and the actual position of the sample within the core region (neutron flux will vary to some extent within the reactor core) This is done by using flux monitors, which are natural mineral samples whose K-content and age are very precisely known Samples for irradiation are individually wrapped in Al foil, stacked in a small sample can with interspersed flux monitors, and all irradiated together. After irradiation, the flux monitors are removed from the sample can and their Ar isotopic composition is measured on the mass spectrometer. By knowing the age of the monitor mineral and its Kcontent we can back-calculate to get the conversion efficiency factor, which is referred to as the J-factor. This factor is then used in calculating the age of unknown samples that were in close proximity to that particular monitor in the sample can

40

Ar/39Ar Age Calculation

The age is calculated from: t = 1\ [ln(40Ar*/39Ar) J +1] Where: J = the efficiency of conversion factor, and
40

Ar*/39Ar = 40Ar/39Armeasured 295.5(36Ar/39Ar)

The J factor for the flux monitor is calculated as follows: J = [e tm 1]/[40Ar*/39Ar] Several flux monitors are in widespread use. One is either biotite or sanidine from the ~28 Ma Fish Canyon Tuff in Colorado. It has recently been shown that the actual age of this unit is slightly older than the age that is being used to calculate J factors in most labs; hence many Ar-Ar ages that have been reported in the literature of as much as 2% too old. In order to evaluate published 40Ar/39Ar ages one must know which flux monitor was used and what age was inferred for the monitor.

Advantages of the 40Ar/39Ar Method over the Conventional KAr Method

1. Avoids sample heterogeneity because only one sample aliquot is used 2. Age is more precise because the age is measured using only Ar isotopes (conventional K analysis is relatively imprecise) 3. Can determine a total fusion age (which is analogous to a conventional K-Ar age but more precise); or 4. Can analyze using step-heating methods, which helps detect episodic Ar loss, contamination by non-atmospheric Ar, and the detailed assessment of the thermal history of a sample

Total fusion or step-heating of samples can be done either using a furnace or a CO2 (or UV) laser

One final problem!!!

Observed that when heating hydrous minerals (micas, hornblendes, etc.) in vacuum, the minerals undergo phase changes. Suggested that the release of Ar from a mineral may reflect these phase changes rather than diffusive loss of Ar simply related to the heating. For example Biotite experiences major dehydration reactions at relatively low temperatures These reactions are strongly correlated with episodic Ar loss. Because of this, unambiguous interpretation of biotite Ar release spectra is somewhat questionable.

Hornblende undergoes a significant phase change at ~1000 degrees C Hornblende structure begins to exsolve Fe oxides. Another major phase change at 1030 degrees (usually the peak temperature when most Ar loss occurs. Hornblende structure decomposes into a fine-grained aggregate of cpx, plagioclase and Fe-Ti oxides.

The release of Ar appears to be unaffected up to ~1000 degrees; however the exact meaning of heating steps above this temperature are somewhat uncertain.