What caused the rapid global warming? Researchers studying carbon isotopes have shown that the sudden increase in temperature implied by rising δ18O values was accompanied by sudden decreases in δ13C. Several hypotheses have been suggested for this, most of which involve warming and the release of large quantities of12C from organic carbon reservoirs. Two rapid spikes in negative δ13C, each occurring over time periods of less than 1000 years, suggest that some releases were extremely rapid. The currently favored hypothesis involves the melting of frozen clathrates in buried ocean floor sediments. Clathrates consist of frozen water in which methane, methanol, and other organic carbon molecules are trapped. The hypothesis is that small amounts of warming caused clathrates to melt, releasing large volumes of methane to the atmosphere in sudden bursts. This would account for the sudden negative δ13C spikes. Because methane (CH4) is a very effective greenhouse gas (10–20 times more effective than CO2), this theory also accounts for the sudden warming of Earth's surface and the extinction and mammalian radiation events that mark the Paleocene–Eocene boundary. Of course scientists wonder if the current episode of global warming that already involves an order of magnitude larger release of CO2 (Ivany et al. 2018) might be accelerated by triggering a sudden release of clathrates, and how long the effects of such releases might linger.
Because the Cretaceous was an unusually warm period in Earth's history, with high evaporation rates, PDB has an unusually high18O/16O ratio. As a result, most Pliocene–Pleistocene samples have a negative δ18O, with small negative numbers recording maximum glacial ice volumes and larger negative numbers recording minimum glacial ice volumes. Because different organisms selectively fractionate18O and16O, a range of organisms must be analyzed and the results averaged when determining global changes in18O/16O. Nothing is ever as easy as it first seems.
It should be noted that many δ18O analyses have used a different standard. This standard is the average18O/16 ratio in ocean water known as standard mean ocean water (SMOW). Of course, that has been complicated by global warming, that generally increases evaporation rates, changing the ratios in natural waters.
Because the original SMOW and PDB standards have been used up in comparative analyses, yet another standard, Vienna standard mean ocean water (VSMOW), is also used. This name is misleading as the Vienna standard is actually a pure water sample with no dissolved solids. There is currently much discussion concerning the notion of which standards are most appropriate and how δ18O and other isotope values should be reported.
Oxygen isotope analyses, as well as carbon isotopes discussed below, contribute essential data regarding Earth's paleoclimate as well as dynamic climate changes currently affecting Earth.
Carbon isotopes
Three isotopes of carbon occur naturally in Earth materials: carbon‐12 (12C), carbon‐13 (13C) and the radioactive carbon‐14 (14C), used in radiocarbon dating. Each carbon isotope contains six protons in its nucleus; the remaining mass results from the number of neutrons (six, seven or eight) in the nucleus.12C constitutes >98.9% of the stable carbon on Earth, and13C constitutes most of the other 1.1%.
When organisms synthesize organic molecules, they selectively utilize12C in preference to13C so that organic molecules have lower than average13C/12C ratios. Enrichment of the organic material in12C causes the13C/12C in the water column to increase. Ordinarily, there is a rough balance between the selective removal of12C from water during organic synthesis and its release back to the water column by bacterial decomposition, respiration, and other processes. Mixing processes produce a relatively constant13C/12C ratio in the water column. However, during periods of stagnant circulation in the oceans or other water bodies, disoxic–anoxic conditions develop in the lower part of the water column and/or in bottom sediments. These conditions inhibit bacterial decomposition (Chapters 11 and 14) and lead to the accumulation of12C‐rich organic sediments. These sediments have unusually low13C/12C ratios. As they accumulate, the remaining water column, depleted in12C, develops a higher ratio of13C/12C. However, any process, such as the return of vigorous circulation and oxidizing conditions, that rapidly release the12C‐rich carbon from organic sediments, is associated with a rapid decrease in13C/12C. By carefully plotting changes in13C/12C ratios over time, paleo‐oceanographers have been able to document both local and global changes in oceanic circulation. In addition, because different organisms selectively incorporate different ratios of12C to13C, the evolution of new groups of organisms and/or the extinction of old groups of organisms can sometimes be tracked by rapid changes in the13C/12C ratios of carbonate shells in marine sediments or organic materials in terrestrial soils.
13C/12C ratios are generally expressed with respect to a standard in terms of δ13C. The standard once again is the13C/12C ratio of the Pee Dee Belemnite, or PDB. δ13C is usually expressed in parts per thousand (mils) and calculated from:
Box 3.1 illustrates an excellent example of how oxygen and carbon isotope ratios can be used to document Earth history, in this case a period of sudden global warming that occurred 55 million years ago.
3.3.2 Radioactive isotopes
Radioactive isotopes possess unstable nuclei whose nuclear configurations tend to be spontaneously transformed by radioactive decay. Radioactive decay occurs when the nucleus of an unstable parent isotope is transformed into that of a daughter isotope. Daughter isotopes have different atomic numbers and/or different atomic mass numbers from their parent isotopes. Three major radioactive decay processes (Figure 3.12) have been recognized: alpha (α) decay, beta (β) decay, and electron capture.
Alpha decay involves the ejection of an alpha (α) particle plus gamma (γ) rays and heat from the nucleus. An alpha particle consists of two protons and two neutrons, which is the composition of a helium (4He) nucleus. The ejection of an alpha particle from the nucleus of a radioactive element reduces the atomic number of the element by two (2p+)