This chapter reviews the methods to estimate quantitatively the age of very old groundwaters (beyond 14C dating range to tens of millions of years) includ-ing 4He, 36Cl, 40Ar, 81Kr, 129I, and uranium disequilibrium series, especially the 234U/238U method. The principles, limitations, requirements, relevant equations, advantages, case histories, field sampling, and laboratory measurements of each method are described. Included in this chapter are the specifications of the potential aquifers that these methods are applicable to, such as deep sed-imentary basins, regional flow systems, and groundwater in the Earth’s crust. It also includes reasons why quantitative age measurements of very old groundwaters have not been quite successful as yet. Table 6.7 lists the advan-tages and disadvantages of each method. Note that 4He is also used for dat-ing young groundwaters (Chapter 4), and some other potential—yet to be proven—very old dating methods such as that based on 87Sr/86Sr are briefly discussed in Chapter 8. With regard to 36Cl and 4He methods, there are sub-stantial reviews by Phillips (2000) and Pinti and Marty (1998), Solomon (2000), Mazor (2004), respectively, which are suggested for consultation if in-depth understanding of these methods is sought. For all aspects of noble gases includ-ing groundwater dating, Porcelli et al. (2002) is recommended for study and research purposes.
6.1 KRYPTON-81
General information about krypton and its isotopes is found in Section 4.5, where 85Kr is described as a tracer to date young groundwaters. Krypton-81 has since long been proposed as a groundwater dating tool (Loosli and Oeschger, 1969). It has, however, not been used as a tracer in other hydrolog-ical fields.
6.1.1 Production of 81Kr
Krypton-81 is produced in the upper atmosphere by cosmic-ray-induced spal-lation of five heavier Kr isotopes (from 82Kr to 86Kr), e.g.,
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