For many people, a visit to a cave is a wondrous event directing our minds to ponder the mysteries presented by these unique places
and inspiring questions: How old is the cave? What was the role of water in forming the cave and where did the water come from?
How is the cave connected to the surface environment? These are intriguing questions to ask, and karst scientists use isotope
geochemistry to help solve these mysteries.
Isotopes are atoms of the same chemical element that have the same number of protons but vary in their number of neutrons. As a
result of their atomic mass difference, isotopes of a single element may exhibit slightly different chemical behavior. Radioisotopes are
unstable and the nucleus of a parent isotope will spontaneously break apart (decay), releasing energy and changing into another element
(daughter product) by loss or gain of protons, neutrons, or electrons. Stable isotopes, as implied by the name, are stable and do not
spontaneously decay. These two types of isotopes are used widely by scientists to understand ancient and modern karst systems.
Generally, radioisotopes are used for absolute dating karst water, cave sediments, cave formations (speleothems), and other
material preserved in caves (such as bones). Stable isotopes can provide information about relative ages of cave water and speleothems.
An absolute age provides a numeric date—such as 100,000 years old—whereas a relative age provides information that
something is older or younger than something else—such as cave art is younger than a speleothem found in the same cave. Stable
isotopes are used to study ancient karst systems because isotopic signals of past climate (paleoclimate) and environmental conditions
(paleoenvironment) are preserved in speleothems and sediments. Stable isotopes are also used to understand modern
systems, primarily through studies that distinguish sources of karst water, cave air, or contaminants, mixing of those sources,
and biologic or chemical reactions that process compounds, such as breakdown of contaminants or organic matter.
The variation in mass among isotopes is small, and isotope abundances are measured as a ratio of a common isotope to its less
common isotopic counterparts (stable isotopes) or the abundance of a parent compared to daughter isotope (radioisotopes). As an
example, hydrogen (H) has three naturally occurring isotopes. Most H comprises one proton (1H), but the rarer stable isotope
(called deuterium) comprises one proton and one neutron (2H), and the radioisotope (called tritium) comprises one proton
and two neutrons (3H). Because scientists use the minute differences in isotopes to test hypotheses, a scientist must understand
the accuracy, precision, and error of the available methods, the assumptions about the chemical conditions of interest, and the
limitations of the isotopic method being used. Many isotopic studies employ multiple isotopic tracers to better leverage the
strengths and offset the limitations of using a single isotope. This article focuses on isotopes used to study the geology and
hydrology of caves, but much additional isotopic work has been used to characterize the biology of caves.