Plutonium concern

Because of the high rate of emission of alpha particles and the element being specifically absorbed on bone the surface and collected in the liver, plutonium, as well as all of the other transuranium elements except neptunium, are radiological poisons and must be handled with very special equipment and precautions. Plutonium is a very dangerous radiological hazard. Precautions must also be taken to prevent the unintentional formulation of a critical mass. Plutonium in liquid solution is more likely to become critical than solid plutonium. The shape of the mass must also be considered where criticality is concerned. 

The Hanford N Reactor. The Hanford N reactor was built in 1964 for purposes of plutonium production during the Cold War. It used graphite as moderator, pierced by over 1000 Zircaloy 2 tubes. These pressure tubes contained slightly enriched uranium fuel cooled by high temperature light water. The reactor also provided 800 MWe to the Washington PubHc Power Supply System. This reactor was shut down in 1992 because of age and concern for safety. The similarity to the Chemobyl-type reactors played a role in the decision. 

The recycling option is being utilized outside the United States. Whereas the technology of this option has been completely demonstrated ia the United States, the economics have not been favorable. Moreover, concerns have been raised as to the diversion of the plutonium to weapons use. Thus, the throwaway option is the only one ia use ia the United States as of this writing. 

The primary issue is to prevent groundwater from becoming radioactively contaminated. Thus, the property of concern of the long-lived radioactive species is their solubility in water. The long-lived actinides such as plutonium are metallic and insoluble even if water were to penetrate into the repository. Certain fission-product isotopes such as iodine-129 and technicium-99 are soluble, however, and therefore represent the principal although very low level hazard. Studies of Yucca Mountain, Nevada, tentatively chosen as the site for the spent fuel and high level waste repository, are underway (44). 

Concern about the potential diversion of separated reactor-grade plutonium has led to a reduction ia U.S. governmental support of development of both plutonium recycle and the Hquid metal reactor. This latter ultimately depends on chemical reprocessing to achieve its long-range purpose of generating more nuclear fuel than it bums ia generating electricity. 

The first and second spectra of plutonium are probably the most thoroughly studied of any in the periodic table insofar as experimental description of the observed spectra and the term analysis is concerned, but a detailed quantum mechanical treatment has been handicapped by their great complexity. Fortunately, the lowest odd and lowest even configurations for both Pu I and Pu II are relatively simple, and parametric studies of the lowest levels of the 5f67s2, 5f56d7s2 and... 

Although the effect of reflux on polymer formation has been recognized for many years, little detailed information is available concerning the extent to which changes in temperature, acidity, and plutonium concentration affect it. 

The large and widespread production of plutonium in nuclear power stations combined with its high radiotoxicity has caused great public concern about "plutonium poisoning". Consequently, the spread of plutonium in the environment has been extensively studied for several decades. The results have been reported in journals and more recently in a number of monographs and conference proceedings (e.g. L- 7). ... 

Disproportionation of Pu(IV). There are several needs associated witn the occurrence, detection, and mitigation of the disproportionation of Pu(IV) in applied plutonium recovery/ purification procedures. First, there is a great need for much more detailed information concerning the effect of typical process conditions [e.g., temperature, concentration of plutonium, hydrogen ion, nitrate ion, nitrite ion, fluoride ion, other metal ions (e.g., A13+, Fe3+, etc.), etc.] on the occurrence and extent of the reaction ... 

In addition, we are evaluating problems in the areas of process and equipment design have been evaluated. Most recent efforts are concerned with the recovery and recycle of plutonium values in the residues. 

There was considerable corridor discussion after a presentation by Dr. G. L. Silver, who "got the attention of the audience" by taking plutonium chemists to task concerning (according to him) their erroneous use of a (too) simplified summary equation involving the disproportionation of Pu(IV) and their lack of appreciation of alpha coefficients. Dr. Silver stressed the use of alpha coefficients and equations which explicitly involve acidity, hydrolysis of Pu(IV), and especially the presence of Pu(V), which is too frequently ignored. 

Phil Horwitz asked me to comment on what I saw as potential disadvantages of the various plutonium pyrochemical processes extolled by speakers in the Tuesday sessions. I, too, am a fan of pyrochemical techniques. I recognize that pyrochemical processes for Pu processing are just in their infancy - on batch plant-scale. To be truly useful, such processes need to be operated on a continuous basis. Scientists and engineers concerned with such technology need to develop equipment and procedures required to operate pyrochemical processes in a cost-effective, continuous manner."... 

Notwithstanding the Iraqi lesson learned that the possibility of undeclared nuclear activities must be taken seriously and their possible existence sought out, the concern with undeclared activities as a proliferation risk is not new and their possible existence has always been recognized, indeed, presumed, in ary serious analysis of safeguards. Even purified plutonium or highly enriched uranium metals are harmless in bulk form. Further steps, specifically fabrication into weapons components, are necessary before these materials can result in proliferation and these steps, while perhaps not demanding, are not trivial. They are necessarily presumed to exist if the diversion of separated plutonium or HEU is discovered, since no reliable means for their detection are available. 

Proliferation concerns have been and continue to be the basic cause ofthe official US. opposition to reprocessing and plutonium recycle, and have thus led to the official U.S. categorization of spent fuel as nuclear waste which should be permanently buried in geologic repositories. 

Another option is to use nuclear energy. Whereas technologically, with the development of breeder reactors, the uranium resources can be considered non-exhaustible and reactor technology can be considered safe [4] a serious concern is the proliferation of plutonium for nuclear weapons. There is also the unproven solution for disposal of radioactive material. 

Since there is now considerable concern in the technologically advanced countries concerning the contamination of the environment by actinides, such as plutonium, americium and curium, this review attempts to present an understanding of how the actinides could concentrate and/or become transported through the biosphere to man. 

Since plutonium is the actinide generating most concern at the moment this review will be concerned primarily with this element. However, in the event of the fast breeder reactors being introduced the behaviour of americium and curium will be emphasised. As neptunium is of no major concern in comparison to plutonium there has been little research conducted on its behaviour in the biosphere. This review will not discuss the behaviour of berkelium, californium, einsteinium, fermium, mendelevium, nobelium and lawrencium which are of no concern in the nuclear power programme although some of these actinides may be used in nuclear powered pacemakers. Occasionally other actinides, and some lanthanides, are referred to but merely to illustrate a particular fact of the actinides with greater clarity. 

There have been many reviews concerned with the behaviour of plutonium and the other higher actinides in man and a variety of experimental animals (175). In view of this wealth of literature this section is restricted to a brief highlighting of the bioinorganic chemistry of the actinides in animals. 

Since transport by water is virtually the only available mechanism for escape, we will be predominantly concerned with the chemistry of aqueous solutions at the interface with inorganic solids - mainly oxides. These will be at ordinary to somewhat elevated temperatures, 20-200 C, because of the heating effects of radioactive decay during the first millennium. The elements primarily of interest (Table I) are the more persistent fission products which occur in various parts of the periodic table, and the actinides, particularly uranium and thorium and, most important of all, plutonium. 

Since the water movement will be very slow compared with the rate at which the wastes dissolve, we are concerned first and foremost with equilibrium solubility. Also, if only to relate behaviour on the geological time scale to that on the laboratory time scale, we will need to know about the mechanisms and kinetics of dissolution and leaching. The waste forms envisaged at present are glass blocks containing separated fission products and residual actinides fused into the glass and, alternatively, the uranium dioxide matrix of the used fuel containing unseparated fission products and plutonium. In the... 

The remaining exceptions concern the lanthanide series, where samarium at room temperature has a particular hexagonal structure and especially the lower actinides uranium, neptunium, and plutonium. Here the departure from simple symmetry is particularly pronounced. Comparing these three elements with other metals having partly filled inner shells (transition elements and lanthanides), U, Pu, Np have the lowest symmetry at room temperature, normal pressure. This particular crystallographic character is the reason why Pearson did not succeed to fit the alpha forms of U, Pu, and Np, as well as gamma-Pu into his comprehensive classification of metallic structures and treated them as idiosyncratic structures . Recent theoretical considerations reveal that the appearance of low symmetries in the actinide series is intimately linked to the behaviour of the 5f electrons. 

The majority of literature concerning the electrochemical behavior of plutonium is focused on results obtained in acidic aqueous or molten salts solutions. Several reviews have appeared on the redox properties of plutonium in... 

Even when the analysis is being performed splendidly, the limitation of any measurement due to measurement uncertainty always leads to some doubt about the result. See chapter 6 for an example of uncertainty concerning the amount of weapons-grade plutonium in the world. 

Within the last two years, major concerns over the proliferation problems associated with the recycle of uranium and plutonium have lead the President of the United States to call for an indefinite delay in future plans for reprocessing pending an evaluation... 

In the present paper the chemistry of plutonium is reviewed, with particular reference to the ambient conditions likely to be encountered in natural waters. In addition, experimental work is presented concerning the effects of such variables as pH, plutonium concentration, ionic strength, and the presence of complexing agents on the particle size distributions of aqueous plutonium. In subsequent papers it will be shown that these variables, as they influence the particle size distribution of the aqueous plutonium, greatly affect its interaction with mineral surfaces. The orientation of these studies is the understanding of the likely behavior and fate of plutonium in environmental waters, particularly as related to its interaction with suspended and bottom sediments. 

Spent fuel from a reactor contains unused uranium as well as plutonium-239 which has been created by bombardment of neutrons during the fission process. Mixed with these useful materials are other highly radioactive and hazardous fission products, such as cesium-137 and strontium-90. Since reprocessed fuels contain plutonium, well suited for making nuclear weapons, concern has been expressed over the possible capture of some of this material by agents or terrorists operating on behalf of unfriendly governments that do not have a nuclear weapons capability. 

---