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Monday, September 14, 2015

Water


From Wikipedia, the free encyclopedia

Sunday, September 13, 2015

Carbon cycle

From Wikipedia, the free encyclopedia


This diagram of the fast carbon cycle shows the movement of carbon between land, atmosphere, and oceans in billions of tons of carbon per year. Yellow numbers are natural fluxes, red are human contributions in billions of tons of carbon per year. White numbers indicate stored carbon.

The carbon cycle is the biogeochemical cycle by which carbon is exchanged among the biosphere, pedosphere, geosphere, hydrosphere, and atmosphere of the Earth. Along with the nitrogen cycle and the water cycle, the carbon cycle comprises a sequence of events that are key to making the Earth capable of sustaining life; it describes the movement of carbon as it is recycled and reused throughout the biosphere.

The global carbon budget is the balance of the exchanges (incomes and losses) of carbon between the carbon reservoirs or between one specific loop (e.g., atmosphere <-> biosphere) of the carbon cycle. An examination of the carbon budget of a pool or reservoir can provide information about whether the pool or reservoir is functioning as a source or sink for carbon dioxide.

The carbon cycle was initially discovered by Joseph Priestley and Antoine Lavoisier, and popularized by Humphry Davy.[1]

Relevance for the global climate

Carbon-based molecules are crucial for life on Earth, because it is the main component of biological compounds. Carbon is also a major component of many minerals. Carbon also exists in various forms in the atmosphere. Carbon dioxide (CO2) is partly responsible for the greenhouse effect and is the most important human-contributed greenhouse gas.[2]

In the past two centuries, human activities have seriously altered the global carbon cycle, most significantly in the atmosphere. Although carbon dioxide levels have changed naturally over the past several thousand years, human emissions of carbon dioxide into the atmosphere exceed natural fluctuations.[2] Changes in the amount of atmospheric CO2 are considerably altering weather patterns and indirectly influencing oceanic chemistry. Records from ice cores have shown that, although global temperatures can change without changes in atmospheric CO2 levels, CO2 levels cannot change significantly without affecting global temperatures. Current carbon dioxide levels in the atmosphere exceed measurements from the last 420,000 years and levels are rising faster than ever recorded,[3] making it of critical importance to better understand how the carbon cycle works and what its effects are on the global climate.[2]

Main components

Carbon pools in the major reservoirs on earth.[2]
Pool Quantity (gigatons)
Atmosphere 720
Oceans (total) 38,400
Total inorganic 37,400
Total organic 1,000
Surface layer 670
Deep layer 36,730
Lithosphere
Sedimentary carbonates > 60,000,000
Kerogens 15,000,000
Terrestrial biosphere (total) 2,000
Living biomass 600 - 1,000
Dead biomass 1,200
Aquatic biosphere 1 - 2
Fossil fuels (total) 4,130
Coal 3,510
Oil 230
Gas 140
Other (peat) 250
The global carbon cycle is now usually divided into the following major reservoirs of carbon interconnected by pathways of exchange:
The carbon exchanges between reservoirs occur as the result of various chemical, physical, geological, and biological processes. The ocean contains the largest active pool of carbon near the surface of the Earth.[2] The natural flows of carbon between the atmosphere, ocean, and sediments is fairly balanced, so that carbon levels would be roughly stable without human influence.[4]

Atmosphere

Carbon in the earth's atmosphere exists in two main forms: carbon dioxide and methane. Both of these gases absorb and retain heat in the atmosphere and are partially responsible for the greenhouse effect. Methane produces a large greenhouse effect per volume as compared to carbon dioxide, but it exists in much lower concentrations and is more short-lived than carbon dioxide, making carbon dioxide the more important greenhouse gas of the two.[5]
Carbon dioxide leaves the atmosphere through photosynthesis, thus entering the terrestrial and oceanic biospheres. Carbon dioxide also dissolves directly from the atmosphere into bodies of water (oceans, lakes, etc.), as well as dissolving in precipitation as raindrops fall through the atmosphere. When dissolved in water, carbon dioxide reacts with water molecules and forms carbonic acid, which contributes to ocean acidity. It can then be absorbed by rocks through weathering. It also can acidify other surfaces it touches or be washed into the ocean.[6]

Human activity over the past two centuries has significantly increased the amount of carbon in the atmosphere, mainly in the form of carbon dioxide, both by modifying ecosystems' ability to extract carbon dioxide from the atmosphere and by emitting it directly, e.g., by burning fossil fuels and manufacturing concrete.[2]

Terrestrial biosphere

The terrestrial biosphere includes the organic carbon in all land-living organisms, both alive and dead, as well as carbon stored in soils. About 500 gigatons of carbon are stored above ground in plants and other living organisms,[4] while soil holds approximately 1,500 gigatons of carbon.[7] 
 
Most carbon in the terrestrial biosphere is organic carbon, while about a third of soil carbon is stored in inorganic forms, such as calcium carbonate.[8] Organic carbon is a major component of all organisms living on earth. Autotrophs extract it from the air in the form of carbon dioxide, converting it into organic carbon, while heterotrophs receive carbon by consuming other organisms.

A portable soil respiration system measuring soil CO2 flux

Because carbon uptake in the terrestrial biosphere is dependent on biotic factors, it follows a diurnal and seasonal cycle. In CO2 measurements, this cycle is often called a Keeling curve[citation needed]. It is strongest in the northern hemisphere, because this hemisphere has more land mass than the southern hemisphere and thus more room for ecosystems to absorb and emit carbon.

Carbon leaves the terrestrial biosphere in several ways and on different time scales. The combustion or respiration of organic carbon releases it rapidly into the atmosphere. It can also be exported into the oceans through rivers or remain sequestered in soils in the form of inert carbon. Carbon stored in soil can remain there for up to thousands of years before being washed into rivers by erosion or released into the atmosphere through soil respiration. Between 1989 and 2008 soil respiration increased by about 0.1% per year.[9] In 2008, the global total of CO2 released from the soil reached roughly 98 billion tonnes, about 10 times more carbon than humans are now putting into the atmosphere each year. There are a few plausible explanations for this trend, but the most likely explanation is that increasing temperatures have increased rates of decomposition of soil organic matter, which has increased the flow of CO2. The length of carbon sequestering in soil is dependent on local climatic conditions and thus changes in the course of climate change. From pre-industrial era to 2010, the terrestrial biosphere represented a net source of atmospheric CO2 prior to 1940, switching subsequently to a net sink.[10]

Oceans

Oceans contain the greatest quantity of actively cycled carbon in this world and are second only to the lithosphere in the amount of carbon they store.[2] The oceans' surface layer holds large amounts of dissolved organic carbon that is exchanged rapidly with the atmosphere. The deep layer's concentration of dissolved inorganic carbon (DIC) is about 15% higher than that of the surface layer.[11] DIC is stored in the deep layer for much longer periods of time.[4] Thermohaline circulation exchanges carbon between these two layers.[2]
Carbon enters the ocean mainly through the dissolution of atmospheric carbon dioxide, which is converted into carbonate. It can also enter the oceans through rivers as dissolved organic carbon. It is converted by organisms into organic carbon through photosynthesis and can either be exchanged throughout the food chain or precipitated into the ocean's deeper, more carbon rich layers as dead soft tissue or in shells as calcium carbonate. It circulates in this layer for long periods of time before either being deposited as sediment or, eventually, returned to the surface waters through thermohaline circulation.[4]

Oceanic absorption of CO2 is one of the most important forms of carbon sequestering limiting the human-caused rise of carbon dioxide in the atmosphere. However, this process is limited by a number of factors. Because the rate of CO2 dissolution in the ocean is dependent on the weathering of rocks and this process takes place slower than current rates of human greenhouse gas emissions, ocean CO2 uptake will decrease in the future.[2] CO2 absorption also makes water more acidic, which affects ocean biosystems. The projected rate of increasing oceanic acidity could slow the biological precipitation of calcium carbonates, thus decreasing the ocean's capacity to absorb carbon dioxide.[12][13]

Geological carbon cycle

The geologic component of the carbon cycle operates slowly in comparison to the other parts of the global carbon cycle. It is one of the most important determinants of the amount of carbon in the atmosphere, and thus of global temperatures.[14]

Most of the earth's carbon is stored inertly in the earth's lithosphere.[2] Much of the carbon stored in the earth's mantle was stored there when the earth formed.[15] Some of it was deposited in the form of organic carbon from the biosphere.[16] Of the carbon stored in the geosphere, about 80% is limestone and its derivatives, which form from the sedimentation of calcium carbonate stored in the shells of marine organisms. The remaining 20% is stored as kerogens formed through the sedimentation and burial of terrestrial organisms under high heat and pressure. Organic carbon stored in the geosphere can remain there for millions of years.[14]

Carbon can leave the geosphere in several ways. Carbon dioxide is released during the metamorphosis of carbonate rocks when they are subducted into the earth's mantle. This carbon dioxide can be released into the atmosphere and ocean through volcanoes and hotspots.[15] It can also be removed by humans through the direct extraction of kerogens in the form of fossil fuels. After extraction, fossil fuels are burned to release energy, thus emitting the carbon they store into the atmosphere.

Human influence

Human perturbation of the carbon cycle
Human activity since the industrial era has changed the balance in the natural carbon cycle. Units are in gigatons.[4]

Since the industrial revolution, human activity has modified the carbon cycle by changing its component's functions and directly adding carbon to the atmosphere.[2]

The largest and most direct human influence on the carbon cycle is through direct emissions from burning fossil fuels, which transfers carbon from the geosphere into the atmosphere. Humans also influence the carbon cycle indirectly by changing the terrestrial and oceanic biosphere.

Over the past several centuries, human-caused land use and land cover change (LUCC) has led to the loss of biodiversity, which lowers ecosystems' resilience to environmental stresses and decreases their ability to remove carbon from the atmosphere. More directly, it often leads to the release of carbon from terrestrial ecosystems into the atmosphere. Deforestation for agricultural purposes removes forests, which hold large amounts of carbon, and replaces them, generally with agricultural or urban areas. Both of these replacement land cover types store comparatively small amounts of carbon, so that the net product of the process is that more carbon stays in the atmosphere.

Other human-caused changes to the environment change ecosystems' productivity and their ability to remove carbon from the atmosphere. Air pollution, for example, damages plants and soils, while many agricultural and land use practices lead to higher erosion rates, washing carbon out of soils and decreasing plant productivity.

Higher temperatures and CO2 levels in the atmosphere increase decomposition rates in soil, thus returning CO2 stored in plant material more quickly to the atmosphere.[citation needed]

However, increased levels of CO2 in the atmosphere can also lead to higher gross primary production. It increases photosynthesis rates by allowing plants to more efficiently use water, because they no longer need to leave their stomata open for such long periods of time in order to absorb the same amount of carbon dioxide. This type of carbon dioxide fertilization affects mainly C3 plants, because C4 plants can already concentrate CO2 effectively.[citation needed]

Humans also affect the oceanic carbon cycle. Current trends in climate change lead to higher ocean temperatures, thus modifying ecosystems. Also, acid rain and polluted runoff from agriculture and industry change the ocean's chemical composition. Such changes can have dramatic effects on highly sensitive ecosystems such as coral reefs, thus limiting the ocean's ability to absorb carbon from the atmosphere on a regional scale and reducing oceanic biodiversity globally.

Saturday, September 12, 2015

Nuclear chemistry


From Wikipedia, the free encyclopedia

Nuclear chemistry is the subfield of chemistry dealing with radioactivity, nuclear processes, such as nuclear transmutation, and nuclear properties.

It is the chemistry of radioactive elements such as the actinides, radium and radon together with the chemistry associated with equipment (such as nuclear reactors) which are designed to perform nuclear processes. This includes the corrosion of surfaces and the behavior under conditions of both normal and abnormal operation (such as during an accident). An important area is the behavior of objects and materials after being placed into a nuclear waste storage or disposal site.

It includes the study of the chemical effects resulting from the absorption of radiation within living animals, plants, and other materials. The radiation chemistry controls much of radiation biology as radiation has an effect on living things at the molecular scale, to explain it another way the radiation alters the biochemicals within an organism, the alteration of the biomolecules then changes the chemistry which occurs within the organism, this change in chemistry then can lead to a biological outcome. As a result, nuclear chemistry greatly assists the understanding of medical treatments (such as cancer radiotherapy) and has enabled these treatments to improve.

It includes the study of the production and use of radioactive sources for a range of processes. These include radiotherapy in medical applications; the use of radioactive tracers within industry, science and the environment; and the use of radiation to modify materials such as polymers.[1]

It also includes the study and use of nuclear processes in non-radioactive areas of human activity. For instance, nuclear magnetic resonance (NMR) spectroscopy is commonly used in synthetic organic chemistry and physical chemistry and for structural analysis in macromolecular chemistry.

History

After the discovery of X-rays by Wilhelm Röntgen, many scientists began to work on ionizing radiation. One of these was Henri Becquerel, who investigated the relationship between phosphorescence and the blackening of photographic plates. When Becquerel (working in France) discovered that, with no external source of energy, the uranium generated rays which could blacken (or fog) the photographic plate, radioactivity was discovered. Marie Curie (working in Paris) and her husband Pierre Curie isolated two new radioactive elements from uranium ore. They used radiometric methods to identify which stream the radioactivity was in after each chemical separation; they separated the uranium ore into each of the different chemical elements that were known at the time, and measured the radioactivity of each fraction. They then attempted to separate these radioactive fractions further, to isolate a smaller fraction with a higher specific activity (radioactivity divided by mass). In this way, they isolated polonium and radium. It was noticed in about 1901 that high doses of radiation could cause an injury in humans. Henri Becquerel had carried a sample of radium in his pocket and as a result he suffered a high localised dose which resulted in a radiation burn[6] this injury resulted in the biological properties of radiation being investigated, which in time resulted in the development of medical treatments.

Ernest Rutherford, working in Canada and England, showed that radioactive decay can be described by a simple equation (a linear first degree derivative equation, now called first order kinetics), implying that a given radioactive substance has a characteristic "half-life" (the time taken for the amount of radioactivity present in a source to diminish by half). He also coined the terms alpha, beta and gamma rays, he converted nitrogen into oxygen, and most importantly he supervised the students who did the Geiger–Marsden experiment (gold leaf experiment) which showed that the 'plum pudding model' of the atom was wrong. In the plum pudding model, proposed by J. J. Thomson in 1904, the atom is composed of electrons surrounded by a 'cloud' of positive charge to balance the electrons' negative charge. To Rutherford, the gold foil experiment implied that the positive charge was confined to a very small nucleus leading first to the Rutherford model, and eventually to the Bohr model of the atom, where the positive nucleus is surrounded by the negative electrons.

In 1934 Marie Curie's daughter (Irène Joliot-Curie) and her husband were the first to create artificial radioactivity: they bombarded boron with alpha particles to make the neutron-poor isotope nitrogen-13; this isotope emitted positrons.[2] In addition, they bombarded aluminium and magnesium with neutrons to make new radioisotopes.

Main areas

Radiochemistry is the chemistry of radioactive materials, where radioactive isotopes of elements are used to study the properties and chemical reactions of non-radioactive isotopes (often within radiochemistry the absence of radioactivity leads to a substance being described as being inactive as the isotopes are stable).

Radiation chemistry

Radiation chemistry is the study of the chemical effects of radiation on matter; this is very different from radiochemistry as no radioactivity needs to be present in the material which is being chemically changed by the radiation. An example is the conversion of water into hydrogen gas and hydrogen peroxide.

Chemistry for nuclear power

Radiochemistry, radiation chemistry and nuclear chemical engineering play a very important role for uranium and thorium fuel precursors synthesis, starting from ores of these elements, fuel fabrication, coolant chemistry, fuel reprocessing, radioactive waste treatment and storage, monitoring of radioactive elements release during reactor operation and radioactive geological storage, etc. [3]

Study of nuclear reactions

A combination of radiochemistry and radiation chemistry is used to study nuclear reactions such as fission and fusion. Some early evidence for nuclear fission was the formation of a short-lived radioisotope of barium which was isolated from neutron irradiated uranium (139Ba, with a half-life of 83 minutes and 140Ba, with a half-life of 12.8 days, are major fission products of uranium). At the time, it was thought that this was a new radium isotope, as it was then standard radiochemical practice to use a barium sulfate carrier precipitate to assist in the isolation of radium.[7]. More recently, a combination of radiochemical methods and nuclear physics has been used to try to make new 'superheavy' elements; it is thought that islands of relative stability exist where the nuclides have half-lives of years, thus enabling weighable amounts of the new elements to be isolated. For more details of the original discovery of nuclear fission see the work of Otto Hahn.[4]

The nuclear fuel cycle

This is the chemistry associated with any part of the nuclear fuel cycle, including nuclear reprocessing. The fuel cycle includes all the operations involved in producing fuel, from mining, ore processing and enrichment to fuel production (Front end of the cycle). It also includes the 'in-pile' behaviour (use of the fuel in a reactor) before the back end of the cycle. The back end includes the management of the used nuclear fuel in either a spent fuel pool or dry storage, before it is disposed of into an underground waste store or reprocessed.

Normal and abnormal conditions

The nuclear chemistry associated with the nuclear fuel cycle can be divided into two main areas, one area is concerned with operation under the intended conditions while the other area is concerned with maloperation conditions where some alteration from the normal operating conditions has occurred or (more rarely) an accident is occurring.

Reprocessing

Law
In the United States it is normal to use fuel once in a power reactor before placing it in a waste store. The long term plan is currently to place the used civilian reactor fuel in a deep store. This non-reprocessing policy was started in March 1977 because of concerns about nuclear weapons proliferation. President [Jimmy Carter] issued a [Presidential directive] which indefinitely suspended the commercial reprocessing and recycling of plutonium in the United States. This directive was likely an attempt by the United States to lead other countries by example, but many other nations continue to reprocess spent nuclear fuels. The Russian government under President Vladimir Putin repealed a law which had banned the import of used nuclear fuel, which makes it possible for Russians to offer a reprocessing service for clients outside Russia (similar to that offered by BNFL).
PUREX chemistry
The current method of choice is to use the PUREX liquid-liquid extraction process which uses a tributyl phosphate/hydrocarbon mixture to extract both uranium and plutonium from nitric acid. This extraction is of the nitrate salts and is classed as being of a solvation mechanism. For example, the extraction of plutonium by an extraction agent (S) in a nitrate medium occurs by the following reaction.

Pu4+aq + 4NO3aq + 2Sorganic --> [Pu(NO3)4S2]organic

A complex bond is formed between the metal cation, the nitrates and the tributyl phosphate, and a model compound of a dioxouranium(VI) complex with two nitrates and two triethyl phosphates has been characterised by X-ray crystallography.[5]

When the nitric acid concentration is high the extraction into the organic phase is favoured, and when the nitric acid concentration is low the extraction is reversed (the organic phase is stripped of the metal). It is normal to dissolve the used fuel in nitric acid, after the removal of the insoluble matter the uranium and plutonium are extracted from the highly active liquor. It is normal to then back extract the loaded organic phase to create a medium active liquor which contains mostly uranium and plutonium with only small traces of fission products. This medium active aqueous mixture is then extracted again by tributyl phosphate/hydrocarbon to form a new organic phase, the metal bearing organic phase is then stripped of the metals to form an aqueous mixture of only uranium and plutonium. The two stages of extraction are used to improve the purity of the actinide product, the organic phase used for the first extraction will suffer a far greater dose of radiation. The radiation can degrade the tributyl phosphate into dibutyl hydrogen phosphate. The dibutyl hydrogen phosphate can act as an extraction agent for both the actinides and other metals such as ruthenium. The dibutyl hydrogen phosphate can make the system behave in a more complex manner as it tends to extract metals by an ion exchange mechanism (extraction favoured by low acid concentration), to reduce the effect of the dibutyl hydrogen phosphate it is common for the used organic phase to be washed with sodium carbonate solution to remove the acidic degradation products of the tributyl phosphate.
New methods being considered for future use
The PUREX process can be modified to make a UREX (URanium EXtraction) process which could be used to save space inside high level nuclear waste disposal sites, such as Yucca Mountain nuclear waste repository, by removing the uranium which makes up the vast majority of the mass and volume of used fuel and recycling it as reprocessed uranium.

The UREX process is a PUREX process which has been modified to prevent the plutonium being extracted. This can be done by adding a plutonium reductant before the first metal extraction step. In the UREX process, ~99.9% of the Uranium and >95% of Technetium are separated from each other and the other fission products and actinides. The key is the addition of acetohydroxamic acid (AHA) to the extraction and scrub sections of the process. The addition of AHA greatly diminishes the extractability of Plutonium and Neptunium, providing greater proliferation resistance than with the plutonium extraction stage of the PUREX process.

Adding a second extraction agent, octyl(phenyl)-N, N-dibutyl carbamoylmethyl phosphine oxide(CMPO) in combination with tributylphosphate, (TBP), the PUREX process can be turned into the TRUEX (TRansUranic EXtraction) process this is a process which was invented in the USA by Argonne National Laboratory, and is designed to remove the transuranic metals (Am/Cm) from waste. The idea is that by lowering the alpha activity of the waste, the majority of the waste can then be disposed of with greater ease. In common with PUREX this process operates by a solvation mechanism.

As an alternative to TRUEX, an extraction process using a malondiamide has been devised. The DIAMEX (DIAMideEXtraction) process has the advantage of avoiding the formation of organic waste which contains elements other than Carbon, Hydrogen, Nitrogen, and Oxygen. Such an organic waste can be burned without the formation of acidic gases which could contribute to acid rain. The DIAMEX process is being worked on in Europe by the French CEA. The process is sufficiently mature that an industrial plant could be constructed with the existing knowledge of the process. In common with PUREX this process operates by a solvation mechanism.[8][9]

Selective Actinide Extraction (SANEX). As part of the management of minor actinides it has been proposed that the lanthanides and trivalent minor actinides should be removed from the PUREX raffinate by a process such as DIAMEX or TRUEX. In order to allow the actinides such as americium to be either reused in industrial sources or used as fuel the lanthanides must be removed. The lanthanides have large neutron cross sections and hence they would poison a neutron driven nuclear reaction. To date the extraction system for the SANEX process has not been defined, but currently several different research groups are working towards a process. For instance the French CEA is working on a bis-triaiznyl pyridine (BTP) based process.

Other systems such as the dithiophosphinic acids are being worked on by some other workers.
This is the UNiversal EXtraction process which was developed in Russia and the Czech Republic, it is a process designed to remove all of the most troublesome (Sr, Cs and minor actinides) radioisotopes from the raffinates left after the extraction of uranium and plutonium from used nuclear fuel. [10][11] The chemistry is based upon the interaction of caesium and strontium with poly ethylene oxide (poly ethylene glycol) [12] and a cobalt carborane anion (known as chlorinated cobalt dicarbollide) . The actinides are extracted by CMPO, and the diluent is a polar aromatic such as nitrobenzene. Other dilents such as meta-nitrobenzotrifluoride and phenyl trifluoromethyl sulfone [13] have been suggested as well.

Absorption of fission products on surfaces

Another important area of nuclear chemistry is the study of how fission products interact with surfaces; this is thought to control the rate of release and migration of fission products both from waste containers under normal conditions and from power reactors under accident conditions. It is interesting to note that, like chromate and molybdate, the 99TcO4 anion can react with steel surfaces to form a corrosion resistant layer. In this way, these metaloxo anions act as anodic corrosion inhibitors. The formation of 99TcO2 on steel surfaces is one effect which will retard the release of 99Tc from nuclear waste drums and nuclear equipment which has been lost before decontamination (e.g. submarine reactors lost at sea). This 99TcO2 layer renders the steel surface passive, inhibiting the anodic corrosion reaction. The radioactive nature of technetium makes this corrosion protection impractical in almost all situations. It has also been shown that 99TcO4 anions react to form a layer on the surface of activated carbon (charcoal) or aluminium.[6][14]. A short review of the biochemical properties of a series of key long lived radioisotopes can be read on line.[15]

99Tc in nuclear waste may exist in chemical forms other than the 99TcO4 anion, these other forms have different chemical properties.[16]

Similarly, the release of iodine-131 in a serious power reactor accident could be retarded by absorption on metal surfaces within the nuclear plant.[7]

Spinout areas

Some methods first developed within nuclear chemistry and physics have become so widely used within chemistry and other physical sciences that they may be best thought of as separate from normal nuclear chemistry. For example, the isotope effect is used so extensively to investigate chemical mechanisms and the use of cosmogenic isotopes and long-lived unstable isotopes in geology that it is best to consider much of isotopic chemistry as separate from nuclear chemistry.

Kinetics (use within mechanistic chemistry)

The mechanisms of chemical reactions can be investigated by observing how the kinetics of a reaction is changed by making an isotopic modification of a substrate, known as the kinetic isotope effect. This is now a standard method in organic chemistry. Briefly, replacing normal hydrogen (protons) by deuterium within a molecule causes the molecular vibrational frequency of X-H (for example C-H, N-H and O-H) bonds to decrease, which leads to a decrease in vibrational zero-point energy. This can lead to a decrease in the reaction rate if the rate-determining step involves breaking a bond between hydrogen and another atom.[8] Thus, if the reaction changes in rate when protons are replaced by deuteriums, it is reasonable to assume that the breaking of the bond to hydrogen is part of the step which determines the rate.

Uses within geology, biology and forensic science

Cosmogenic isotopes are formed by the interaction of cosmic rays with the nucleus of an atom. These can be used for dating purposes and for use as natural tracers. In addition, by careful measurement of some ratios of stable isotopes it is possible to obtain new insights into the origin of bullets, ages of ice samples, ages of rocks, and the diet of a person can be identified from a hair or other tissue sample. (See Isotope geochemistry and Isotopic signature for further details).

Biology

Within living things, isotopic labels (both radioactive and nonradioactive) can be used to probe how the complex web of reactions which makes up the metabolism of an organism converts one substance to another. For instance a green plant uses light energy to convert water and carbon dioxide into glucose by photosynthesis. If the oxygen in the water is labeled, then the label appears in the oxygen gas formed by the plant and not in the glucose formed in the chloroplasts within the plant cells.
For biochemical and physiological experiments and medical methods, a number of specific isotopes have important applications.
  • Stable isotopes have the advantage of not delivering a radiation dose to the system being studied; however, a significant excess of them in the organ or organism might still interfere with its functionality, and the availability of sufficient amounts for whole-animal studies is limited for many isotopes. Measurement is also difficult, and usually requires mass spectrometry to determine how much of the isotope is present in particular compounds, and there is no means of localizing measurements within the cell.
  • H-2 (deuterium), the stable isotope of hydrogen, is a stable tracer, the concentration of which can be measured by mass spectrometry or NMR. It is incorporated into all cellular structures. Specific deuterated compounds can also be produced.
  • N-15, the stable isotope of nitrogen, has also been used. It is incorporated mainly into proteins.
  • Radioactive isotopes have the advantages of being detectable in very low quantities, in being easily measured by scintillation counting or other radiochemical methods, and in being localizable to particular regions of a cell, and quantifiable by autoradiography. Many compounds with the radioactive atoms in specific positions can be prepared, and are widely available commercially. In high quantities they require precautions to guard the workers from the effects of radiation—and they can easily contaminate laboratory glassware and other equipment. For some isotopes the half-life is so short that preparation and measurement is difficult.
By organic synthesis it is possible to create a complex molecule with a radioactive label that can be confined to a small area of the molecule. For short-lived isotopes such as 11C, very rapid synthetic methods have been developed to permit the rapid addition of the radioactive isotope to the molecule. For instance a palladium catalysed carbonylation reaction in a microfluidic device has been used to rapidly form amides[9] and it might be possible to use this method to form radioactive imaging agents for PET imaging.[17]
  • ³H, Tritium, the radioisotope of hydrogen, it available at very high specific activities, and compounds with this isotope in particular positions are easily prepared by standard chemical reactions such as hydrogenation of unsaturated precursors. The isotope emits very soft beta radiation, and can be detected by scintillation counting.
  • 11C, Carbon-11 is usually produced by cyclotron bombardment of 14N with protons. The resulting nuclear reaction is 14N(p,α)11C.[10] Additionally, Carbon-11 can also be made using a cyclotron; boron in the form of boric oxide is reacted with protons in a (p,n) reaction. Another alternative route is to react 10B with deuterons. By rapid organic synthesis, the 11C compound formed in the cyclotron is converted into the imaging agent which is then used for PET.
  • 14C, Carbon-14 can be made (as above), and it is possible to convert the target material into simple inorganic and organic compounds. In most organic synthesis work it is normal to try to create a product out of two approximately equal sized fragments and to use a convergent route, but when a radioactive label is added, it is normal to try to add the label late in the synthesis in the form of a very small fragment to the molecule to enable the radioactivity to be localised in a single group. Late addition of the label also reduces the number of synthetic stages where radioactive material is used.
  • 18F, fluorine-18 can be made by the reaction of neon with deuterons, 20Ne reacts in a (d,4He) reaction. It is normal to use neon gas with a trace of stable fluorine (19F2). The 19F2 acts as a carrier which increases the yield of radioactivity from the cyclotron target by reducing the amount of radioactivity lost by absorption on surfaces. However, this reduction in loss is at the cost of the specific activity of the final product.

Nuclear magnetic resonance (NMR)

NMR spectroscopy uses the net spin of nuclei in a substance upon energy absorption to identify molecules. This has now become a standard spectroscopic tool within synthetic chemistry. One major use of NMR is to determine the bond connectivity within an organic molecule.

NMR imaging also uses the net spin of nuclei (commonly protons) for imaging. This is widely used for diagnostic purposes in medicine, and can provide detailed images of the inside of a person without inflicting any radiation upon them. In a medical setting, NMR is often known simply as "magnetic resonance" imaging, as the word 'nuclear' has negative connotations for many people.

Israel and apartheid

From Wikipedia, the free encyclopedia https://en.wikipedia.org/wiki/Israel_and_apartheid A Palestinian c...