5 AGE-DATING OLDGROUNDWATERS

The methods to age-date old groundwaters (60–50,000 years old) include mostly 14C, but less used and indirect methods such as 32Si, 39Ar, 18O, 2H, and conservative and reactive tracers are also explained. In addition to presenting some new data from salinized watersheds in Australia, various aspects of 14C dating such as initial value problem, 14C modifying geochemical reactions, half-life variations, and Sanford correction for diffusion in fractured-rock and aquifer-aquitard environments are discussed. The principle, characteristics, limitations, requirements, correction factors applicable to each method, rele-vant formulas and equations, advantages, working examples, field sampling and laboratory measurements, and associated costs of each method are also spelled out (at the end of the chapter, advantages and disadvantages of all the dating methods are presented in Table 5.3). With regard to 14C, however, there are at least three major book chapters (Clark and Fritz, 1997; Kalin, 2000; Mazor, 2004) that discuss the topic in detail. This has caused us to refrain from going deep into all aspects of the method because it would inevitably be a repetition of the previous books. We have therefore limited our discussion to major aspects.
Silicon-32 (t0.5 ∼ 140 years) and argon-39 (t0.5 = 269 years) have been classi-fied as old groundwaters-dating methods because their half-lives are much longer than those of isotopes for dating young groundwaters. Also, it was intended to have a correspondence between human average life expectancy and the age of young groundwaters. Silicon-32 and 39Ar dating methods have been applied to very limited extent, and the related publications are only a few. As a consequence, not much emphasis is needed to be placed here on these methods. Another point worthy of note is that in a number of references the 4He method is referred to as a dating method that could cover old ground-water age ranges (say from about 1,000 years and longer), in addition to both young and very old groundwaters. Practically, however, this has not been satisfactorily demonstrated as yet and we have therefore discussed the 4He method in the context of young and very old groundwaters only, i.e., Chapters 4 and 6.
5.1 SILICON-32
Silicon, discovered by Jons Berzelius in 1822, has the relative atomic weight of 28 and 3 stable isotopes: 28Si (92.27%), 29Si (4.68%), and 30Si (3.05%). It also has a number of radioactive isotopes such as 26Si, 27Si, 31Si, and 32Si; but only 32Si is of hydrologic and geoscientific interest. Despite being the second most abundant element (after oxygen) in the Earth’s crust, forming 25.7% of the Earth’s crust by weight, silicon isotopes are not widely used in geosciences because the nature of Si compounds is such that the δ30Si variations are small and the fractionation processes are limited (Attendorn and Bowen, 1997). The cosmic abundance of silicon, however, is only 0.05% by weight (Cameron, 1973, cited by Attendorn and Bowen, 1997).
The half-life of silicon-32 was and still is under intense investigation and doubt; estimates range from 60 to 700 years (Alburger et al., 1986). The most recent estimation, which is the weighted average of a number of earlier meas-urements, puts it at 140 ± 6 years (Morgenstern et al., 1996). However, one could argue that this is not quite satisfactory because the latest related report, i.e., Lal (2001), tends to adapt the 150-year estimate.
5.1.1 Production of 32Si
Silicon-32 is produced in the upper atmosphere by cosmic-ray spallation of argon according to the reaction: