Isotopic signature

Isotopic signature

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An isotopic signature is a ratio of stable or unstable isotope
Isotope
Isotopes are variants of atoms of a particular chemical element, which have differing numbers of neutrons. Atoms of a particular element by definition must contain the same number of protons but may have a distinct number of neutrons which differs from atom to atom, without changing the designation...

s of particular elements found in an investigated material. The atomic mass
Atomic mass
The atomic mass is the mass of a specific isotope, most often expressed in unified atomic mass units. The atomic mass is the total mass of protons, neutrons and electrons in a single atom....

 of different isotopes affect their chemical kinetic
Chemical kinetics
Chemical kinetics, also known as reaction kinetics, is the study of rates of chemical processes. Chemical kinetics includes investigations of how different experimental conditions can influence the speed of a chemical reaction and yield information about the reaction's mechanism and transition...

 behavior, leading to natural isotope separation
Isotope separation
Isotope separation is the process of concentrating specific isotopes of a chemical element by removing other isotopes, for example separating natural uranium into enriched uranium and depleted uranium. This is a crucial process in the manufacture of uranium fuel for nuclear power stations, and is...

 processes.

Isotopic signature is identified by isotope analysis
Isotope analysis
Isotope analysis is the identification of isotopic signature, the distribution of certain stable isotopes and chemical elements within chemical compounds. This can be applied to a food web to make it possible to draw direct inferences regarding diet, trophic level, and subsistence...

.

Carbon isotopes



For example, different sources and sinks of methane
Methane
Methane is a chemical compound with the chemical formula . It is the simplest alkane, the principal component of natural gas, and probably the most abundant organic compound on earth. The relative abundance of methane makes it an attractive fuel...

 have different affinity for the 12C
Carbon-12
Carbon-12 is the more abundant of the two stable isotopes of the element carbon, accounting for 98.89% of carbon; it contains 6 protons, 6 neutrons, and 6 electrons....

 and 13C
Carbon-13
Carbon-13 is a natural, stable isotope of carbon and one of the environmental isotopes. It makes up about 1.1% of all natural carbon on Earth.- Detection by mass spectrometry :...

 isotopes, which allows distinguishing between different sources by the 13C/12C ratio in methane in the air. In geochemistry
Geochemistry
The field of geochemistry involves study of the chemical composition of the Earth and other planets, chemical processes and reactions that govern the composition of rocks, water, and soils, and the cycles of matter and energy that transport the Earth's chemical components in time and space, and...

, paleoclimatology
Paleoclimatology
Paleoclimatology is the study of changes in climate taken on the scale of the entire history of Earth. It uses a variety of proxy methods from the Earth and life sciences to obtain data previously preserved within rocks, sediments, ice sheets, tree rings, corals, shells and microfossils; it then...

 and paleoceanography
Paleoceanography
Paleoceanography is the study of the history of the oceans in the geologic past with regard to circulation, chemistry, biology, geology and patterns of sedimentation.- Source of information :...

 this ratio is called δ13C.

Similarly, carbon in inorganic carbonate
Carbonate
In chemistry, a carbonate is a salt of carbonic acid, characterized by the presence of the carbonate ion, . The name may also mean an ester of carbonic acid, an organic compound containing the carbonate group C2....

s shows little isotopic fractionation, while carbon in materials originated by photosynthesis
Photosynthesis
Photosynthesis is a chemical process that converts carbon dioxide into organic compounds, especially sugars, using the energy from sunlight. Photosynthesis occurs in plants, algae, and many species of bacteria, but not in archaea. Photosynthetic organisms are called photoautotrophs, since they can...

 is depleted of the heavier isotopes. In addition, there are two types of plants with different biochemical pathways; the C3 carbon fixation
C3 carbon fixation
carbon fixation is a metabolic pathway for carbon fixation in photosynthesis. This process converts carbon dioxide and ribulose bisphosphate into 3-phosphoglycerate through the following reaction:...

, where the isotope separation effect is more pronounced, C4 carbon fixation
C4 carbon fixation
C4 carbon fixation is one of three biochemical mechanisms, along with and CAM photosynthesis, used in carbon fixation. It is named for the 4-carbon molecule present in the first product of carbon fixation in these plants, in contrast to the 3-carbon molecule products in plants. fixation is an...

, where the heavier 13C is less depleted, and Crassulacean Acid Metabolism
Crassulacean acid metabolism
Crassulacean acid metabolism, also known as CAM photosynthesis, is a carbon fixation pathway that evolved in some plants as an adaptation to arid conditions. The stomata in the leaves remain shut during the day to reduce evapotranspiration, but open at night to collect carbon dioxide...

 (CAM) plants, where the effect is similar but less pronounced than with C4 plants. The different isotope ratios for the two kinds of plants propagate through the food chain
Food chain
A food web depicts feeding connections in an ecological community. Ecologists can broadly lump all life forms into one of two categories called trophic levels: 1) the autotrophs, and 2) the heterotrophs...

, thus it is possible to determine if the principal diet of a human or an animal consists primarily of C3 plants (rice
Rice
Rice is the seed of the monocot plants Oryza sativa or Oryza glaberrima . As a cereal grain, it is the most important staple food for a large part of the world's human population, especially in East Asia, Southeast Asia, South Asia, the Middle East, and the West Indies...

, wheat
Wheat
Wheat is a cereal grain, originally from the Levant region of the Near East, but now cultivated worldwide. In 2007 world production of wheat was 607 million tons, making it the third most-produced cereal after maize and rice...

, soybeans, potato
Potato
The potato is a starchy, tuberous crop from the perennial Solanum tuberosum of the Solanaceae family . The word potato may refer to the plant itself as well as the edible tuber. In the region of the Andes, there are some other closely related cultivated potato species...

es) or C4 plants (corn
Maize
Maize known in many English-speaking countries as corn or mielie/mealie, is a grain domesticated by indigenous peoples in Mesoamerica in prehistoric times. The leafy stalk produces ears which contain seeds called kernels. Though technically a grain, maize kernels are used in cooking as a vegetable...

, or corn-fed
Corn-fed
"Corn-fed" may refer to:* Corn-fed beef, beef from cattle that is raised on corn rather than pasture.* As a pejorative:** said of a woman, corn-fed means one who is strong and healthy, but lacks sophistication, typically an overweight girl or woman from the Midwestern United States.** said of a...

 beef
Beef
Beef is the culinary name for meat from bovines, especially domestic cattle. Beef can be harvested from cows, bulls, heifers or steers. It is one of the principal meats used in the cuisine of the Middle East , Australia, Argentina, Brazil, Europe and the United States, and is also important in...

) by isotope analysis
Isotope analysis
Isotope analysis is the identification of isotopic signature, the distribution of certain stable isotopes and chemical elements within chemical compounds. This can be applied to a food web to make it possible to draw direct inferences regarding diet, trophic level, and subsistence...

 of their flesh and bone collagen. 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 ‰


Limestone
Limestone
Limestone is a sedimentary rock composed largely of the minerals calcite and aragonite, which are different crystal forms of calcium carbonate . Many limestones are composed from skeletal fragments of marine organisms such as coral or foraminifera....

s formed by precipitation in sea
Sea
A sea generally refers to a large body of salt water, but the term is used in other contexts as well. Most commonly, it means a large expanse of saline water connected with an ocean, and is commonly used as a synonym for ocean...

s from the atmospheric carbon dioxide contain normal proportion of 13C. Conversely, calcite
Calcite
Calcite is a carbonate mineral and the most stable polymorph of calcium carbonate . The other polymorphs are the minerals aragonite and vaterite. Aragonite will change to calcite at 380-470°C, and vaterite is even less stable.-Properties:...

 found in salt dome
Salt dome
A salt dome is a type of structural dome formed when a thick bed of evaporite minerals found at depth intrudes vertically into surrounding rock strata, forming a diapir....

s originates from carbon dioxide formed by oxidation of petroleum
Petroleum
Petroleum or crude oil is a naturally occurring, flammable liquid consisting of a complex mixture of hydrocarbons of various molecular weights and other liquid organic compounds, that are found in geologic formations beneath the Earth's surface. Petroleum is recovered mostly through oil drilling...

, which due to its plant origin is 13C-depleted.

The 14C isotope
Carbon-14
Carbon-14, 14C, or radiocarbon, is a radioactive isotope of carbon with a nucleus containing 6 protons and 8 neutrons. Its presence in organic materials is the basis of the radiocarbon dating method pioneered by Willard Libby and colleagues , to date archaeological, geological, and hydrogeological...

 is important in distinguishing biosynthetized materials from man-made ones. Biogenic chemicals are derived from biospheric carbon, which contains 14C. Carbon in artificially made chemicals is usually derived from fossil fuel
Fossil fuel
Fossil fuels are fuels formed by natural processes such as anaerobic decomposition of buried dead organisms. The age of the organisms and their resulting fossil fuels is typically millions of years, and sometimes exceeds 650 million years...

s like coal
Coal
Coal is a combustible black or brownish-black sedimentary rock usually occurring in rock strata in layers or veins called coal beds or coal seams. The harder forms, such as anthracite coal, can be regarded as metamorphic rock because of later exposure to elevated temperature and pressure...

 or petroleum
Petroleum
Petroleum or crude oil is a naturally occurring, flammable liquid consisting of a complex mixture of hydrocarbons of various molecular weights and other liquid organic compounds, that are found in geologic formations beneath the Earth's surface. Petroleum is recovered mostly through oil drilling...

, where the 14C originally present has decayed below detectable limits. The amount of 14C currently present in a sample therefore indicates the proportion of carbon of biogenic origin.

Nitrogen isotopes


The ratio of 15N
Nitrogen
Nitrogen is a chemical element that has the symbol N, atomic number of 7 and atomic mass 14.00674 u. Elemental nitrogen is a colorless, odorless, tasteless, and mostly inert diatomic gas at standard conditions, constituting 78.08% by volume of Earth's atmosphere...

/14N presents a characteristic distinction between herbivore
Herbivore
Herbivores are organisms that are anatomically and physiologically adapted to eat plant-based foods. Herbivory is a form of consumption in which an organism principally eats autotrophs such as plants, algae and photosynthesizing bacteria. More generally, organisms that feed on autotrophs in...

s and carnivore
Carnivore
A carnivore meaning 'meat eater' is an organism that derives its energy and nutrient requirements from a diet consisting mainly or exclusively of animal tissue, whether through predation or scavenging...

s, as the movement up along the food chain
Food chain
A food web depicts feeding connections in an ecological community. Ecologists can broadly lump all life forms into one of two categories called trophic levels: 1) the autotrophs, and 2) the heterotrophs...

 tends to concentrate the 15N isotope, by 3-4‰ with each step of the food chain (terrestrial plants, with the exception of legumes, have an isotopic ratio of 2-6‰ of N). The tissues and hair
Hair
Hair is a filamentous biomaterial, that grows from follicles found in the dermis. Found exclusively in mammals, hair is one of the defining characteristics of the mammalian class....

 of vegans therefore contain significantly lower percentage of 15N than the bodies of people who eat mostly meat. Isotopic analysis of hair
Hair analysis
Hair analysis may refer to the chemical analysis of a hair sample, but can also refer to microscopic analysis or comparison. Chemical hair analysis may be considered for retrospective purposes when blood and urine are no longer expected to contain a particular contaminant, typically a year or less...

 is an important source of information for archaeologists
Archaeology
Archaeology, or archeology , is the study of human society, primarily through the recovery and analysis of the material culture and environmental data that they have left behind, which includes artifacts, architecture, biofacts and cultural landscapes...

, providing clues about the ancient diets; a terrestrial diet produces a different signature than a marine-based diet and this phenomenon has been used in analysing differing cultural attitudes to food sources.

Oxygen isotopes


Oxygen comes in three variants, but the 17O
Oxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...

 is so rare that it is very difficult to detect (~0.04% abundant). The ratio of 18O/16O in water depends on the amount of evaporation the water experienced (as 18O is heavier and therefore less likely to vaporize). As the vapor tension depends on the concentration of dissolved salts, the 18O
Oxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...

/16O ratio shows correlation on the salinity
Salinity
Salinity is the saltiness or dissolved salt content of a body of water. It is a general term used to describe the levels of different salts such as sodium chloride, magnesium and calcium sulfates, and bicarbonates...

 and temperature of water. As oxygen gets built into the shells of calcium carbonate
Calcium carbonate
Calcium carbonate is a chemical compound with the formula CaCO3. It is a common substance found in rocks in all parts of the world, and is the main component of shells of marine organisms, snails, coal balls, pearls, and eggshells. Calcium carbonate is the active ingredient in agricultural lime,...

 secreting organisms, such sediments prove a chronological record of temperature and salinity of the water in the area.

Oxygen isotope ratio in atmosphere varies predictably with time of year and geographic location; e.g. there is a 2% difference between 18O-rich precipitation in Montana and 18O-depleted precipitation in Florida Keys. This variability can be used for approximate determination of geographic location of origin of a material; e.g. it is possible to determine where a shipment of uranium oxide
Uranium oxide
Uranium oxide is an oxide of the element uranium.The metal uranium forms several oxides:* Uranium dioxide or uranium oxide * Uranium trioxide or uranium oxide...

 was produced. The rate of exchange of surface isotopes with the environment has to be taken in account.

Lead isotopes


Lead consists of four stable isotopes
Isotopes of lead
Lead has four stable isotopes: 204Pb, 206Pb, 207Pb, 208Pb. Lead-204 is entirely a primordial nuclide and is not a radiogenic nuclide. The three isotopes lead-206, lead-207, and lead-208 represent the ends of three decay chains called the uranium series , the actinium series, and the thorium...

: 204Pb, 206Pb, 207Pb, and 208Pb. Local variations in uranium
Uranium
Uranium is a silvery-white metallic chemical element in the actinide series of the periodic table, with atomic number 92. It is assigned the chemical symbol U. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons...

/thorium
Thorium
Thorium is a natural radioactive chemical element with the symbol Th and atomic number 90. It was discovered in 1828 and named after Thor, the Norse god of thunder....

/lead
Lead
Lead is a main-group element in the carbon group with the symbol Pb and atomic number 82. Lead is a soft, malleable poor metal. It is also counted as one of the heavy metals. Metallic lead has a bluish-white color after being freshly cut, but it soon tarnishes to a dull grayish color when exposed...

 content cause a wide location-specific variation of isotopic ratios for lead from different localities. Lead emitted to the atmosphere by industrial processes has an isotopic composition different from lead in minerals. Combustion of gasoline
Gasoline
Gasoline , or petrol , is a toxic, translucent, petroleum-derived liquid that is primarily used as a fuel in internal combustion engines. It consists mostly of organic compounds obtained by the fractional distillation of petroleum, enhanced with a variety of additives. Some gasolines also contain...

 with tetra-ethyl lead
Tetra-ethyl lead
Tetraethyllead , abbreviated TEL, is an organolead compound with the formula 4Pb. An inexpensive additive, its addition to gasoline from the 1920's allowed octane ratings and thus engine compression to be boosted significantly, increasing power and fuel economy...

 additive led to formation of ubiquitous micrometer-sized lead-rich particulates in car exhaust smoke
Smoke
Smoke is a collection of airborne solid and liquid particulates and gases emitted when a material undergoes combustion or pyrolysis, together with the quantity of air that is entrained or otherwise mixed into the mass. It is commonly an unwanted by-product of fires , but may also be used for pest...

; especially in urban areas the man-made lead particles are much more common than natural ones. The differences in isotopic content in particles found in objects can be used for approximate geolocation of the object's origin.

Radioactive isotopes


Hot particles, radioactive particles of nuclear fallout
Nuclear fallout
Fallout is the residual radioactive material propelled into the upper atmosphere following a nuclear blast, so called because it "falls out" of the sky after the explosion and shock wave have passed. It commonly refers to the radioactive dust and ash created when a nuclear weapon explodes...

 and radioactive waste
Radioactive waste
Radioactive wastes are wastes that contain radioactive material. Radioactive wastes are usually by-products of nuclear power generation and other applications of nuclear fission or nuclear technology, such as research and medicine...

, also exhibit distinct isotopic signatures. Their radionuclide composition (and thus their age and origin) can be determined by mass spectrometry
Mass spectrometry
Mass spectrometry is an analytical technique that measures the mass-to-charge ratio of charged particles.It is used for determining masses of particles, for determining the elemental composition of a sample or molecule, and for elucidating the chemical structures of molecules, such as peptides and...

 or by gamma spectrometry
Gamma ray spectrometer
A Gamma-Ray Spectrometer, or , is an instrument for measuring the distribution of the intensity of gamma radiation versus the energy of each photon....

. For example, particles generated by a nuclear blast contain detectable amounts of 60Co
Cobalt
Cobalt is a chemical element with symbol Co and atomic number 27. It is found naturally only in chemically combined form. The free element, produced by reductive smelting, is a hard, lustrous, silver-gray metal....

 and 152Eu
Europium
Europium is a chemical element with the symbol Eu and atomic number 63. It is named after the continent of Europe. It is a moderately hard silvery metal which readily oxidizes in air and water...

. The Chernobyl accident did not release these particles but did release 125Sb
Antimony
Antimony is a toxic chemical element with the symbol Sb and an atomic number of 51. A lustrous grey metalloid, it is found in nature mainly as the sulfide mineral stibnite...

 and 144Ce
Cerium
Cerium is a chemical element with the symbol Ce and atomic number 58. It is a soft, silvery, ductile metal which easily oxidizes in air. Cerium was named after the dwarf planet . Cerium is the most abundant of the rare earth elements, making up about 0.0046% of the Earth's crust by weight...

. Particles from underwater bursts will consist mostly of irradiated sea salts. Ratios of 152Eu
Europium
Europium is a chemical element with the symbol Eu and atomic number 63. It is named after the continent of Europe. It is a moderately hard silvery metal which readily oxidizes in air and water...

/155Eu, 154Eu/155Eu, and 238Pu
Plutonium
Plutonium is a transuranic radioactive chemical element with the chemical symbol Pu and atomic number 94. It is an actinide metal of silvery-gray appearance that tarnishes when exposed to air, forming a dull coating when oxidized. The element normally exhibits six allotropes and four oxidation...

/239Pu are also different for fusion and fission nuclear weapon
Nuclear weapon
A nuclear weapon is an explosive device that derives its destructive force from nuclear reactions, either fission or a combination of fission and fusion. Both reactions release vast quantities of energy from relatively small amounts of matter. The first fission bomb test released the same amount...

s, which allows identification of hot particles of unknown origin.

Forensics use


With the advent of stable isotope ratio mass spectrometry, isotopic signatures of materials find increasing use in forensics
Forensics
Forensic science is the application of a broad spectrum of sciences to answer questions of interest to a legal system. This may be in relation to a crime or a civil action...

, distinguishing the origin of otherwise similar materials and tracking the materials to their common source. For example the isotope signatures of plants can be to a degree influenced by the growth conditions, including moisture and nutrient availability. In case of synthetic materials, the signature is influenced by the conditions during the chemical reaction. The isotopic signature profiling is useful in cases where other kinds of profiling, e.g. characterization of impurities, are not optimal.

A study was published demonstrating the possibility of determination of the origin of a common brown PSA
Pressure sensitive adhesive
Pressure sensitive adhesive is adhesive which forms a bond when pressure is applied to marry the adhesive with the adherend...

 packaging tape by using the carbon, oxygen, and hydrogen isotopic signature of the backing polymer, additives, and adhesive
Adhesive
An adhesive, or glue, is a mixture in a liquid or semi-liquid state that adheres or bonds items together. Adhesives may come from either natural or synthetic sources. The types of materials that can be bonded are vast but they are especially useful for bonding thin materials...

.

Measurement of carbon isotopic ratios can be used for detection of adulteration of honey
Honey
Honey is a sweet food made by bees using nectar from flowers. The variety produced by honey bees is the one most commonly referred to and is the type of honey collected by beekeepers and consumed by humans...

. Addition of sugars originated from corn or sugar cane (C4 plants) skews the isotopic ratio of sugars present in honey, but does not influence the isotopic ratio of proteins; in an unadulterated honey the carbon isotopic ratios of sugars and proteins should match. As low as 7% level of addition can be detected.

Nuclear explosions form 10Be
Beryllium-10
Beryllium-10 is a radioactive isotope of beryllium. It is formed mainly by cosmic ray spallation. Be-10 has a half-life of 1.36 × 106 years, and decays by beta decay to stable Boron-10 with a maximum energy of 556.2 keV....

by a reaction of fast neutrons with 13C in the carbon dioxide in air. This is one of the historical indicators of past activity at nuclear test sites.

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