An isotopic signature (also isotopic fingerprint) is a ratio of non-radiogenic stable isotopes, stable radiogenic isotopes, or unstable radioactive isotopes of particular elements in an investigated material. The ratios of isotopes in a sample material are measured by isotope-ratio mass spectrometry against an isotopic reference material. This process is called isotope analysis.
Stable isotopes The atomic mass of different isotopes affect their chemical kinetic behavior, leading to natural isotope separation processes.
Carbon isotopes
For example, different sources and sinks of methane have different affinity for the 12C and 13C isotopes, which allows distinguishing between different sources by the 13C/12C ratio in methane in the air. In geochemistry, paleoclimatology and paleoceanography this ratio is called δ13C. The ratio is calculated with respect to Pee Dee Belemnite (PDB) standard:
δ C 13 s a m p l e = ( C 13 / 12 C sample C 13 / 12 C s t a n d a r d − 1 ) ⋅ 1000 {\displaystyle \delta {\ce {^{13}C}}_{\mathrm {sample} }=\left({\frac {{\ce {^{13}C/^{12}C}}_{{\ce {sample}}}}{{\ce {^{13}C/^{12}C}}_{\mathrm {standard} }}}-1\right)\cdot 1000} ‰ Similarly, carbon in inorganic carbonates shows little isotopic fractionation, while carbon in materials originated by photosynthesis is depleted of the heavier isotopes. In addition, there are two types of plants with different biochemical pathways; the C3 carbon fixation, where the isotope separation effect is more pronounced, C4 carbon fixation, where the heavier 13C is less depleted, and Crassulacean Acid Metabolism (CAM) plants, where the effect is similar but less pronounced than with C4 plants. Isotopic fractionation in plants is caused by physical (slower diffusion of 13C in plant tissues due to increased atomic weight) and biochemical (preference of 12C by two enzymes: RuBisCO and phosphoenolpyruvate carboxylase) factors. The different isotope ratios for the two kinds of plants propagate through the food chain, thus it is possible to determine if the principal diet of a human or an animal consists primarily of C3 plants (rice, wheat, soybeans, potatoes) or C4 plants (corn, or corn-fed beef) by isotope analysis of their flesh and bone collagen (however, to obtain more accurate determinations, carbon isotopic fractionation must be also taken into account, since several studies have reported significant 13C discrimination during biodegradation of simple and complex substrates). Within C3 plants processes regulating changes in δ13C are well understood, particularly at the leaf level, but also during wood formation. Many recent studies combine leaf level isotopic fractionation with annual patterns of wood formation (i.e. tree ring δ13C) to quantify the impacts of climatic variations and atmospheric composition on physiological processes of individual trees and forest stands. The next phase of understanding, in terrestrial ecosystems at least, seems to be the combination of multiple isotopic proxies to decipher interactions between plants, soils and the atmosphere, and predict how changes in land use will affect climate change. Similarly, marine fish contain more 13C than freshwater fish, with values approximating the C4 and C3 plants respectively. The ratio of carbon-13 and carbon-12 isotopes in these types of plants is as follows:
C4 plants: −16‰ to −10‰ CAM plants: −20‰ to −10‰ C3 plants: −33‰ to −24‰ Limestones formed by precipitation in seas from the atmospheric carbon dioxide contain normal proportion of 13C. Conversely, calcite found in salt domes originates from carbon dioxide formed by oxidation of petroleum, which due to its plant origin is 13C-depleted. The layer of limestone deposited at the Permian extinction 252 Mya can be identified by the 1% drop in 13C/12C.
Nitrogen isotopes
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