Stable isotope ratio

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The term stable isotope has a meaning similar to stable nuclide, but is preferably used when speaking of nuclides of a specific element. Hence, the plural form stable isotopes usually refers to isotopes of the same element. The relative abundance of such stable isotopes can be measured experimentally (isotope analysis), yielding an isotope ratio that can be used as a research tool. Theoretically, such stable isotopes could include the radiogenic daughter products of radioactive decay, used in radiometric dating. However, the expression stable-isotope ratio is preferably used to refer to isotopes whose relative abundances are affected by isotope fractionation in nature. This field is termed stable isotope geochemistry.

Contents

Stable-isotope ratios

Measurement of the ratios of naturally occurring stable isotopes (isotope analysis) plays an important role in isotope geochemistry, but stable isotopes (mostly hydrogen, carbon, nitrogen, oxygen and sulfur) are also finding uses in ecological and biological studies. Other workers have used oxygen isotope ratios to reconstruct historical atmospheric temperatures, making them important tools for paleoclimatology.

These isotope systems for lighter elements that exhibit more than one primordial isotope for each element have been under investigation for many years in order to study processes of isotope fractionation in natural systems. The long history of study of these elements is in part because the proportions of stable isotopes in these light and volatile elements is relatively easy to measure. However, recent advances in isotope ratio mass spectrometry (i.e. multiple-collector inductively coupled plasma mass spectrometry) now enable the measurement of isotope ratios in heavier stable elements, such as iron, copper, zinc, molybdenum, etc.

Applications

The variations in oxygen and hydrogen isotope ratios have applications in hydrology since most samples lie between two extremes, ocean water and Arctic/Antarctic snow. [1] Given a sample of water from an aquifer, and a sufficiently sensitive tool to measure the variation in the isotopic ratio of hydrogen in the sample, it is possible to infer the source, be it ocean water or precipitation seeping into the aquifer, and even to estimate the proportions from each source. [2] Stable isotopologues of water are also used in partitioning water sources for plant transpiration and groundwater recharge. [3] [4]

Another application is in paleotemperature measurement for paleoclimatology. For example, one technique is based on the variation in isotopic fractionation of oxygen by biological systems with temperature. [5] Species of Foraminifera incorporate oxygen as calcium carbonate in their shells. The ratio of the oxygen isotopes oxygen-16 and oxygen-18 incorporated into the calcium carbonate varies with temperature and the oxygen isotopic composition of the water. This oxygen remains "fixed" in the calcium carbonate when the foraminifera dies, falls to the sea bed, and its shell becomes part of the sediment. It is possible to select standard species of foraminifera from sections through the sediment column, and by mapping the variation in oxygen isotopic ratio, deduce the temperature that the Forminifera encountered during life if changes in the oxygen isotopic composition of the water can be constrained. [6] Paleotemperature relationships have also enabled isotope ratios from calcium carbonate in barnacle shells to be used to infer the movement and home foraging areas of the sea turtles and whales on which some barnacles grow. [7]

In ecology, carbon and nitrogen isotope ratios are widely used to determine the broad diets of many free-ranging animals. They have been used to determine the broad diets of seabirds, and to identify the geographical areas where individuals spend the breeding and non-breeding season in seabirds [8] and passerines. [9] Numerous ecological studies have also used isotope analyses to understand migration, food-web structure, diet, and resource use, [10] such as hydrogen isotopes to measure how much energy from stream-side trees supports fish growth in aquatic habitats. [11] Determining diets of aquatic animals using stable isotopes has been particularly common, as direct observations are difficult. [12] They also enable researchers to measure how human interactions with wildlife, such as fishing, may alter natural diets. [13]

In forensic science, research suggests that the variation in certain isotope ratios in drugs derived from plant sources ( cannabis , cocaine) can be used to determine the drug's continent of origin. [14]

In food science, stable isotope ratio analysis has been used to determine the composition of beer, [15] shoyu sauce [16] and dog food. [17]

Stable isotope ratio analysis also has applications in doping control, to distinguish between endogenous and exogenous (synthetic) sources of hormones. [18] [19]

The accurate measurement of stable isotope ratios relies on proper procedures of analysis, sample preparation and storage. [20]

Chondrite meteorites are classified using the oxygen isotope ratios. In addition, an unusual signature of carbon-13 confirms the non-terrestrial origin for organic compounds found in carbonaceous chondrites, as in the Murchison meteorite.

The uses of stable isotope ratios described above pertain to measurements of naturally occurring ratios. Scientific research also relies on the measurement of stable isotope ratios that have been artificially perturbed by the introduction of isotopically enriched material into the substance, process or system under study. Isotope dilution involves adding enriched stable isotope to a substance in order to quantify the amount of that substance by measuring the resulting isotope ratios. Isotope labeling uses enriched isotope to label a substance in order to trace its progress through, for example, a chemical reaction, metabolic pathway or biological system. Some applications of isotope labeling rely on the measurement of stable isotope ratios to accomplish this.

See also

Bibliography

Related Research Articles

<span class="mw-page-title-main">Calcium</span> Chemical element, symbol Ca and atomic number 20

Calcium is a chemical element; it has symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to its heavier homologues strontium and barium. It is the fifth most abundant element in Earth's crust, and the third most abundant metal, after iron and aluminium. The most common calcium compound on Earth is calcium carbonate, found in limestone and the fossilised remnants of early sea life; gypsum, anhydrite, fluorite, and apatite are also sources of calcium. The name derives from Latin calx "lime", which was obtained from heating limestone.

<span class="mw-page-title-main">Isotope analysis</span> Analytical technique used to study isotopes

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.

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.

Isotopic labeling is a technique used to track the passage of an isotope through chemical reaction, metabolic pathway, or a biological cell. The reactant is 'labeled' by replacing one or more specific atoms with their isotopes. The reactant is then allowed to undergo the reaction. The position of the isotopes in the products is measured to determine the sequence the isotopic atom followed in the reaction or the cell's metabolic pathway. The nuclides used in isotopic labeling may be stable nuclides or radionuclides. In the latter case, the labeling is called radiolabeling.

In chemistry, isotopologues are molecules that differ only in their isotopic composition. They have the same chemical formula and bonding arrangement of atoms, but at least one atom has a different number of neutrons than the parent.

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.

<span class="mw-page-title-main">Oxygen isotope ratio cycle</span> Cyclical variations in the ratio of the abundance of oxygen

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.

An isoscape is a geologic map of isotope distribution. It is a spatially explicit prediction of elemental isotope ratios (δ) that is produced by executing process-level models of elemental isotope fractionation or distribution in a geographic information system (GIS).

The environmental isotopes are a subset of isotopes, both stable and radioactive, which are the object of isotope geochemistry. They are primarily used as tracers to see how things move around within the ocean-atmosphere system, within terrestrial biomes, within the Earth's surface, and between these broad domains.

In geochemistry, paleoclimatology and paleoceanography δ18O or delta-O-18 is a measure of the 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.

Harmon Craig was an American geochemist who worked briefly for the University of Chicago (1951-1955) before spending the majority of his career at Scripps Institution of Oceanography (1955-2003).

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Thure E. Cerling is a Distinguished Professor of Geology and Geophysics and a Distinguished Professor of Biology at the University of Utah. Cerling is a leading expert in the evolution of modern landscapes including modern mammals and their associated grassland ecologies and stable isotope analyses of the atmosphere. Cerling lives in Salt Lake City, Utah.

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.

Hydrogen isotope biogeochemistry is the scientific study of biological, geological, and chemical processes in the environment using the distribution and relative abundance of hydrogen isotopes. There are two stable isotopes of hydrogen, protium 1H and deuterium 2H, which vary in relative abundance on the order of hundreds of permil. The ratio between these two species can be considered the hydrogen isotopic fingerprint of a substance. Understanding isotopic fingerprints and the sources of fractionation that lead to variation between them can be applied to address a diverse array of questions ranging from ecology and hydrology to geochemistry and paleoclimate reconstructions. Since specialized techniques are required to measure natural hydrogen isotope abundance ratios, the field of hydrogen isotope biogeochemistry provides uniquely specialized tools to more traditional fields like ecology and geochemistry.

Isotopic reference materials are compounds with well-defined isotopic compositions and are the ultimate sources of accuracy in mass spectrometric measurements of isotope ratios. Isotopic references are used because mass spectrometers are highly fractionating. As a result, the isotopic ratio that the instrument measures can be very different from that in the sample's measurement. Moreover, the degree of instrument fractionation changes during measurement, often on a timescale shorter than the measurement's duration, and can depend on the characteristics of the sample itself. By measuring a material of known isotopic composition, fractionation within the mass spectrometer can be removed during post-measurement data processing. Without isotope references, measurements by mass spectrometry would be much less accurate and could not be used in comparisons across different analytical facilities. Due to their critical role in measuring isotope ratios, and in part, due to historical legacy, isotopic reference materials define the scales on which isotope ratios are reported in the peer-reviewed scientific literature.

Vital effects are biological impacts on geochemical records. Many marine organisms, ranging from zooplankton to phytoplankton to reef builders, create shells or skeletons from chemical compounds dissolved in seawater. This process, which is also called biomineralization, therefore records the chemical signature of seawater during the time of shell formation. However, different species have different metabolism and physiology, causing them to create their shells in different ways. These biological distinctions cause species to record slightly different chemical signatures in their shells; these differences are known as vital effects.

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.

Global paleoclimate indicators are the proxies sensitive to global paleoclimatic environment changes. They are mostly derived from marine sediments. Paleoclimate indicators derived from terrestrial sediments, on the other hand, are commonly influenced by local tectonic movements and paleogeographic variations. Factors governing the earth climate system include plate tectonics, which controls the configuration of continents, the interplay between the atmosphere and the ocean, and the earth's orbital characteristics. Global paleoclimate indicators are established based on the information extracted from the analyses of geologic materials, including biological, geochemical and mineralogical data preserved in marine sediments. Indicators are generally grouped into three categories; paleontological, geochemical and lithological.

Isotope analysis has many applications in archaeology, from dating sites and artefacts, determination of past diets and migration patterns and for environmental reconstruction.

References

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