Actinides in the environment
Encyclopedia : A : AC : ACT : Actinides in the environment
This article about actinides in the environment is about the sources, environmental behaviour and effects of actinides in the environment. This is a subpage of Environmental radioactivity, if you want to read about the environmental aspects of radioisotopes other than the actinides then please go to this page. An set of overviews of some of the chemistry of uranium, neptunium, plutonium and americium in wastes can be seen at [link][link].
In general for the insoluble actinide oxides such as high fired uranium dioxide and MOX fuel if it is swallowed then it will pass through the digestive system with very little actinide dissolving. As the actinide oxide can not dissolve, it can not be absorbed into the body of the person or animal. With such an oxide the dose a person is committed to after a given intake of activity is higher for inhalation than for ingestion as the insoluble conpound will remain in the lungs, it will then irradiate the lung tissue.
Low fired oxides and soluble salts such as the nitrates can be absorbed with greater ease through the digestive system. So they are able to enter the blood-stream after being swallowed. If they are inhaled then it is possible for the solid to dissolve and leave the lungs. Hence the dose to the lungs will be lower for the soluble form.
These elements are not actinides -- they are both radioactive daughters from the decay of uranium. Aspects of their biology and environmental behaviour is discussed at radium in the environment.
In India a large amount of thorium ore can be found in the form of monazite in placer deposits of the Western and Eastern coastal dune sands, particulaly in the Tamil Nadu coastal areas. The residents of this area are exposed to a naturally occurring radiation dose ten times higher than the worldwide average.[link].
A good set of gamma activity maps for part of the USA can be found at http://www.csbsju.edu/MNradon/maps/surface.html.
Occurrence
Monazite, a rare-earth-and-thorium-phosphate mineral is the primary source of the world's thorium
Thorium is found in small amounts in most rocks and soils, where it is about three times more abundant than uranium, and is about as common as lead. Soil commonly contains an average of around 6 parts per million (ppm) of thorium. Thorium occurs in several minerals, the most common being the rare earth-thorium-phosphate mineral, monazite, which contains up to about 12% thorium oxide. There are substantial deposits in several countries. 232Th decays very slowly (its half-life is about three times the age of the earth) but other thorium isotopes occur in the thorium and uranium decay chains. Most of these are short-lived and hence much more radioactive than 232Th, though on a mass basis they are negligible.
Effects in humans
Thorium has been linked to liver cancer, in the past thoria (thorium dioxide) was used as a contrast agent for medical X-ray radioagraphy but its use has been discontinued. It was sold under the name Thorotrast.
Uranium in the environment
For details of uranium in the environment please see the main article at Uranium in the environment. Uranium is a natural metal which is widely found, it is present in almost all soils and it is more plentiful than antimony, beryllium, cadmium, gold, mercury, silver, or tungsten and is about as abundant as arsenic or molybdenum. Significant concentrations of uranium occur in some substances such as phosphate rock deposits, and minerals such as lignite, and monazite sands in uranium-rich ores (it is recovered commercially from these sources).
Seawater is very rich in uranium, as uranium(VI) forms soluble carbonate complexes; in the past the extraction of uranium from seawater has been considered as a means of obtaining the element.
Due to the very low specific activity of uranium the chemical effects of it upon living things can often outweigh the effects of its radioactivity.
Additional uranium has been added to the environment in some locations as a result of the nuclear fuel cycle and the use of depleted uranium in munitions.
Like plutonium, neptunium has a high affinity for soil.[link]
Sources
Bomb detonations
About 3.5 tons of plutonium have been released into the environment by atomic bomb tests. While this might sound a large amount it has only resulted in a very small dose to the majority of the humans on the earth. Overall the health effects of the fission products are far greater than the effects of the actinides released by a nuclear bomb detonation. The plutonium from the Pu fuel of the bomb is converted into a high fired oxide which is carried high into the air. It slowly falls to earth as global fallout and is not soluble, hence as a result it is difficult for this plutonium to be incorporated into an animal if taken by mouth. Much of this plutonium will become tightly absorbed onto sediments of lakes, rivers and oceans. However about 66% of the plutonium from a bomb explosion is formed by the neutron capture of uranium-238, this plutonium is not converted by the bomb into a high fired oxide as it is formed more slowly. As a result this formed plutonium is more soluble and more able to cause harm when it falls to earth. (source Radiochemistry and Nuclear Chemistry, G. Choppin, J-O. Liljenzin and J. Rydberg, 3rd Ed, ButterworthHeinemann, 2002)
Some of the plutonium can be desposited close to the point of detonation. The glassy trinitite formed by the first atom bomb has been examined to determine what actinides and other radioisotopes it contained. A recent paper (P.P. Parekh, T.M. Semkow, M.A. Torres, D.K. Haines, J.M. Cooper, P.M. Rosenberg and M.E. Kitto, Journal of Environmental Radioactivity, 2006, 85, 103-120) reports the levels of long lived radioisotopes in the trinitite. The trinitite was formed from feldspar and quartz which were melted by the heat. Two samples of trinitite were used, the first (left hand side bars) was taken from between 40 and 65 meters of ground zero while the other sample was taken from further away from the ground zero point.
Levels of radioactivity in the trinity glass from two different samples as measured by gamma spectrscopy on lumps of the glass. The americium content is the current content while all the other isotopes have been back calculated to shortly after the moment of detonation.
The 152Eu and 154Eu was mainly formed by the neutron activation of the europium in the soil, it is clear that the level of radioactivity for these isotopes is highest where the neutron dose to the soil was larger. Some of the 60Co is generated by activation of the cobalt in the soil, but some was also generated by the activation of the cobalt in the steel (100 foot) tower. This 60Co from the tower would have been scattered over the site reducing the difference in the soil levels.
The 133Ba and 241Am are due to the neutron activation of barium and plutonium inside the bomb. The barium was present in the form of the nitrate in the chemical explosives used while the plutonium was the fissile fuel used.
It is interesting to note that the 137Cs level is higher in the sample which was further away from the ground zero point, this is through to be because the precursors to the 137Cs (137I and 137Xe) and the cesium to a lesser degree are volitile. The natural radioisotopes in the glass are about the same in both locations.
In this paper a sample of the glass was digested and the plutonium extracted from it, the mass ratio of the isotopes was calculated from the radiometric measurements. In light green the isotopic siganture for the plutonium used for making the bomb is shown, and on the right in dark green the signature of the plutonium in the trinity glass is shown. It is very clear that 238Pu and 241Pu were generated during the detonation, it is reasonable to conclude that some 240Pu was formed during the detonation.
Isotropic signatures of the plutonium before and after the detonation.
Bomb safety trials
One form of release of plutionium into the environment has been safety trials in these experiments nuclear bombs have been subjected to simulated accidents or have been detonated with an abnormal initiation of the chemical explosives. An abnormal implosion will result in a compression of the pit which is less uniform and smaller than the designed compression in the device. Such an abnormal implosion could result from an accident which triggers one or more of the detonators which trigger the chemical explosive charges.
As a result of these experiments (where no or very little nuclear fission occurs) plutonium metal has been scattered around near the site of the experiemnt. While some of these tests have been done inside holes in the ground, other such tests were conducted in open air. A paper on the radioisotopes left on an island by the French nuclear bombs tests of the 20th centry has been printed by the IAEA and a section of this report deals with plutonium contamination resulting from such tests.[link]
Other related trials were conducted at Maralinga, South Australia here both normal bomb detonations and "safety trials" have been conducted. While the activity from the fission products has decayed away almost totally (as of 2006) the plutonium remains active. A report (warning it is jolly big) can be read at [link] while a smaller report can be seen at [link].
Atomic batteries
Space
Diagram of an RTG used on the Cassini probe
Another potential source of plutonium being introduced into the environment is the reentry of artificial satellites containing atomic batteries. There have been several such incidents, the most prominent being the Apollo 13 mission. The Apollo Lunar Surface Experiment Package carried on the Lunar Module re-entered the atmosphere over the South Pacific. Many atomic batteries have been of the Radioisotope thermoelectric generator (RTG) type.
Image of (mostly) thermally isolated, RTG pellet glowing red hot due to incandescence.
Chain reactions do not occur inside RTGs, so such a nuclear meltdown is impossible. In fact, some RTGs are designed so that fission does not occur at all; rather, forms of radioactive decay which cannot trigger other radioactive decays are used instead. As a result, the fuel in an RTG is consumed much more slowly and much less power is produced.
RTGs are still a potential source of radioactive contamination: if the container holding the fuel leaks, the radioactive material will contaminate the environment. The main concern is that if an accident were to occur during launch or a subsequent passage of a spacecraft close to Earth, harmful material could be released into the atmosphere. However, this event is extremely unlikely with current RTG cask designs.
In order to minimise the risk of the radioactive material being released, the fuel is typically stored in individual modular units with their own heat shielding. They are surrounded by a layer of iridium metal and encased in high-strength graphite blocks. These two materials are corrosion and heat-resistant. Surrounding the graphite blocks is an aeroshell, designed to protect the entire assembly against the heat of reentering the earth's atmosphere. The plutonium fuel is also stored in a ceramic form that is heat-resistant, minimising the risk of vaporization and aerosolization. The ceramic is also highly insoluble.
The US Department of Energy has conducted seawater tests and determined that the graphite casing, which was designed to withstand reentry, is stable and no release of plutonium should occur. Subsequent investigations have found no increase in the natural background radiation in the area. The Apollo 13 accident represents an extreme scenario due to the high re-entry velocities of the craft returning from cislunar space. This accident has served to validate the design of later-generation RTGs as highly safe.
The Plutonium-238 used in RTGs has a half-life of 88 years, as opposed to the plutonium-239 used in nuclear weapons and reactors, which has a half-life of 24,100 years.
Pacemakers
Some heart pacemakers which are powered by RTGs using 238Pu have been made.Nuclear fuel cycle
Plutonium has been released into the environment in aqueous solution from nuclear reprocessing and uranium enrichment plants. The chemistry of this plutonium is different to that of the metal oxides formed from nuclear bomb detonations.
One example of a site (military not civil) where plutonium entered the soil is Rocky Flats where in the recent past XANES (a X-ray spectrscopy) has been used to determine the chemical nature of the plutonium in the soil.[link]. The XANES was used to determine the oxidation state of the plutonium, while EXAFS was used to investigate the strucutre of the plutonium compound present in the soil and concrete.[link]
The XANES experiments done on plutonium in soil, concrete and standards of the different oxidation states.
Chernobyl
Because plutonium oxide is very involatile, most of the plutonium in the reactor was not released during the fire. However that which was released can be measured. V.I. Yoschenko et. al. reported that grass and forest fires can make the cesium, strontium and plutonium become mobile in the air again. (Journal of Environmental Radioactivity, 2006, 86, 143-163.) As an experiment fires were set and the levels of the radioactivity in the air downwind of these fires was measured.
The rate of delivery of radioactivity which has been made mobile by a grass fire.
Nuclear crime
One case exists of a German man who attempted to poison his ex-wife with plutonium stolen from WAK (Wiederaufbereitungsanlage Karlsruhe). WAK was a small scale reprocessing plant where he worked. He did not steal a large amount of plutonium, just some rags used for wiping surfaces and a small amount of liquid waste. This man was sent to prison for his crime. [link] [link] At least two people (besides the criminal) were contaminated by the plutonium. [link]. Two flats in Rhineland-Palatinate were contaminated. These were later cleaned at a cost of two million euro.
For photographs of the case and details of other nuclear crimes see [link] which was presented by a worker at the ITU.
The details of how the two flats were cleaned has been recorded [link]. The flats were in a place called Landau.
Environmental chemistry
Plutonium like other actinides readily forms a dioxide plutonyl core (PuO2). In the environment, this plutonyl core readily complexes with carbonate as well as other oxygen moeities (OH-, NO2-, NO3-, and SO4-2) to form charged complexes which can be readily mobile with low affinities to soil.
- PuO2(CO3)1-2
- PuO2(CO3)2-4
- PuO2(CO3)3-6
PuO2 formed from neutralizing highly acidic nitric acid solutions tends to form polymeric PuO2 which is resistant to complexation. Plutonium also readily shifts valences between the +3, +4, +5 and +6 states. It is common for some fraction of plutonium in solution to exist in all of these states in equilibrium.
Plutonium is known to bind to soil particles very strongly, see above for a X-ray spectrscopic study of plutonium in soil and concrete. While cesium has very different chemistry to the actinides, it is well known that both cesium and many of the actinides bind strongly to the minerals in soil. Hence it has been possible to use 134Cs labeled soil to study the migration of Pu and Cs is soils. It has been shown that colloidal transport processes control the migration of Cs (and will control the migration of Pu) in the soil at the Waste Isolation Pilot Plant according to R.D. Whicker and S.A. Ibrahim, Journal of Environmental Radioactivity, 2006, 88, 171-188.Biology
Plutonium in humans is transported in the transferrin based iron(III) transport system and then is stored in the liver in the iron store (ferritin), after an exposure to plutonium it is important to rapidly inject the subject with the calcium complex[link] of DTPA[link] [link]. This antidote is useful for a single one off exposure such as that which would occur if a glove box worker was to cut their hand with a Pu contaminated object. The calcium complex has faster metal binding kinetics than the zinc complex but if the calcium complex is used for a long time it tends to remove important minerals from the person. The zinc complex is less able to cause these effects.
Americium often enters landfills from discarded smoke detectors. The rules associated with the disposal of smoke detectors are very relaxed in most municipalities. For instance in the UK it is permissible to dispose of an americium containing smoke detector by placing it in the dustbin with normal household rubbish, but each dustbin worth of rubbish is limited to only containing one smoke detector.
In France a truck transporting 900 smoke detectors has been reported to have caught fire, it is claimed that this lead to a release of americium into the environment.[link]
Humans have become contaminated with americium, the worst case was that of Harold McCluskey. It is interesting to note that Harold McCluskey did not die of cancer but of heart disease (which he had before the accident). It is likely that the medical care which he was given saved his life, it should be noted that due to the difference in the chemistry of americium(the +3 oxidation state is the very stable) to plutonium (where the +4 state can form in the human body) the americium has very different biochemistry to plutonium.
Further reading
Radioactivity, Ionizing Radiation and Nuclear Energy, by J. Hala and J.D. Navratil
Environmental science
Atmospheric sciences | Ecology | Geosciences | Soil science| Hydrology
Related fields: Biology | Chemistry | Environmental design | Environmental economics | Environmental ethics | Environmental law | Physics
Environmental technology
From Wikipedia, the Free Encyclopedia. Original article here. Support Wikipedia by contributing or donating.
All text is available under the terms of the GNU Free Documentation License See Wikipedia Copyrights for details.
These elements are not actinides -- they are both radioactive daughters from the decay of uranium. Aspects of their biology and environmental behaviour is discussed at radium in the environment.
In India a large amount of thorium ore can be found in the form of monazite in placer deposits of the Western and Eastern coastal dune sands, particulaly in the Tamil Nadu coastal areas. The residents of this area are exposed to a naturally occurring radiation dose ten times higher than the worldwide average.[link].
A good set of gamma activity maps for part of the USA can be found at http://www.csbsju.edu/MNradon/maps/surface.html.
Occurrence
Monazite, a rare-earth-and-thorium-phosphate mineral is the primary source of the world's thorium
Thorium is found in small amounts in most rocks and soils, where it is about three times more abundant than uranium, and is about as common as lead. Soil commonly contains an average of around 6 parts per million (ppm) of thorium. Thorium occurs in several minerals, the most common being the rare earth-thorium-phosphate mineral, monazite, which contains up to about 12% thorium oxide. There are substantial deposits in several countries. 232Th decays very slowly (its half-life is about three times the age of the earth) but other thorium isotopes occur in the thorium and uranium decay chains. Most of these are short-lived and hence much more radioactive than 232Th, though on a mass basis they are negligible.
Effects in humans
Thorium has been linked to liver cancer, in the past thoria (thorium dioxide) was used as a contrast agent for medical X-ray radioagraphy but its use has been discontinued. It was sold under the name Thorotrast.
Uranium in the environment
For details of uranium in the environment please see the main article at Uranium in the environment. Uranium is a natural metal which is widely found, it is present in almost all soils and it is more plentiful than antimony, beryllium, cadmium, gold, mercury, silver, or tungsten and is about as abundant as arsenic or molybdenum. Significant concentrations of uranium occur in some substances such as phosphate rock deposits, and minerals such as lignite, and monazite sands in uranium-rich ores (it is recovered commercially from these sources).
Seawater is very rich in uranium, as uranium(VI) forms soluble carbonate complexes; in the past the extraction of uranium from seawater has been considered as a means of obtaining the element.
Due to the very low specific activity of uranium the chemical effects of it upon living things can often outweigh the effects of its radioactivity.
Additional uranium has been added to the environment in some locations as a result of the nuclear fuel cycle and the use of depleted uranium in munitions.
Like plutonium, neptunium has a high affinity for soil.[link]
Sources
Bomb detonations
About 3.5 tons of plutonium have been released into the environment by atomic bomb tests. While this might sound a large amount it has only resulted in a very small dose to the majority of the humans on the earth. Overall the health effects of the fission products are far greater than the effects of the actinides released by a nuclear bomb detonation. The plutonium from the Pu fuel of the bomb is converted into a high fired oxide which is carried high into the air. It slowly falls to earth as global fallout and is not soluble, hence as a result it is difficult for this plutonium to be incorporated into an animal if taken by mouth. Much of this plutonium will become tightly absorbed onto sediments of lakes, rivers and oceans. However about 66% of the plutonium from a bomb explosion is formed by the neutron capture of uranium-238, this plutonium is not converted by the bomb into a high fired oxide as it is formed more slowly. As a result this formed plutonium is more soluble and more able to cause harm when it falls to earth. (source Radiochemistry and Nuclear Chemistry, G. Choppin, J-O. Liljenzin and J. Rydberg, 3rd Ed, ButterworthHeinemann, 2002)
Some of the plutonium can be desposited close to the point of detonation. The glassy trinitite formed by the first atom bomb has been examined to determine what actinides and other radioisotopes it contained. A recent paper (P.P. Parekh, T.M. Semkow, M.A. Torres, D.K. Haines, J.M. Cooper, P.M. Rosenberg and M.E. Kitto, Journal of Environmental Radioactivity, 2006, 85, 103-120) reports the levels of long lived radioisotopes in the trinitite. The trinitite was formed from feldspar and quartz which were melted by the heat. Two samples of trinitite were used, the first (left hand side bars) was taken from between 40 and 65 meters of ground zero while the other sample was taken from further away from the ground zero point.
Levels of radioactivity in the trinity glass from two different samples as measured by gamma spectrscopy on lumps of the glass. The americium content is the current content while all the other isotopes have been back calculated to shortly after the moment of detonation.
The 152Eu and 154Eu was mainly formed by the neutron activation of the europium in the soil, it is clear that the level of radioactivity for these isotopes is highest where the neutron dose to the soil was larger. Some of the 60Co is generated by activation of the cobalt in the soil, but some was also generated by the activation of the cobalt in the steel (100 foot) tower. This 60Co from the tower would have been scattered over the site reducing the difference in the soil levels.
The 133Ba and 241Am are due to the neutron activation of barium and plutonium inside the bomb. The barium was present in the form of the nitrate in the chemical explosives used while the plutonium was the fissile fuel used.
It is interesting to note that the 137Cs level is higher in the sample which was further away from the ground zero point, this is through to be because the precursors to the 137Cs (137I and 137Xe) and the cesium to a lesser degree are volitile. The natural radioisotopes in the glass are about the same in both locations.
In this paper a sample of the glass was digested and the plutonium extracted from it, the mass ratio of the isotopes was calculated from the radiometric measurements. In light green the isotopic siganture for the plutonium used for making the bomb is shown, and on the right in dark green the signature of the plutonium in the trinity glass is shown. It is very clear that 238Pu and 241Pu were generated during the detonation, it is reasonable to conclude that some 240Pu was formed during the detonation.
Isotropic signatures of the plutonium before and after the detonation.
Bomb safety trials
One form of release of plutionium into the environment has been safety trials in these experiments nuclear bombs have been subjected to simulated accidents or have been detonated with an abnormal initiation of the chemical explosives. An abnormal implosion will result in a compression of the pit which is less uniform and smaller than the designed compression in the device. Such an abnormal implosion could result from an accident which triggers one or more of the detonators which trigger the chemical explosive charges.
As a result of these experiments (where no or very little nuclear fission occurs) plutonium metal has been scattered around near the site of the experiemnt. While some of these tests have been done inside holes in the ground, other such tests were conducted in open air. A paper on the radioisotopes left on an island by the French nuclear bombs tests of the 20th centry has been printed by the IAEA and a section of this report deals with plutonium contamination resulting from such tests.[link]
Other related trials were conducted at Maralinga, South Australia here both normal bomb detonations and "safety trials" have been conducted. While the activity from the fission products has decayed away almost totally (as of 2006) the plutonium remains active. A report (warning it is jolly big) can be read at [link] while a smaller report can be seen at [link].
Atomic batteries
Space
Diagram of an RTG used on the Cassini probe
Another potential source of plutonium being introduced into the environment is the reentry of artificial satellites containing atomic batteries. There have been several such incidents, the most prominent being the Apollo 13 mission. The Apollo Lunar Surface Experiment Package carried on the Lunar Module re-entered the atmosphere over the South Pacific. Many atomic batteries have been of the Radioisotope thermoelectric generator (RTG) type.
Image of (mostly) thermally isolated, RTG pellet glowing red hot due to incandescence.
Chain reactions do not occur inside RTGs, so such a nuclear meltdown is impossible. In fact, some RTGs are designed so that fission does not occur at all; rather, forms of radioactive decay which cannot trigger other radioactive decays are used instead. As a result, the fuel in an RTG is consumed much more slowly and much less power is produced.
RTGs are still a potential source of radioactive contamination: if the container holding the fuel leaks, the radioactive material will contaminate the environment. The main concern is that if an accident were to occur during launch or a subsequent passage of a spacecraft close to Earth, harmful material could be released into the atmosphere. However, this event is extremely unlikely with current RTG cask designs.
In order to minimise the risk of the radioactive material being released, the fuel is typically stored in individual modular units with their own heat shielding. They are surrounded by a layer of iridium metal and encased in high-strength graphite blocks. These two materials are corrosion and heat-resistant. Surrounding the graphite blocks is an aeroshell, designed to protect the entire assembly against the heat of reentering the earth's atmosphere. The plutonium fuel is also stored in a ceramic form that is heat-resistant, minimising the risk of vaporization and aerosolization. The ceramic is also highly insoluble.
The US Department of Energy has conducted seawater tests and determined that the graphite casing, which was designed to withstand reentry, is stable and no release of plutonium should occur. Subsequent investigations have found no increase in the natural background radiation in the area. The Apollo 13 accident represents an extreme scenario due to the high re-entry velocities of the craft returning from cislunar space. This accident has served to validate the design of later-generation RTGs as highly safe.
The Plutonium-238 used in RTGs has a half-life of 88 years, as opposed to the plutonium-239 used in nuclear weapons and reactors, which has a half-life of 24,100 years.
Pacemakers
Some heart pacemakers which are powered by RTGs using 238Pu have been made.Nuclear fuel cycle
Plutonium has been released into the environment in aqueous solution from nuclear reprocessing and uranium enrichment plants. The chemistry of this plutonium is different to that of the metal oxides formed from nuclear bomb detonations.
One example of a site (military not civil) where plutonium entered the soil is Rocky Flats where in the recent past XANES (a X-ray spectrscopy) has been used to determine the chemical nature of the plutonium in the soil.[link]. The XANES was used to determine the oxidation state of the plutonium, while EXAFS was used to investigate the strucutre of the plutonium compound present in the soil and concrete.[link]
The XANES experiments done on plutonium in soil, concrete and standards of the different oxidation states.
Chernobyl
Because plutonium oxide is very involatile, most of the plutonium in the reactor was not released during the fire. However that which was released can be measured. V.I. Yoschenko et. al. reported that grass and forest fires can make the cesium, strontium and plutonium become mobile in the air again. (Journal of Environmental Radioactivity, 2006, 86, 143-163.) As an experiment fires were set and the levels of the radioactivity in the air downwind of these fires was measured.
The rate of delivery of radioactivity which has been made mobile by a grass fire.
Nuclear crime
One case exists of a German man who attempted to poison his ex-wife with plutonium stolen from WAK (Wiederaufbereitungsanlage Karlsruhe). WAK was a small scale reprocessing plant where he worked. He did not steal a large amount of plutonium, just some rags used for wiping surfaces and a small amount of liquid waste. This man was sent to prison for his crime. [link] [link] At least two people (besides the criminal) were contaminated by the plutonium. [link]. Two flats in Rhineland-Palatinate were contaminated. These were later cleaned at a cost of two million euro.
For photographs of the case and details of other nuclear crimes see [link] which was presented by a worker at the ITU.
The details of how the two flats were cleaned has been recorded [link]. The flats were in a place called Landau.
Environmental chemistry
Plutonium like other actinides readily forms a dioxide plutonyl core (PuO2). In the environment, this plutonyl core readily complexes with carbonate as well as other oxygen moeities (OH-, NO2-, NO3-, and SO4-2) to form charged complexes which can be readily mobile with low affinities to soil.
- PuO2(CO3)1-2
- PuO2(CO3)2-4
- PuO2(CO3)3-6
PuO2 formed from neutralizing highly acidic nitric acid solutions tends to form polymeric PuO2 which is resistant to complexation. Plutonium also readily shifts valences between the +3, +4, +5 and +6 states. It is common for some fraction of plutonium in solution to exist in all of these states in equilibrium.
Plutonium is known to bind to soil particles very strongly, see above for a X-ray spectrscopic study of plutonium in soil and concrete. While cesium has very different chemistry to the actinides, it is well known that both cesium and many of the actinides bind strongly to the minerals in soil. Hence it has been possible to use 134Cs labeled soil to study the migration of Pu and Cs is soils. It has been shown that colloidal transport processes control the migration of Cs (and will control the migration of Pu) in the soil at the Waste Isolation Pilot Plant according to R.D. Whicker and S.A. Ibrahim, Journal of Environmental Radioactivity, 2006, 88, 171-188.Biology
Plutonium in humans is transported in the transferrin based iron(III) transport system and then is stored in the liver in the iron store (ferritin), after an exposure to plutonium it is important to rapidly inject the subject with the calcium complex[link] of DTPA[link] [link]. This antidote is useful for a single one off exposure such as that which would occur if a glove box worker was to cut their hand with a Pu contaminated object. The calcium complex has faster metal binding kinetics than the zinc complex but if the calcium complex is used for a long time it tends to remove important minerals from the person. The zinc complex is less able to cause these effects.
Americium often enters landfills from discarded smoke detectors. The rules associated with the disposal of smoke detectors are very relaxed in most municipalities. For instance in the UK it is permissible to dispose of an americium containing smoke detector by placing it in the dustbin with normal household rubbish, but each dustbin worth of rubbish is limited to only containing one smoke detector.
In France a truck transporting 900 smoke detectors has been reported to have caught fire, it is claimed that this lead to a release of americium into the environment.[link]
Humans have become contaminated with americium, the worst case was that of Harold McCluskey. It is interesting to note that Harold McCluskey did not die of cancer but of heart disease (which he had before the accident). It is likely that the medical care which he was given saved his life, it should be noted that due to the difference in the chemistry of americium(the +3 oxidation state is the very stable) to plutonium (where the +4 state can form in the human body) the americium has very different biochemistry to plutonium.
Further reading
Radioactivity, Ionizing Radiation and Nuclear Energy, by J. Hala and J.D. Navratil
Environmental science
Atmospheric sciences | Ecology | Geosciences | Soil science| Hydrology
Related fields: Biology | Chemistry | Environmental design | Environmental economics | Environmental ethics | Environmental law | Physics
Environmental technology
From Wikipedia, the Free Encyclopedia. Original article here. Support Wikipedia by contributing or donating.
All text is available under the terms of the GNU Free Documentation License See Wikipedia Copyrights for details.
Like plutonium, neptunium has a high affinity for soil.[link]
Sources
Bomb detonations
About 3.5 tons of plutonium have been released into the environment by atomic bomb tests. While this might sound a large amount it has only resulted in a very small dose to the majority of the humans on the earth. Overall the health effects of the fission products are far greater than the effects of the actinides released by a nuclear bomb detonation. The plutonium from the Pu fuel of the bomb is converted into a high fired oxide which is carried high into the air. It slowly falls to earth as global fallout and is not soluble, hence as a result it is difficult for this plutonium to be incorporated into an animal if taken by mouth. Much of this plutonium will become tightly absorbed onto sediments of lakes, rivers and oceans. However about 66% of the plutonium from a bomb explosion is formed by the neutron capture of uranium-238, this plutonium is not converted by the bomb into a high fired oxide as it is formed more slowly. As a result this formed plutonium is more soluble and more able to cause harm when it falls to earth. (source Radiochemistry and Nuclear Chemistry, G. Choppin, J-O. Liljenzin and J. Rydberg, 3rd Ed, ButterworthHeinemann, 2002)
Some of the plutonium can be desposited close to the point of detonation. The glassy trinitite formed by the first atom bomb has been examined to determine what actinides and other radioisotopes it contained. A recent paper (P.P. Parekh, T.M. Semkow, M.A. Torres, D.K. Haines, J.M. Cooper, P.M. Rosenberg and M.E. Kitto, Journal of Environmental Radioactivity, 2006, 85, 103-120) reports the levels of long lived radioisotopes in the trinitite. The trinitite was formed from feldspar and quartz which were melted by the heat. Two samples of trinitite were used, the first (left hand side bars) was taken from between 40 and 65 meters of ground zero while the other sample was taken from further away from the ground zero point.
The 152Eu and 154Eu was mainly formed by the neutron activation of the europium in the soil, it is clear that the level of radioactivity for these isotopes is highest where the neutron dose to the soil was larger. Some of the 60Co is generated by activation of the cobalt in the soil, but some was also generated by the activation of the cobalt in the steel (100 foot) tower. This 60Co from the tower would have been scattered over the site reducing the difference in the soil levels.
The 133Ba and 241Am are due to the neutron activation of barium and plutonium inside the bomb. The barium was present in the form of the nitrate in the chemical explosives used while the plutonium was the fissile fuel used.
It is interesting to note that the 137Cs level is higher in the sample which was further away from the ground zero point, this is through to be because the precursors to the 137Cs (137I and 137Xe) and the cesium to a lesser degree are volitile. The natural radioisotopes in the glass are about the same in both locations.
In this paper a sample of the glass was digested and the plutonium extracted from it, the mass ratio of the isotopes was calculated from the radiometric measurements. In light green the isotopic siganture for the plutonium used for making the bomb is shown, and on the right in dark green the signature of the plutonium in the trinity glass is shown. It is very clear that 238Pu and 241Pu were generated during the detonation, it is reasonable to conclude that some 240Pu was formed during the detonation.
One form of release of plutionium into the environment has been safety trials in these experiments nuclear bombs have been subjected to simulated accidents or have been detonated with an abnormal initiation of the chemical explosives. An abnormal implosion will result in a compression of the pit which is less uniform and smaller than the designed compression in the device. Such an abnormal implosion could result from an accident which triggers one or more of the detonators which trigger the chemical explosive charges.
As a result of these experiments (where no or very little nuclear fission occurs) plutonium metal has been scattered around near the site of the experiemnt. While some of these tests have been done inside holes in the ground, other such tests were conducted in open air. A paper on the radioisotopes left on an island by the French nuclear bombs tests of the 20th centry has been printed by the IAEA and a section of this report deals with plutonium contamination resulting from such tests.[link]
Other related trials were conducted at Maralinga, South Australia here both normal bomb detonations and "safety trials" have been conducted. While the activity from the fission products has decayed away almost totally (as of 2006) the plutonium remains active. A report (warning it is jolly big) can be read at [link] while a smaller report can be seen at [link].
Another potential source of plutonium being introduced into the environment is the reentry of artificial satellites containing atomic batteries. There have been several such incidents, the most prominent being the Apollo 13 mission. The Apollo Lunar Surface Experiment Package carried on the Lunar Module re-entered the atmosphere over the South Pacific. Many atomic batteries have been of the Radioisotope thermoelectric generator (RTG) type.
Chain reactions do not occur inside RTGs, so such a nuclear meltdown is impossible. In fact, some RTGs are designed so that fission does not occur at all; rather, forms of radioactive decay which cannot trigger other radioactive decays are used instead. As a result, the fuel in an RTG is consumed much more slowly and much less power is produced.
RTGs are still a potential source of radioactive contamination: if the container holding the fuel leaks, the radioactive material will contaminate the environment. The main concern is that if an accident were to occur during launch or a subsequent passage of a spacecraft close to Earth, harmful material could be released into the atmosphere. However, this event is extremely unlikely with current RTG cask designs.
In order to minimise the risk of the radioactive material being released, the fuel is typically stored in individual modular units with their own heat shielding. They are surrounded by a layer of iridium metal and encased in high-strength graphite blocks. These two materials are corrosion and heat-resistant. Surrounding the graphite blocks is an aeroshell, designed to protect the entire assembly against the heat of reentering the earth's atmosphere. The plutonium fuel is also stored in a ceramic form that is heat-resistant, minimising the risk of vaporization and aerosolization. The ceramic is also highly insoluble.
The US Department of Energy has conducted seawater tests and determined that the graphite casing, which was designed to withstand reentry, is stable and no release of plutonium should occur. Subsequent investigations have found no increase in the natural background radiation in the area. The Apollo 13 accident represents an extreme scenario due to the high re-entry velocities of the craft returning from cislunar space. This accident has served to validate the design of later-generation RTGs as highly safe.
The Plutonium-238 used in RTGs has a half-life of 88 years, as opposed to the plutonium-239 used in nuclear weapons and reactors, which has a half-life of 24,100 years.
Some heart pacemakers which are powered by RTGs using 238Pu have been made.
Plutonium has been released into the environment in aqueous solution from nuclear reprocessing and uranium enrichment plants. The chemistry of this plutonium is different to that of the metal oxides formed from nuclear bomb detonations.
One example of a site (military not civil) where plutonium entered the soil is Rocky Flats where in the recent past XANES (a X-ray spectrscopy) has been used to determine the chemical nature of the plutonium in the soil.[link]. The XANES was used to determine the oxidation state of the plutonium, while EXAFS was used to investigate the strucutre of the plutonium compound present in the soil and concrete.[link]
Because plutonium oxide is very involatile, most of the plutonium in the reactor was not released during the fire. However that which was released can be measured. V.I. Yoschenko et. al. reported that grass and forest fires can make the cesium, strontium and plutonium become mobile in the air again. (Journal of Environmental Radioactivity, 2006, 86, 143-163.) As an experiment fires were set and the levels of the radioactivity in the air downwind of these fires was measured.
One case exists of a German man who attempted to poison his ex-wife with plutonium stolen from WAK (Wiederaufbereitungsanlage Karlsruhe). WAK was a small scale reprocessing plant where he worked. He did not steal a large amount of plutonium, just some rags used for wiping surfaces and a small amount of liquid waste. This man was sent to prison for his crime. [link] [link] At least two people (besides the criminal) were contaminated by the plutonium. [link]. Two flats in Rhineland-Palatinate were contaminated. These were later cleaned at a cost of two million euro.
For photographs of the case and details of other nuclear crimes see [link] which was presented by a worker at the ITU.
The details of how the two flats were cleaned has been recorded [link]. The flats were in a place called Landau.
Plutonium like other actinides readily forms a dioxide plutonyl core (PuO2). In the environment, this plutonyl core readily complexes with carbonate as well as other oxygen moeities (OH-, NO2-, NO3-, and SO4-2) to form charged complexes which can be readily mobile with low affinities to soil.
Plutonium is known to bind to soil particles very strongly, see above for a X-ray spectrscopic study of plutonium in soil and concrete. While cesium has very different chemistry to the actinides, it is well known that both cesium and many of the actinides bind strongly to the minerals in soil. Hence it has been possible to use 134Cs labeled soil to study the migration of Pu and Cs is soils. It has been shown that colloidal transport processes control the migration of Cs (and will control the migration of Pu) in the soil at the Waste Isolation Pilot Plant according to R.D. Whicker and S.A. Ibrahim, Journal of Environmental Radioactivity, 2006, 88, 171-188.
Plutonium in humans is transported in the transferrin based iron(III) transport system and then is stored in the liver in the iron store (ferritin), after an exposure to plutonium it is important to rapidly inject the subject with the calcium complex[link] of DTPA[link] [link]. This antidote is useful for a single one off exposure such as that which would occur if a glove box worker was to cut their hand with a Pu contaminated object. The calcium complex has faster metal binding kinetics than the zinc complex but if the calcium complex is used for a long time it tends to remove important minerals from the person. The zinc complex is less able to cause these effects.
Americium often enters landfills from discarded smoke detectors. The rules associated with the disposal of smoke detectors are very relaxed in most municipalities. For instance in the UK it is permissible to dispose of an americium containing smoke detector by placing it in the dustbin with normal household rubbish, but each dustbin worth of rubbish is limited to only containing one smoke detector.
In France a truck transporting 900 smoke detectors has been reported to have caught fire, it is claimed that this lead to a release of americium into the environment.[link]
Humans have become contaminated with americium, the worst case was that of Harold McCluskey. It is interesting to note that Harold McCluskey did not die of cancer but of heart disease (which he had before the accident). It is likely that the medical care which he was given saved his life, it should be noted that due to the difference in the chemistry of americium(the +3 oxidation state is the very stable) to plutonium (where the +4 state can form in the human body) the americium has very different biochemistry to plutonium.
Radioactivity, Ionizing Radiation and Nuclear Energy, by J. Hala and J.D. Navratil
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PuO2 formed from neutralizing highly acidic nitric acid solutions tends to form polymeric PuO2 which is resistant to complexation. Plutonium also readily shifts valences between the +3, +4, +5 and +6 states. It is common for some fraction of plutonium in solution to exist in all of these states in equilibrium.Biology
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