Mass-independent isotope fractionation or Non-mass-dependent fractionation (NMD), [1] refers to any chemical or physical process that acts to separate isotopes, where the amount of separation does not scale in proportion with the difference in the masses of the isotopes. Most isotopic fractionations (including typical kinetic fractionations and equilibrium fractionations) are caused by the effects of the mass of an isotope on atomic or molecular velocities, diffusivities or bond strengths. Mass-independent fractionation processes are less common, occurring mainly in photochemical and spin-forbidden reactions. Observation of mass-independently fractionated materials can therefore be used to trace these types of reactions in nature and in laboratory experiments.
The most notable examples of mass-independent fractionation in nature are found in the isotopes of oxygen and sulfur. The first example was discovered by Robert N. Clayton, Toshiko Mayeda, and Lawrence Grossman in 1973, [2] in the oxygen isotopic composition of refractory calcium–aluminium-rich inclusions in the Allende meteorite. The inclusions, thought to be among the oldest solid materials in the Solar System, show a pattern of low 18O/16O and 17O/16O relative to samples from the Earth and Moon. Both ratios vary by the same amount in the inclusions, although the mass difference between 18O and 16O is almost twice as large as the difference between 17O and 16O. Originally this was interpreted as evidence of incomplete mixing of 16O-rich material (created and distributed by a large star in a supernova) into the Solar nebula. However, recent measurement of the oxygen-isotope composition of the Solar wind, using samples collected by the Genesis spacecraft, shows that the most 16O-rich inclusions are close to the bulk composition of the solar system. This implies that Earth, the Moon, Mars, and asteroids all formed from 18O- and 17O-enriched material. Photodissociation of carbon monoxide in the Solar nebula has been proposed to explain this isotope fractionation.
Mass-independent fractionation also has been observed in ozone. Large, 1:1 enrichments of 18O/16O and 17O/16O in ozone were discovered in laboratory synthesis experiments by Mark Thiemens and John Heidenreich in 1983, [3] and later found in stratospheric air samples measured by Konrad Mauersberger. [4] These enrichments were eventually traced to the three-body ozone formation reaction. [5]
Theoretical calculations [6] by Rudolph Marcus and others suggest that the enrichments are the result of a combination of mass-dependent and mass-independent kinetic isotope effects (KIE) involving the excited state O3* intermediate related to some unusual symmetry properties. The mass-dependent isotope effect occurs in asymmetric species, and arises from the difference in zero-point energy of the two formation channels available (e.g., 18O16O + 16O vs 18O + 16O16O for formation of 18O16O16O.) These mass-dependent zero-point energy effects cancel one another out and do not affect the enrichment in heavy isotopes observed in ozone. [7] The mass-independent enrichment in ozone is still not fully understood, but may be due to isotopically symmetric O3* having a shorter lifetime than asymmetric O3*, thus not allowing a statistical distribution of energy throughout all the degrees of freedom, resulting in a mass-independent distribution of isotopes.
The mass-independent distribution of isotopes in stratospheric ozone can be transferred to carbon dioxide (CO2). [8] This anomalous isotopic composition in CO2 can be used to quantify gross primary production, the uptake of CO2 by vegetation through photosynthesis. This effect of terrestrial vegetation on the isotopic signature of atmospheric CO2 was simulated with a global model [9] and confirmed experimentally. [10]
Mass-independent fractionation of sulfur can be observed in ancient sediments, [11] where it preserves a signal of the prevailing environmental conditions. The creation and transfer of the mass-independent signature into minerals would be unlikely in an atmosphere containing abundant oxygen, constraining the Great Oxygenation Event to some time after 2,450 million years ago. Prior to this time, the MIS record implies that sulfate-reducing bacteria did not play a significant role in the global sulfur cycle, and that the MIS signal is due primarily to changes in volcanic activity. [12]
Isotope analysis is the identification of isotopic signature, abundance of certain stable isotopes of chemical elements within organic and inorganic compounds. Isotopic analysis can be used to understand the flow of energy through a food web, to reconstruct past environmental and climatic conditions, to investigate human and animal diets, for food authentification, and a variety of other physical, geological, palaeontological and chemical processes. Stable isotope ratios are measured using mass spectrometry, which separates the different isotopes of an element on the basis of their mass-to-charge ratio.
Magnesite is a mineral with the chemical formula MgCO
3. Iron, manganese, cobalt, and nickel may occur as admixtures, but only in small amounts.
Isotope geochemistry is an aspect of geology based upon the study of natural variations in the relative abundances of isotopes of various elements. Variations in isotopic abundance are measured by isotope-ratio mass spectrometry, and can reveal information about the ages and origins of rock, air or water bodies, or processes of mixing between them.
Vienna Standard Mean Ocean Water (VSMOW) is an isotopic standard for water, that is, a particular sample of water whose proportions of different isotopes of hydrogen and oxygen are accurately known. VSMOW is distilled from ocean water and does not contain salt or other impurities. Published and distributed by the Vienna-based International Atomic Energy Agency in 1968, the standard and its essentially identical successor, VSMOW2, continue to be used as a reference material.
Kinetic fractionation is an isotopic fractionation process that separates stable isotopes from each other by their mass during unidirectional processes. Biological processes are generally unidirectional and are very good examples of "kinetic" isotope reactions. All organisms preferentially use lighter isotopic species, because "energy costs" are lower, resulting in a significant fractionation between the substrate (heavier) and the biologically mediated product (lighter). As an example, photosynthesis preferentially takes up the light isotope of carbon 12C during assimilation of an atmospheric CO2 molecule. This kinetic isotope fractionation explains why plant material (and thus fossil fuels, which are derived from plants) is typically depleted in 13C by 25 per mil (2.5 per cent) relative to most inorganic carbon on Earth.
An isotopic signature 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.
Oxygen isotope ratio cycles are cyclical variations in the ratio of the abundance of oxygen with an atomic mass of 18 to the abundance of oxygen with an atomic mass of 16 present in some substances, such as polar ice or calcite in ocean core samples, measured with the isotope fractionation. The ratio is linked to ancient ocean temperature which in turn reflects ancient climate. Cycles in the ratio mirror climate changes in the geological history of Earth.
The atmosphere of Mars is the layer of gases surrounding Mars. It is primarily composed of carbon dioxide (95%), molecular nitrogen (2.85%), and argon (2%). It also contains trace levels of water vapor, oxygen, carbon monoxide, hydrogen, and noble gases. The atmosphere of Mars is much thinner and colder than Earth's having a max density 20g/m3 with a temperature generally below zero down to -60 Celsius. The average surface pressure is about 610 pascals (0.088 psi) which is less than 1% of the Earth's value.
In geochemistry, paleoclimatology and paleoceanography δ18O or delta-O-18 is a measure of the deviation in ratio of stable isotopes oxygen-18 (18O) and oxygen-16 (16O). It is commonly used as a measure of the temperature of precipitation, as a measure of groundwater/mineral interactions, and as an indicator of processes that show isotopic fractionation, like methanogenesis. In paleosciences, 18O:16O data from corals, foraminifera and ice cores are used as a proxy for temperature.
Isotope fractionation describes fractionation processes that affect the relative abundance of isotopes, phenomena which are taken advantage of in isotope geochemistry and other fields. Normally, the focus is on stable isotopes of the same element. Isotopic fractionation can be measured by isotope analysis, using isotope-ratio mass spectrometry or cavity ring-down spectroscopy to measure ratios of isotopes, an important tool to understand geochemical and biological systems. For example, biochemical processes cause changes in ratios of stable carbon isotopes incorporated into biomass.
Oxygen-17 (17O) is a low-abundance, natural, stable isotope of oxygen.
The Dole effect, named after Malcolm Dole, describes an inequality in the ratio of the heavy isotope 18O to the lighter 16O, measured in the atmosphere and seawater. This ratio is usually denoted δ18O.
Equilibrium isotope fractionation is the partial separation of isotopes between two or more substances in chemical equilibrium. Equilibrium fractionation is strongest at low temperatures, and forms the basis of the most widely used isotopic paleothermometers : D/H and 18O/16O records from ice cores, and 18O/16O records from calcium carbonate. It is thus important for the construction of geologic temperature records. Isotopic fractionations attributed to equilibrium processes have been observed in many elements, from hydrogen (D/H) to uranium (238U/235U). In general, the light elements are most susceptible to fractionation, and their isotopes tend to be separated to a greater degree than heavier elements.
The Global Meteoric Water Line (GMWL) describes the global annual average relationship between hydrogen and oxygen isotope (oxygen-18 and deuterium) ratios in natural meteoric waters. The GMWL was first developed in 1961 by Harmon Craig, and has subsequently been widely used to track water masses in environmental geochemistry and hydrogeology.
The surface color of the planet Mars appears reddish from a distance because of rusty atmospheric dust. From close up, it looks more of a butterscotch, and other common surface colors include golden, brown, tan, and greenish, depending on minerals.
Clumped isotopes are heavy isotopes that are bonded to other heavy isotopes. The relative abundance of clumped isotopes (and multiply-substituted isotopologues) in molecules such as methane, nitrous oxide, and carbonate is an area of active investigation. The carbonate clumped-isotope thermometer, or "13C–18O order/disorder carbonate thermometer", is a new approach for paleoclimate reconstruction, based on the temperature dependence of the clumping of 13C and 18O into bonds within the carbonate mineral lattice. This approach has the advantage that the 18O ratio in water is not necessary (different from the δ18O approach), but for precise paleotemperature estimation, it also needs very large and uncontaminated samples, long analytical runs, and extensive replication. Commonly used sample sources for paleoclimatological work include corals, otoliths, gastropods, tufa, bivalves, and foraminifera. Results are usually expressed as Δ47 (said as "cap 47"), which is the deviation of the ratio of isotopologues of CO2 with a molecular weight of 47 to those with a weight of 44 from the ratio expected if they were randomly distributed.
Marilyn L. Fogel was an American geo-ecologist and Professor of Geo-ecology at UC Riverside in Riverside, California. She is known for her research using stable isotope mass spectrometry to study a variety of subjects including ancient climates, biogeochemical cycles, animal behavior, ecology, and astrobiology. Fogel served in many leadership roles, including Program Director at the National Science Foundation in geobiology and low-temperature geochemistry.
Microbial oxidation of sulfur is the oxidation of sulfur by microorganisms to build their structural components. The oxidation of inorganic compounds is the strategy primarily used by chemolithotrophic microorganisms to obtain energy to survive, grow and reproduce. Some inorganic forms of reduced sulfur, mainly sulfide (H2S/HS−) and elemental sulfur (S0), can be oxidized by chemolithotrophic sulfur-oxidizing prokaryotes, usually coupled to the reduction of oxygen (O2) or nitrate (NO3−). Anaerobic sulfur oxidizers include photolithoautotrophs that obtain their energy from sunlight, hydrogen from sulfide, and carbon from carbon dioxide (CO2).
Mark Howard Thiemens is a distinguished professor and the John Doves Isaacs Endowed Chair in Natural Philosophy of Physical Sciences in the department of chemistry and biochemistry at the University of California San Diego. He is best known for the discovery of a new physical chemical phenomenon termed the mass independent isotope effect.
Sulfur isotope biogeochemistry is the study of the distribution of sulfur isotopes in biological and geological materials. In addition to its common isotope, 32S, sulfur has three rare stable isotopes: 34S, 36S, and 33S. The distribution of these isotopes in the environment is controlled by many biochemical and physical processes, including biological metabolisms, mineral formation processes, and atmospheric chemistry. Measuring the abundance of sulfur stable isotopes in natural materials, like bacterial cultures, minerals, or seawater, can reveal information about these processes both in the modern environment and over Earth history.
The disappearance of distinctive non-mass-dependent (NMD) sulphur isotope fractionations in sedimentary rocks deposited after about 2.4–2.3 Gyr ago16 (Fig. 2). Almost all fractionations among isotopes of a given element scale to differences in their masses; NMD fractionations deviate from this typical behaviour. The remarkable NMD signals are tied to photochemical reactions at short wavelengths involving gaseous sulphur compounds released from volcanoes into the atmosphere.