Nuclear Fuel Cycle

RADIOCHEMISTRY AND NUCLEAR CHEMISTRY Nuclear Waste Management and the Nuclear Fuel Cycle - Patricia. A.
. Baisden, Gregory R. Choppin
NUCLEAR WASTE MANAGEMENT AND THE NUCLEAR FUEL CYCLE

Patricia. A. Baisden National Ignition Facility Programs Directorate, Lawrence Livermore National Laboratory, Livermore, CA, USA Gregory R. Choppin Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL, USA
Contents
1. Introduction 2. Classification of radioactive wastes 3. Who is responsible for radioactive wastes? 4. Splitting the atom for energy 5. Status of nuclear power world-wide 6. Nature of HLW as a function of time 7. Fast reactors 8. The nuclear fuel cycle 9. Important characteristics of actinides 10. Separations technologies for the nuclear fuel cycle 11. Advanced fuel cycle concepts and partitioning and transmutation (P&T) 12. Aqueous chemical processing 13. Non-aqueous chemical processing 14. Transmutation devices for the advanced fuel cycle 15. Strategies for implementation of an advanced fuel cycle 16. Generation IV nuclear energy systems 17. Future of P&T Appendix Glossary Bibliography Biographical sketches To cite this chapter Summary
In addition to a rapidly growing demand for more electricity, especially in Asia, concerns over energy resource availability, climate change, air quality, and energy security suggest a larger and more important role for nuclear power in the future. However, it is unlikely the public will accept growth of nuclear power until issues associated with nuclear waste management, reactor safety, economics, and non-
Encyclopedia of Life Support Systems (EOLSS)
E SA SC M O PL -E E O C LS H AP S TE R
Keywords: actinide chemistry, advanced fuel cycle, aqueous and non-aqueous separations technologies, fast reactors, Gen IV nuclear energy systems, nuclear fuel cycle, nuclear power and spent fuel, nuclear waste, partitioning and transmutation.
RADIOCHEMISTRY AND NUCLEAR CHEMISTRY Nuclear Waste Management and the Nuclear Fuel Cycle - Patricia. A. Baisden, Gregory R. Choppin
proliferation are addressed by both the nuclear industry and government. In this chapter, the management of nuclear waste from power generation is described in terms the three major fuel cycle options that are under consideration by various countries around the world. The importance of the actinide elements and certain fission products as the long term waste issues is discussed along with both aqueous and non-aqueous separation technologies that can be used to partition these from spent fuel for subsequent transmutation using reactor or accelerator-driven devices in an advanced fuel cycle scenario. The strategy and challenges associated with the deployment of Generation IV Energy systems currently under development are also discussed. 1. Introduction
In general, three options exist for managing radioactive waste: (1) concentrate and contain (concentrate and isolate the wastes in an appropriate environment); (2) dilute and disperse (dilute to regulatory-acceptable levels and then discharge to the environment); and; (3) delay to decay (allow the radioactive constituents to decay to an acceptable or background level). The first two options are common to managing nonradioactive waste but the third is unique to radioactive waste. Eventually all radioactive wastes become benign because they decay to stable elements while non-radioactive, hazardous waste remains hazardous forever or until their chemical speciation is changed By far the largest source of radioactive waste from the civilian sector results from the generation of power in nuclear reactors. Much smaller quantities of civilian radioactive waste result from use of radionuclides for scientific research as well as from industrial sources such as medical isotope production for diagnostic and therapeutic use and from X-ray and neutron sources. The other significant sources of radioactive waste are due to defense related activities that support the production and manufacture of nuclear weapons. This chapter deals primarily with the management of civilian nuclear waste and focuses on that generated from nuclear power. 2. Classification of Radioactive Wastes
In order to manage nuclear wastes, it is useful to classify or group them into categories based on the properties of the waste, which can be done in a number of ways. For example, radioactive waste can be classified by the level of radioactivity present (high, intermediate, low, or below regulatory concern), by the dominant type of radiation emitted (alpha, beta, gamma, or X-ray) or, by its half-life (a length of time required for the material to decay to half of its original value). Also, radioactive wastes can be classified by their physical characteristics (primarily, solid or liquid, but they can also exist in the gaseous state). A quantitative way to classify radioactive waste is by specific activity or activity concentration; i.e., by the activity per quantity of waste (mass or volume). The heat generated in a sample (that depends on half-life,
Radioactive waste, like other wastes, may be composed of materials varying in origin, chemical composition, and physical state. However, what differentiates radioactive waste from other waste forms is that it contains components that are unstable due to radioactive decay. Managing radioactive waste requires different approaches to ensure the protection of both humans and the environment from the radiation.
concentration, and type of radiation) can also be used for classification. Finally, waste can be classified for security and non-proliferation purposes (e.g., designated as special nuclear materials), for worker safety, and for transportation. These various classifications have advantages and disadvantages depending upon how the information is used. In the United States and many places around the world, radioactive wastes have traditionally been classified on the basis of their characteristics and how the waste was produced via a top down, generator-oriented approach. This has resulted in inconsistencies, overlaps, and omissions which lead to conflicts between the source-defined classifications and the waste acceptance criteria developed from the disposal systems. Such generator-oriented waste classifications do not fully capture the associated hazards and, thus, are insufficient to ensure public health and environmental safety. Whatever qualitative framework is used, the length of time radioactive waste must be isolated from the public is determined primarily by its half-life and energy. The heat generation, concentration, and type of radiation determine the shielding and handling requirements for the disposal of the waste. Although the classification of radioactive wastes varies from country to country, three groupings are generally accepted internationally. 2.1. High-level Waste (HLW)
HLW generally refers to the radioactive nuclides at high levels from nuclear power generation, (i.e. reprocessing waste streams or unprocessed spent fuel) or from the isolation of fissile radionuclides from irradiated materials associated with nuclear weapons production. When the spent nuclear fuel from reactor operations (civilian or defense) is chemically processed, the radioactive wastes include nuclides from the aqueous phase from the first extraction cycle (and other reprocessing waste streams) as it contains high concentrations of radioactive fission products. As a result, HLW is highly radioactive, generates a significant amount of heat, and contains long-lived radionuclides. Typically these aqueous waste streams are treated by the principle of concentrate and contain, as the HLW is normally further processed and solidified into either a glass (vitrification) or a ceramic matrix waste form. Spent nuclear fuel not reprocessed is also considered as HLW. Because of the highly radioactive fission products contained within the spent fuel, it must be stored for cooling for many years before final disposal by isolation from the environment. This final disposal of HLW is placement within deep geologic formations. Relative to the total volume of waste produced from commercial power generation, HWL constitutes only a small fraction (a few percent). However, the vast majority of the radioactivity (> 95%) resides in the HLW. The only disposal option for this class of waste is burial in a deep geologic repository. 2.2. Intermediate-level Waste (ILW) ILW contains lower amounts of radioactivity than HLW but still requires use of special shielding to assure worker safety. Reactor components, contaminated materials from reactor decommissioning, sludge from spent fuel cooling and storage areas, and materials used to clean coolant systems such as resins and filters are generally classified
as ILW. The most common management option is delay to decay for short-lived solid waste, but for the long-lived waste, the concentrate and contain principle (solidification for deep geologic disposal) is required. ILW comprises about 7% of the volume and, roughly, 4% of the radioactivity of all radioactive wastes. The disposal options for this class of waste are burial in a deep geologic repository for the long-lived radionuclides and near-surface burial for the short-lived ones. 2.3. Low-level Waste (LLW) All civilian and defense-related facilities that use or handle radioactive materials generate some LLW. These include research laboratories, hospitals using radionuclides for diagnostic and therapeutic procedures, as well as nuclear power plants. LLW includes materials that become contaminated by exposure to radiation or by contact with radioactive materials. Items such as paper, rags, tools, protective clothing, filters and other lightly contaminated materials that contain small amounts of short-lived nuclides are usually classified as LLW. By its nature, LLW does not require shielding during normal handling and transportation and both principles of delay to decay and dilute and disperse can be employed for disposal depending on the exact nature of the waste. Often, it is advantageous to reduce the volume of LLW by compaction or incineration before disposal. Worldwide it constitutes ~90% of the volume but only ~1% of the radioactivity associated with all radioactive waste. However, wastes containing small amounts of long-lived radionuclides can be included under the LLW classification. The disposal options for this class of waste are near-surface burial or no restrictions depending on level of radioactivity. The International Atomic Energy Agency (IAEA) noted that these classifications, HLW, ILW and LLW, although useful for some purposes, have some important limitations. Specifically the limitations cited are no clear linkage to the safety aspects in radioactive waste managements, especially disposal, the current classification system lacks quantitative boundaries between classes, and no recognition of a class of waste that contains so little radioactive material that it may be exempted from control as a radioactive waste. To overcome these limitations, the IAEA proposed a modified system shown in Figure 1.
Figure 1: From the IAEA publication: Classification of Radioactive Waste, A Safety Guide, Safety Series No 111-G1.1 (1994). In this simple but eloquent scheme, the principal waste classes are exempt waste (explained in the next paragraph), low and intermediate level waste (which may be subdivided into short and long-lived waste and alpha-bearing waste) and high level waste. On the y-axis the radioactivity ranges from very low (simple and conventional disposal) to very high (isolation in a geological repository). As the radioactivity increases so does the heat content, the need for shielding, and need for better and longer isolation from the biosphere. On the x-axis, the decay periods range from very short (seconds) to very long (millions of years) and the associated wastes range in composition from those containing small to significant quantities of long-lived radionuclides. Exempt waste, also identified as below regulatory concern or de minimis, contains very low concentrations of radioactivity. The associated radiological hazards are generally considered to be negligible as they are less than for naturally-occurring radioactivity. To date, the classification scheme proposed by the IAEA has not had universal acceptance although this scheme or slight variations of it are in use in a number of countries. For example, most countries recognize and accept exempt waste as the fourth
principal classification along with HLW, ILW, and LLW. In the United States waste classifications are defined by the US Nuclear Regulatory Commission (NRC): 1. High Level Waste (HLW) (A) The highly radioactive material resulting from the reprocessing of spent nuclear fuel, including liquid waste produced directly in reprocessing and any solid material derived from such liquid waste that contains fission products in sufficient concentrations; and (B) other highly radioactive material for which the NRC, consistent with existing law, requires permanent isolation; 2. Spent Nuclear Fuel (SNF) Fuel that has been withdrawn from a nuclear reactor following irradiation, the constituent elements of which have not been separated by reprocessing; the NRC requires SNF be regulated as HLW; 3. Transuranic (TRU) Waste Waste contaminated with alpha-emitting transuranic elements (Z > 92) with half-lives greater than 20 years and in concentrations higher than 100 nanocuries/gram (3700 Bq g-1); 4. Uranium mining and mill tailings Tailings or wastes produced by the extraction or concentration of uranium or thorium from any ore processed primarily for its source material content (also called by-product material); 5. Low-Level Waste (LLW) Radioactive material that is not high-level radioactive waste, spent nuclear fuel, nor by-product material; low level waste is further subdivided as shown in Table 1; 6. Naturally Occurring and Accelerator produced Radioactive Materials (NORM/NARM). LLW Waste Class Class A
Class B
Class C
Greater than Class C
Table 1: Subclasses of low-level waste according to the US Nuclear Regulatory Commission (US NRC) - U.S. Code of Federal Regulations, Title 10, Part 61 (10 C.F.R. 61).
Definition Low levels of radiation and heat, no shielding required to protect workers or public, rule of thumb states that it should decay to acceptable levels within 100 years Higher concentrations of radioactivity than Class A and requires greater isolation and packaging (and shielding for operations) than Class A waste. Requires isolation from the biosphere for 500 years. Must be buried at least 5m below the surface and must have an engineered barrier (container and grouting) This is the LLW that does not qualify for near-surface burial. This includes commercial transuranics (TRUs) that have half-lives > 5 years and activity > 100 nCi/g.
3. Who is Responsible for Radioactive Wastes? Internationally it is accepted that each country is ethically and legally responsible for the radioactive wastes generated within its borders. Specifics related to what constitutes radioactive waste, the parties responsible, as well as the bodies charged with regulating its use and ultimate disposal, are issues defined by governmental processes. 3.1. Pertinent Legislation in the US Regarding Radioactive Wastes: An Example In the United States, legislation has resulted in laws that govern the production, use, and means of disposal of radioactive materials. In 1946 the McMahon Energy Act created the Atomic Energy Commission (AEC) with a charter to operate the Manhattan Project facilities. The Atomic Energy Act of 1954, as amended, defined responsibilities related to production, use, ownership, liability, and disposal. This legislation also made possible the creation of the civilian nuclear power program within the US. It was not until about 1970 that the AEC defined high level waste. HLW was defined as aqueous waste resulting from solvent extraction cycles associated with reprocessing spent reactor fuel. Four years later, Congress enacted the Energy Reorganization Act that split the AEC into two organizations, the Energy Resource and Development Administration (ERDA) and the Nuclear Regulatory Commission (NRC). ERDA, now the Department of Energy (DOE), was given the task of developing and promoting nuclear power while the NRC was tasked with licensing and regulating the emerging nuclear power industry. In 1980, the Low-Level Radioactive Waste Policy Act and an amendment in 1985, transferred responsibility for disposal of non-defense related low level waste from the federal government to the states but kept commercial transuranic (TRU) waste and certain low-level wastes containing long lived radionuclides within the responsibility of the federal government. This legislation also mandated that the Environmental Protection Agency (EPA) establish radiation protection from LLW. Disposal of HLW and spent fuel was the focus of the Nuclear Waste Policy Act (NWPA) in 1982 which called for the construction of two permanent repositories on the west and east coasts. The NWPA was amended in 1987 to name Yucca Mountain as the only site that would be developed as a repository. The disposal of HLW remains a major public policy issue in the US as well as abroad. Public concerns and political pressures have led to the need to demonstrate the feasibility and safety of HLW disposal and, in some countries, to implement laws that require operational HLW disposal capability in the next 1050 years. Many countries, including the United States, have programs dedicated to the disposal of HLW. However, all HLW produced to date is being stored and no permanent disposal system has been approved. 4. Splitting the Atom for Energy Nuclear power produces energy by fissioning nuclides, most notably 235 U or 239 Pu . When these nuclides fission, the resulting fission fragments and neutrons have a combined mass less than the parent nuclide. During the fission process, the difference in mass is converted to energy and results in the release of about 200 MeV of energy (or
3.21011 joules) for every atom that fissions. The partitioning of the energy resulting from the fission of 235 U is shown in Table 2. Approx. Energy (MeV) 164.5 5.0 7.0 176.50 6.5
Description Kinetic energy of fission fragments Kinetic energy of prompt neutrons (2.5 neutrons/fission event with a average energy of ~2 MeV) prompt -rays Subtotal Kinetic energy of -particles emitted in decay of fission products Neutrinos -rays Subtotal Energy/fission of an atom of U-235 in MeV
Prompt Energy
A great advantage of nuclear power is its ability to extract a tremendous amount of energy from a small volume of fuel. In comparison to fission, the burning of fossil fuels involves only the breaking of chemical bonds, and as a result, only 4 eV or 6.51019 joules/molecule of CO 2 are released in the combustion of a carbon atom. Another advantage is related to the inherent characteristics of the fuel itself. Aside from its potential use in nuclear weapons, uranium ore has little use other than for the production of electricity through nuclear power. In contrast, fossil fuels can potentially be used for a wide variety of applications from the production of pharmaceuticals to various important synthetic materials production and to transportation. A third inherent advantage of nuclear power is that under normal operations, energy is produced with minimal environmental impact in terms of air and water pollution compared with burning of fossil fuel, particularly coal. Fossil fuels release large quantities of CO 2 and sulfur and nitrogen oxides (acid rain) to the atmosphere and substantial amounts of fly ash as solid waste. International concern is increasing over the Greenhouse Gas threat from fossil fuel. Energy created by splitting the atom does not produce greenhouse gases. 5. Status of Nuclear Power World-wide At the present time, nuclear energy provides over 17% of the worlds total electricity as base load power. As of 2006, 441 commercial nuclear reactors operating in 31 countries produce this electricity with a total generating capacity of over 380 GWe (gigawatts of electrical energy). Of the existing commercial power reactors shown in Table 3, the overwhelming majority (> 99%) are thermal reactors, which means that fission is
Delayed Energy 10.5 6.5 23.5 Total 200.0 Table 2: Partitioning of energy in the fission of
235
induced by low energy, thermal neutrons (~0.025 eV). Of the thermal reactors, greater than 80% are light water reactors (LWRs) There are two primary designs or types of LWRs, the pressurized water (PWR) or boiling water (BWR) reactors. In a LWR, normal hydrogen in water is used as the moderating material that reduces the energy of the neutrons released in the fission from approximately 23 MeV to the thermal regime (~0.025 eV). If the neutrons are not so moderated (e.g., in a fast reactor), more energetic neutrons (10s to 100s of keV) can also induce fission. The probability of fission for a given nucleus depends on the energy of the neutron inducing the fission. Some nuclides fission more easily with thermal neutrons while others require more energetic neutrons to induce fission. Reactor Type Pressurized Water Reactor (PWR) Boiling Water Reactor (BWR) Gas-cooled Reactor (Magnox & AGR) Pressurized Heavy Water Reactor CANDU (PHWR) Light Water Graphite Reactor (RBMK) Fast Neutron Reactor (FBR) Country US, France, Japan, Russia Number GWe Fuel Coolant Moderator
Table 3: Types of commercial nuclear reactors.(GWe=capacity in thousands of megawatts)Courtesy of the World Nuclear Association (http://www.worldnuclear.org/info/inf32.html) 5.1. Commercial Nuclear Power Generation The power produced by current commercial reactors ranges from about 1 to 4.5 GWth
268 249 enriched UO2 water water US, Japan, Sweden 94 85 enriched UO2 water water UK 23 12 natural U (metal), enriched UO2 CO2 Canada 40 22 natural UO2 heavy water heavy water Russia 12 12 enriched UO2 water Japan, France, Russia Total 4 1 PuO2 and UO2 liquid sodium none 441 381
graphite
graphite
(gigawatts thermal). These reactors have average efficiencies of about 33% and produce between 500 to 1500 MWe (megawatts of electrical energy). The core of a typical large PWR reactor consists of between 80 to 100 tons of enriched uranium (~3.5% 235 U ) divided into several hundred fuel assemblies. Each fuel assembly is made up of 200-300 fuel rods roughly 3.5 m long. Each fuel rod is composed of ceramic uranium dioxide ( UO2 ) pellets typically ~1 cm in diameter and ~1.5 cm in length. In the operation cycle of a nuclear reactor, several competing processes determine the final radionuclide inventory in the spent fuel. These processes are (1) neutron induced fission which produces energy, 2-3 neutrons on the average, and two fission products for each atom that fissions; (2) neutron capture which produces an isotope of the same element but of one mass unit higher; and (3) radioactive decay. In a nuclear reactor, there are two primary modes of radioactive decay, and alpha decay. For the process of decay, a nuclide of mass number A and atomic number Z is transformed into another nuclide of the same mass number A but with atomic number Z + 1 . Alpha decay results in the formation of a helium nucleus plus a nuclide four mass units and two Z units lower than the original nuclide. The specific amounts of fission products and transuranium nuclides produced in a reactor depend on the mode of operation, i.e., on the energy (low, thermal, or high, fast energy) and the flux of the neutrons (number of neutrons per cm2 per second) inducing the reactions in the reactor fuel. In general, the components in spent fuel include: fission products that range in half-life from a few days or less to hundreds of thousands to millions of years; uranium (element 92), primarily 235 U and 238 U along with 236 U ( T1/ 2 = 2.4107 a) from neutron capture of 235 U ; isotopes of the actinide elements heavier than uranium including Np, Pu, Am and Cm.
At the present time, the majority of spent fuel being stored around the world has been used in LWRs. The breakdown of LWR spent fuel is shown in Table 4. Percentage 95.6 3 Component Disposition Recycled or disposed of as low-level, Class C waste
Uranium Stable or shortlived fission products Major fission products Decays in a short time resulting in no significant disposal problem 0.3 0.1 0.9 0.1 Cesium and strontium are the primary near-term heat sources in HLW: decays in a few centuries Primarily iodine and technetium: can Long-lived fission be stored or removed and products transmuted* Plutonium Can be separated and burned as fuel Long-lived minor Primarily Np, Am, and Cm: can be
actinides
separated and fissioned using fast neutrons
Table 4: Typical percentages of components making up spent nuclear fuel from LWRs along with suggested approaches for disposal.* Transmutation is discussed in Section 11 Some of the isotopes of the transuranium elements ( Z > 92 ) which are formed during reactor operation can undergo fission with release of energy. For example, the loading and discharge inventories associated with a 1 GWe PWR running at a burn rate of ~33 GWd/ton (gigawatt-days of operation/metric ton) is shown in Table 4. From the Table, 674 kg of the original 954 kg of 235 U loaded are consumed in the production of 111 kg of 236 U and 563 kg of fission products. Since the total amount of fission products produced was 946 kg of which 563 kg of fission products were from the fission of 235 U , ~383 kg of fission products must have been produced from the fission of heavier nuclides. Most of the additional fission products may be due to the fission of fissile 239 Pu isotope. Since the probability of fission of 238 U with thermal neutrons in a PWR is very low, the loss of 238 U is due to the neutron capture reaction that produces 239 U which decays by beta emission ( T1/ 2 = 23.5 months) to produce 239 Np which, again, beta decays ( T1/ 2 = 2 d) to produce
238
of U corresponds to the production of approximately 674 kg of 239 Pu . At the end of the reactor cycle, however, only 286 kg of total Pu and higher actinides remain leaving approximately 387 kg of missing 239 Pu . The mass balance between initial and discharge inventories in the table is inaccurate by (1) the mass equivalence of the energy produced (~1 kg) and (2), the mass associated with the neutrons escaping the reactor vessel and those captured in the moderator (~2 kg), the ~387 kg of missing 239 Pu fissions is consistent with the excess fission product estimate of ~383 kg. Thus, during the normal operation of a uranium-fueled PWR, roughly 40% of the energy comes from the fission of 239 Pu produced by neutron capture reactions during the reactor cycle.
239
Pu ( T1/ 2 = 24 000 a). Using this logic, the net loss
Nuclides U-235 U-236 U-238 U Total Pu-239 Pu Total Z > 94 Sr-90 Cs-137 Long-lived FP FP Total Total Mass
Initial Load (kg) Discharge Mass (kg) 954 280 111 26,328 25,655 27,282 26,047 56 266 20 13 30 63 946 27,282 27,279
Z > 94 (transplutonium elements) FP = Fission Products
Table 5: Initial and Discharge Radionuclide Inventory in a nominal 1000 MWe Reactor Courtesy: Elsevier from NIM A463, 428-467 (2001) H. Niefenecker, et. al.Source: P. Schapira, in R. Turlay (Ed.) Les Dechets Nucleaires les Editions de Physique, 1997 Table 6 provides a more detailed breakdown of the isotopics for spent fuel at discharge for a typical 1000 MWe PWR. In the previous discussion, we attributed all the missing fission fragment mass to the fission of 239 Pu . In reality, however, during the course of operation of the reactor, some of the 239 Pu captured a neutron to form 240 Pu ( T1/ 2 = 6600 a). Because of its long half-life and low thermal fission cross section (actinide isotopes with odd mass numbers are more fissile than even mass isotopes). 240 Pu most likely captures a neutron and forms 241 Pu which is a fissile nuclide.
* 1000 MWe LWR, discharge plus 150 d
Table 6: Major and minor actinide content of spent LWR fuel. Courtesy: Benedict et al, Nuclear Chemical Engineering, p. 369, 2nd Ed., McGraw Hill, NY (1981). Source: (NAS 1996) Nuclear Wastes, Technologies for Separations and Transmutation, National Academy Press, p. 25
Actinide Isotope 234 U 235 U 236 U 237 U 238 U 237 Np 239 Np 236 Pu 238 Pu 239 Pu 240 Pu 241 Pu 242 Pu 241 Am 242m Am 243 Am 242 Cm 243 Cm 244 Cm 245 Cm 246 Cm Half-life (years) 2.5 E+5 7.1 E+8 2.4 E+7 1.8 E-2 4.5 E+9 2.1 E+6 6.4 E-3 2.6 E+0 8.6 E+1 2.4 E+4 6.6 E+3 1.3 E+1 3.8 E+5 4.6 E+2 1.5 E+2 7.9 E+3 4.0 E-1 3.2 E+1 1.8 E+2 9.3 E+3 5.5 E+3 Kg/year in Spent Fuel* 3.1 E+0 2.1 E+2 1.1 E+2 9.1 E-7 2.6 E+4 2.0 E+1 2.0 E-6 2.5 E-4 6.0 E+0 1.4 E+2 5.9 E+1 2.8 E+1 9.7 E+0 1.3 E+0 1.2 E-2 2.5 E+0 1.3 E-1 2.0 E-3 9.1 E-1 5.5 E-2 6.2 E-3
Because the fission process is asymmetric, the fission products (FPs) tend to distribute themselves around mass 83-105 (light FP) and mass 129149 (heavy FP). Some of the more common light FPs are 85 Kr, 90 Sr, 95 Zr, 99 Tc 8 and the corresponding heavy FPs are 129 I, 137 Cs, 144 Ce, and 147 Nd . To maintain efficient performance of a nominally 1000 MWe LWR, about one-third of the spent fuel is removed from the reactor core and replaced with fresh fuel each year. However, over time, the concentration of fission products and heavy elements in a fuel bundle increases to the point where it is no longer practical to continue to use the fuel and after 2-3 years, the entire fuel core is replaced with a fresh one.
In the short-term, fission products with half-lives of 30-50 years dominate HLW and constitute the main radiological factor impacting the design of a repository. This is due to the intense gamma radiation and the resulting decay heat associated with the FPs. The heat load initially comes primarily from the decay of 137 Cs ( T1/ 2 = 30 years) and
Sr ( T1/ 2 = 28 years). However, after 300 to 500 years the majority of such short-lived fission products are gone and the dominant hazards in HLW become the actinides and long-lived fission products (LLFP = primarily 99 Tc and 129 I , as well as 79 Se , 93 Zr , and 135 Ce , see Table 7).
90
Table 7: Some long-lived fission products from a thermal reactor.a a After 10 years of cooling a 1 t U as 3.2% enriched UO2 fuel with 33 MWd/kg U burn-up at an average flux of 3.241018 n m-2 s-1 in a typical PWR.
Figure 2 shows the relative levels of the dominant fission products and selected actinides in terms of the parameter, ingestion radiotoxicity, as a function of decay time after discharge from the reactor. From the plot it is clear that 90 Sr and 137 Cs dominate the hazard level of HLW at early times and then after about 30-50 years, Pu isotopes dominate.
Fission Product 99 Tc 129 I 135 Cs 93 Zr 126 Sn 79 Se Half-life (a) 2.13 105 1.57 107 3.0 106 1.5 106 1.0 105 6.5 104 Thermal Fission (TBq/tU) 0.48400 0.00120 0.00980 0.06800 0.02900 0.01510
6. Nature of HLW as a Function of Time
Figure 2: Relative ingestion toxicity of representative fission products and some actinides in spent fuel as a function of time after discharge from a PWR. Courtesy: Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the U.S. Dept. of Energy Source: (NAS 1996) Nuclear Wastes, Technologies for Separations and Transmutation, National Academy Press, p. 24. 7. Fast Reactors Fast reactor technology was developed during the time that thermal reactor technology was being used for commercial power production. Since less than 1% of the energy content of mined uranium is realized in burning 235 U in conventional LWRs, the initial motivation for fast reactors was to breed 239 Pu from 238 U to maximize uranium fuel utilization. In order to exploit a higher fraction of the energy content of uranium, Pu could be produced in fast breeder reactors (FBRs) by placing a blanket of uranium
around the core. In the blanket, 238 U would capture fast neutrons and produce more Pu than consumed in the reactor. In fact, about 70% of all 238 U placed in a fast reactor can be converted to 239 Pu . Since the natural abundance of 238 U is 99.3%, this conversion results in the production of a vast supply of fissile fuel for future centuries. There are several major differences in the design and operation of fast reactors compared with that of thermal reactors. In a fast reactor, no moderator is used and neutrons induce fission at or near the energies at which they are released in the fission reaction (~2 MeV). Although fast reactors do not require a moderator, they do require a coolant. Since water is such an efficient medium for reducing the energy of neutrons, it cannot be used as a coolant; therefore, liquid metals such as sodium, lead, and a lead bismuth alloy or gases, such as helium and carbondioxide have been used. Neutrons travel at such high speeds in fast reactors that the probability of their escaping to the surroundings is much higher. As a result of this neutron leakage, fewer neutrons would be available to react with other fissile nuclides to sustain the chain reaction in fast reactors. To overcome this problem, fast reactor fuel contains a higher ratio of fissile-to-fertile nuclides. Common fast reactor fuel is either highly enriched 235 U or a mixture of 239 Pu and 238 U . As Pu has a rather low fast neutron absorption cross-section, a loading of Pu of at least 2030% is required with 7080% 238 U . In the 1980s, an expected shortage of uranium did not materialize and uranium remained abundant and cheap. Consequently, the need for fast reactors to breed plutonium was neither compelling nor economical. This, along with concerns related to the potential diversion of plutonium to weapons, decreased interest in fast reactors. Prototype demonstration fast reactors such as the BN-600 (600 MWe) in Russia (1980) and the Superphenix (1240 MWe) in France (1985) had started to come on line and the US had initiated the Integral Fast Reactor Program. This program was built on the successful operation of Argonne National Laboratorys experimental breeder reactor, EBR-II, a liquid metal (Na) cooled fast reactor, and its associated pyrochemical process that enabled the practical recycling of a metallic alloy fuel. However, in 1977, President Carter halted reprocessing in the US, and in 1994, the US terminated its fast reactor program. Likewise, the Superphenix reactor in France was shut down in 1999. The Japanese currently have the most active FBR program in the world with both the Joyo (100 MWth) and the Monju (280 MWe) reactors in operation. In the future, many countries are expected to increase their electrical generating capacity by increased reliance on nuclear power. In addition, many countries are exploring ways to reduce the amount of nuclear waste requiring disposal in geologic repositories by exploiting fast reactors to fission the minor actinides. Fast reactor technology is discussed further in later sections describing partitioning and transmutation of waste. 8. The Nuclear Fuel Cycle The nuclear fuel cycle, shown schematically in Figure 3, consists of the processes used to produce electricity from nuclear reactions. The cycle begins with mining the uranium and ends with disposal of the wastes generated. Such wastes include the spent fuel itself
and/or the material from reprocessing to recover the unused fissile material.
Figure 3: Schematic of the nuclear fuel cycle. Courtesy of the World Nuclear Association (http://www.world-nuclear.org/info/inf03.html)
As the term nuclear fuel cycle suggests, the standard scenario envisioned by the nuclear power industry was to reprocess the spent fuel to recover the unburnt uranium and plutonium and recycle it to generate additional energy. In addition, by recovering uranium and returning it to the fuel cycle, the demand for new uranium and the need for enrichment services are reduced by about 30% compared to once-through fuel management. A main advantage of reprocessing in waste management is the large reduction in volume (factor of ~100) of the materials to be disposed of as HLW. Some countries, most notably the US and Canada, at the present time are not reprocessing fuel, and thus do not close the fuel cycle. France, Russia, the United Kingdom, India and some other nations are currently reprocessing spent fuel and recycling plutonium. Japan is expected to join this group with an active reprocessing program. 8.1. Options in the Fuel Cycle that Impact Waste Management The three major back-end fuel cycle options currently under consideration by various countries are:
The fuel cycle is often described in terms of the front-end activities, beginning with mining and milling up through and including burning the uranium fuel in a nuclear reactor and the back-end activities in which the vast majority of the waste is isolated and the unburned uranium and/or plutonium recovered.
a once through fuel option with direct disposal of spent fuel as HLW; reprocessing fuel cycle (RFC) with mixed oxide (MOX) recycle of U and Pu in light water or fast breeder reactors and disposal of HLW; an advanced fuel cycle (AFC), an extension of RFC in which the wastes are partitioned and some are transmuted (P&T) to reduce the long-term radiotoxicity.
These options have different advantages and disadvantages and pose different challenges that vary in complexity to the management of nuclear wastes. 8.1.1. Once-Through Fuel Option In the once through option, shown in Figure 4, fuel is burned in a reactor to make energy.
When energy can no longer be efficiently produced, the spent fuel is removed from the reactor. Because the spent fuel is both thermally hot and intensely radioactive due to the decay of the short-lived fission products, it is normally stored in special, water-filled cooling ponds at or near the reactor. The water serves to absorb and dissipate heat and is also used as a radiation barrier. Since water can moderate the neutron energy, the cooling ponds are designed to physically separate the fuel to prevent criticality. The fuel is allowed to cool for periods varying from 7-10 years to over 20 years depending on the capacity at the reactor site to store spent fuel after which it is removed and placed in
Figure 4: Schematic of the once-through fuel option
casks under a blanket of inert gas to be stored in shielded, dry storage areas for further cooling. The once-through fuel cycle places the largest demand on repository capacities and after 50-100 years poses one of the biggest proliferation concerns since decay of the fission products over time could allow access and retrieval of plutonium. The advantage of the once-through fuel cycle is that, in the near-term, potentially dangerous and expensive handling and processing of spent fuel is avoided. However, in the long term, large, expensive geologic repositories are needed that must be secured over very long times to prevent removal of plutonium. Currently, the US, Sweden, Spain, Canada, and S. Korea are using the once-through fuel option. 8.1.2. The Reprocessing Fuel Cycle (RFC)
RFC, Figure 5, was the option envisioned by the nuclear power industry from the beginning because it offers the following advantages: Uranium and plutonium would be recovered and recycled to make more energy. The volume of material to be disposed of as HLW would be significantly reduced since the uranium and plutonium comprise about 97% of the total mass of spent fuel. Recovered uranium could be re-enriched, and returned to the LWR fuel cycle, reducing the demand for mining and milling new uranium and the need for
Figure 5: Schematic of a simple RFC.
enrichment services by about 30%. The option to reprocess fuel effectively closes the fuel cycle and has the advantages noted above. However, the development of new separation processes that are efficient and can be carried out under a high-radiation environment is required. Recycling Plutonium as MixedOxide Fuel (MOX) Reprocessed plutonium can be used as fuel in modified LWRs. By adding more control rods to manage the reactivity over the reactor volume, LWRs can be configured to operate using fuel consisting of both uranium and plutoniumoxide or what is termed mixedoxide (MOX) fuel. Over the past 10 years, reactors in France, Germany, Switzerland and Belgium have been licensed to use MOX fuel to generate electricity. Japan plans to have one-third of its 53 reactors using MOX fuel by 2010. MOX fuel is made by mixing plutonium with depleted uranium (a by-product of the uranium enrichment process) or natural uranium. Two sources of plutonium are available. The first is reprocessed plutonium from commercial spent fuel and the second is surplus weapons-grade plutonium from the nuclear stockpiles of the nuclear weapons countries. Such material, reactor-grade and weapons-grade plutonium, differ in the content of 239 Pu and the minor plutonium isotopes, especially 240 Pu . Commercial reactor-grade plutonium is nominally about 5560% 239 Pu and has a relatively high amount ~2025% of 240 Pu whereas weapons-grade plutonium contains greater than 95% 239 Pu and a minor amount of 240 Pu . MOX fuel fabrication facilities are currently operating in France, Belgium, the United Kingdom, India, and Japan and collectively produce about 460 tons per year. For the fabrication of MOX fuel, the age of the plutonium (i.e., the time since the plutonium was last separated from americium) is very important. Am-241, which results from the decay of short-lived 241 Pu isotope ( T1/ 2 = 14.4 a), builds up at a rate of about 2 parts per million per month or about 0.5% per year. Since 241 Am emits a 60 keV X-ray, additional shielding and remote handling is required during MOX fabrication if the 241 Am content becomes greater than 56%. As a result, MOX is usually made with recently reprocessed plutonium. As part of a long-term strategy for reducing the inventory of weapons-grade plutonium, both the US and Russia, plan to construct their MOX fabrication facilities to allow burning this excess plutonium in LWRs. Fabrication plants using weapons-grade plutonium would have to incorporate additional controls to monitor and prevent diversion of plutonium for weapons use. In practice, MOX fuel can be made with fairly high (> 50%) loadings of plutonium but to burn such a fuel would require specially designed reactors. Loadings of the order of 5% (for weapons-grade Pu) to 7% (for LWR reprocessed Pu) are more common for use in modified LWRs. The characteristics of MOX fuel containing 57% plutonium are quite similar to those of the more conventional (45% enriched) uraniumoxide fuel. As a result, MOX fuel can be substituted for part of a reactors fuel loading without any
significant changes in its operating conditions and performance. However, reactors burning MOX typically limit the MOX loading to about one-third of the core fuel assemblies. Since most plutonium isotopes have small thermal neutron fission cross sections, the minor actinides, by neutron capture, build up in the fuel over time and recycle of plutonium in LWRs has serious limitations. However, burning plutonium in MOX fuel using conventional LWRs does have two advantages. (1) it produces useable energy and, (2) it reduces the inventory, preventing the accumulation of separated plutonium resulting from reprocessing commercial power reactor spent fuel. If weapons-grade plutonium is burned as MOX fuel, there are additional advantages over and above reducing the inventory of such plutonium. The first is that, while in the reactor, the weapons-grade plutonium in the fuel would be protected against diversion by the intense radioactive field of the fission products. This is similar to the argument used by those who are against any reprocessing of fuel and claim that by not reprocessing, plutonium left in spent fuel is protected against proliferation by the fission products in the fuel, or what is called the spent fuel standard. Second, while in the reactor, the isotopic composition of the weapons-grade Pu would be degraded and, eventually, resemble reactor-grade plutonium (ca. 65% 239 Pu + 241 Pu and high 240 Pu content). Burning plutonium in MOX fuel reduces the overall radiotoxicity compared with untreated LWR spent fuel but the resulting minor actinides and fission products would require disposition in a geologic repository. Within the commercial nuclear power community, recycling of plutonium in MOX fuel in LWRs is viewed as a mature industry. Uranium Recycling
The uranium recovered from the reprocessing of commercial spent fuel usually contains about 1% 235 U , and, because the PUREX process does not remove 100% of the fission products and other actinides, reprocessed uranium is slightly more radioactive than natural uranium. The increased radioactivity is primarily due to the presence of other emitting contaminants. [According to the International Atomic Energy Agency (IAEA 1977), the level of fission products in reprocessed uranium cannot exceed 19 MBq/kg of U. Similarly, reprocessed U can contain no more than 250 kBq/kg U of other nonuranium alpha activity.] During irradiation, the level of 234 U increases over that in natural uranium. In addition, 232 U , not present in natural uranium, is produced by the decay of 2.85 a 236 Pu isotope. Although the total accumulation of 232 U is small, it decays with a 72 a half-life by -emission through a chain of other - and -ray emitters including the 1.9 a 228 Th . The decay chain finally culminates in 208 Tl , a high energy -ray emitter. The long-lived 236 U ( T1/ 2 = 2.4107 a) is also produced by the
(n, ) reaction on 235 U but adds little to the -activity. The (n, ) reaction on 236 U produces the 6.75 d 237U isotope that decays by beta-emission to 237Np. This decay occurs during storage prior to reprocessing and does not impact the radioactivity associated with reprocessed uranium. In addition to these uranium isotopes, small amounts of plutonium and neptunium remain in the uranium fraction after reprocessing which increases the -activity of reprocessed uranium.
For reprocessed uranium to be used again in a reactor, it must be enriched to about 3.5%. Since new uranium is in plentiful supply, it has not been necessary to re-enrich uranium recovered from reprocessing to meet the requirements for new fuel. If and when it becomes necessary to enrich reprocessed uranium, the potential occupational hazard associated with UF6 conversion, enrichment, and fuel fabrication processes due to the small amounts of residual fission products in the uranium have to be addressed. 8.1.3. Advanced Fuel Cycle (AFC) The potential advantages of the AFC are similar in many respects to those described above for the RFC. However, in the AFC, the HLW problem is reduced by removing and destroying the minor actinides and the long-lived fission products through a process called partitioning and transmutation (P&T). Partitioning involves carrying out a complex series of advanced aqueous chemical and/or non-aqueous metallurgical operations to selectively remove or partition the minor actinides (MAs) and long-lived fission products (LLFPs). Transmutation involves the transformation of the nuclear structure of an atom to form a different atom that is either stable or has a shorter halflife and thus is less of a concern than the original atom. P&T is discussed in greater detail in a later section. 9. Important Characteristics of Actinides
To understand the science of actinide separation chemistry, it is necessary to be familiar with certain characteristic properties of actinide elements. The more important of these are discussed subsequently and more complete discussions can be found in the related EOLSS Chapter by N. M. Edelstein and L. Morss (see: Chemistry of the Actinide Elements), as well as in reviews and books cited in the reference list in the Appendix. The actinides of Z < 96 can exist in oxidation states of III to VI in solution, some in 2 or 3 such states in equilibrium. The changes III IV and V VI are rapid, involving only electron exchange. However, the changes III/IV V/VI are slower as chemical bonds must be broken or made in addition to electron exchange since the An(V) and An(VI) species exist as linear dioxo cations. In all oxidation states, the actinide cations are hard acids and show little interaction with soft base donors such as S, P, etc. in aqueous media. Also, as expected for hard-hard interactions, the bonding to donors is primarily ionic. Am(III) and Am(IV) cations have coordination numbers (CN) of 6 to 12 while the dioxo actinyls have CN = 46. These ranges in CN reflect the ionic bonding which results in the coordination number and symmetry being dominated by steric and net charge effects. The complexation strength normally follows the pattern:
An 4+ >AnO 2 2+ >An 3+ >AnO 2 +
This has been attributed to an effective charge on the An in AnO 2 2+ of 3.3 0.1 and in
AnO 2 + of 2.2 0. In designing specific ligands, it is important to be aware of the following properties:
An-N bonds are longer-lived than An-O bonds; An-O bonds promote and may be necessary to the formation of An-N bonds; five-membered chelate rings are the most stable; prearranged structures are more stable; if too rigid, prearranged structures may be too slow to form; bulky steric groups can slow dissociation kinetics; redox, steric effects, high CN, and weak bond covalency (in extractant ligands) can be exploited to improve specificity in separations.
10. Separations Technologies for the Nuclear Fuel Cycle
Separation processing of irradiated nuclear samples has been a major emphasis in nuclear technology since the first separation experiments by W. Crookes and H. Becquerel in the late 1890s. These initial separations, including those that led to the discovery of Po and Ra in 1898, used precipitation as the chemical isolation and purification method for the radionuclides. Precipitation remained the predominant separation technique in radiochemistry even in the Manhattan atomic bomb project of the 1940s, which achieved radiochemical separations of plutonium from uranium and the decay and fission products. Initially, the separation used was the Bismuth Phosphate Process with BiPO4 as the carrier for the insoluble phosphates of Pu(III) and Pu(IV) to obtain separation from the soluble UO 2 2+ phosphate complexes.
The BiPO4 method was replaced by solvent extraction processes which used continuous, remote controlled operations for isolation of uranium and plutonium from the fission products and from each other. The initial solvent extraction system, REDOX, used methylisobutyl ketone (MIBK or kexone) as the extracting solvent. However the
Figure 6: Fuel reprocessing chemistry
REDOX process had the problem of hexone decomposition in the nitric acid solution from the dissolution of the spent fuel. It was displaced by the PUREX (Plutonium Uranium Redox Extraction) which continues to be the major system for spent nuclear fuel processing. Figure 6 summarizes these separation methods. 10.1. PUREX Process The major system used internationally for processing spent nuclear fuel has been PUREX. The PUREX process is shown in Figure 7.
The PUREX process uses tributylphosphate, TBP, dissolved in kerosene to separate UO 2 2+ and Pu 4+ from fission products. The PUREX process depends on the relative ease of redox of plutonium which allows recovery of purified plutonium from much greater concentrations of uranium. In PUREX, both solvent and aqueous reagent streams can be recycled for reuse, reducing the amount of process waste. The plutonium and uranium are separated with decontamination factors greater than 107 from fission products. The amount of plutonium and uranium which remain with the fission products in the aqueous waste streams is usually tenths to a few percent. Depending on the composition of the spent fuel, additional separation steps may have to be added to the PUREX process to obtain satisfactory separation of certain fission products in the wastes. For example, it is possible to selectively remove long-lived fission products (e.g., 137 Cs ) from the waste streams using ion-exchange processes. An
Figure 7: Schematic of the PUREX process
example of an additional solvent extraction system is the SREX process, which uses complexation to a crown ether to remove Sr-90 from the PUREX waste streams. 10.2. DIAMEX Process The DIAMEX process is the result of a research program of the European Union with the goal of improved actinide element separation from fission products in acidic nuclear waste solutions. Bifunctional diamides have advantages for actinide extraction in such waste solutions such as their incinerability and the fact that their radiolytic and hydrolytic degradation products do not hamper the process. The diamide N,N-dimethyldioctylhexyloxyethylmalonamide, (CH 3C8 H17 NCO) 2 CHC2 H 4 OC6 H13 (DMDOHEMA) was found to have the necessary properties for use. It has disadvantages, such as the formation of degradation products which are more soluble in the organic phase due to the replacement of the CH 3C4 H 9 N group by CH 3C8 H17 N . However, these are balanced by its improved separation factors from fission products such as Mo(VI) and Ru as well as from contaminates such as Fe(III). An important factor is that the recovery of An(III) and An(IV) and AnO 2 2+ species is quantitative. The stripping of Pu(IV) and U(VI) from the DIAMEX extractant solution is satisfactory but the extraction and stripping from DIAMEX of Pd, Tc and Np is not satisfactory and is being studied for improvement. 10.3. TRUEX Process
This solvent extraction process is designed to separate transuranic elements from the acidic high-level waste solutions of PUREX. The extractant, octyl(pheny)-N,Ndibutylcarbamoyl-methylphosphine oxide (CMPO), is dissolved in an alkane solvent. CMPO can extract transuranic elements from acidic solutions almost quantitatively and selectively. TRUEX treatment of the waste streams from PUREX separation of plutonium and uranium reduces the concentrations of residual U and Pu in the wastes by factors of 100 to 1000 but does not separate tri- and tetravalent actinides from the lanthanide fission products. A problem with the use of TRUEX is the need for aggressive stripping conditions to recover the An(III) and An(IV) species from the organic phase due to the strength of their complexation by CMPO.
10.4. TRAMEX Process
Liquid cation exchangers, such as trialkylamines and tetraalkylammonium salts dissolved in organic solvents, provide high selectivity in the separation of tri- and tetravalent actinides from lanthanides and most other fission products. This is the basis of the TRAMEX process. The separation is usually accomplished using aqueous solutions with high chloride (e.g., 10 M LiCl) concentrations and requires pretreatment to convert the aqueous nitrate solution of the wastes from the PUREX process to the chloride feed solution. As the strong corrosive nature of the concentrated chloride solution requires special processing equipment, it would be an advantage to develop separations from high nitrate salt solutions. A partitioning/transmutation system (discussed below) requires the separation of actinides as the first step for which the TRAMEX process could be used. 10.5. TALSPEAK Process
The high cross sections for neutron absorption of some lanthanides require their removal from recycled spent fuel as well as from the target material for transmutation of actinides. The TALSPEAK (Trivalent Actinide Lanthanide Separation by Phosphorus Extractants and Aqueous Komplexes) process separates lanthanides from trivalent actinides in acidic solutions of pH 2.53.0. In the normal version of the TALSPEAK process proposed for use in the partitioning/transmutation technologies, the trivalent lanthanides are extracted by di(2-ethylhexyl) phosphoric acid (HDEHP) from an aqueous solution of lactic and diethylenetriaminepentaacetic (DTPA) acids while the trivalent actinides remain in the aqueous phase. In the reversed version, the Am(III)
Figure 8: The TRUEX Process
and Ln(III) cations are extracted into an organic phase containing HDEHP in the first step, followed by stripping of the trivalent actinides into an aqueous phase containing lactic and DTPA acids. Subsequently, the trivalent lanthanides in the organic phase can be recovered by stripping with 6 M nitric acid. A disadvantage of the TALSPEAK process is the formation of radiolytic degradation products of the organic complexing agents and pH buffering agents which could affect control of the process. 10.6. Stereospecific Extractants While many of the extractants discussed have strong complexation properties, their selectivity in the separation of some radionuclides is insufficient. Crown ethers, cryptands and similar macrocyclic ligands can provide the desired high stereoselectivity for specific nuclides that match their cavity size and shape. Good separation factors have been reported between trivalent lanthanides and trivalent actinides for solvent extraction systems based on complexants with soft donor groups (e.g., nitrogen and sulfur). These complexants are based on amide functional groups or on sulfur based diketone extractants. However, redox techniques can separate the actinides, including thorium and uranium, more simply and, usually, more efficiently. Research on soft donor ligand systems for separation of the transplutonium actinides from the lanthanides continues and such a process could be used if a separating ligand with very high radiation stability and low aqueous solubility is found. The efficiency of regeneration of reagents for reuse is a problem if the specificity is due to a strong rigidity and, hence, inertness of the ligand structure.
Sr and 137 Cs are the major sources of radioactivity and heat in nuclear wastes and their removal prior to further separation greatly simplifies subsequent waste handling and storage. A Sr(II) extraction/recovery process, SREX, uses a solution of a crown ether, 4,4(5)-di-t-butylcyclohexano-18-crown-6 (DtBuCH18C6), and TBP in Isopar-L. SREX can remove strontium from the waste streams of the PUREX process. A modification of the process, called CSEX-SREX, provides the removal of both Cs and Sr by extraction with a dibenzo-18-crown-6 derivative of proprietary composition. Both processes achieve very high decontamination factors for Sr and Cs.
90
Table 8 lists a number of aqueous-based separations used or under development to support reprocessing spent nuclear fuels and advanced fuel cycle concepts. Ligand Class Separation Process DIDPA- di-isodecylphosphoric acid uses TBP as a modifier to avoid third phase formation HDEHP di-2-ethyl-hexyl-phosphoric acid TALSPEAK uses HDEHP with TBP as a modifier to avoid third phase formation to extract Ln from an aqueous solution containing lactic or glycolic acid and diethylenetriaminiopentaacetic acid (DPTA). Ac stay in aqueous phase
Phosphoric acid based DIDPA, HDEHP, TBP
CMPO-carbamoylmethylphosphine oxide
Alkyl-phosphine oxides
Azines
Pyridine and Amides
Thio-phosphinic acid based
Crown ethers
Table 8: Some of the aqueous-based separation methods used or under development for reprocessing spent nuclear fuel. 10.7. Non-aqueous Processes Non-aqueous processes have been developed to various levels for separation of radionuclides. These non-aqueous techniques use differences in such properties as volatility and redox behavior of the radioactive elements in molten salt solvents and have been employed successfully in uranium isotope separations, in electrorefining of plutonium, and in the production of metallic fuel for advanced nuclear reactors. Some
Electrochemical redox with heteropolyions
Diamides
TRUEX TRans Uranium EXtraction n-octyl-phenyl-di-isobutyl-carbamoylmethylphosphine-oxide (CMPO),strong complexing makes stripping with conventional dilute solutions difficult, requires more powerful stripping agents that increase quantity of secondary waste TRPO - Trialkyl phosphine oxide, must neutralize feed to allow extraction and then raise the acidity to strip the Ln and Ac, Zr, Mo, Ru and Tc interfere with separation DIAMEX DIAMide EXtraction uses malonamide extractants, extraction/ scrubbing/ stripping cycle similar to TRUEX but no solid secondary waste expected because extractant is fully destroyed by incineration. TPTZ Tripyridyltriazine used with dinonylnapthalenesulfonic acid (HDNNS) to selectively extract An Picolinamides N and O chelating agents that can selectively extract Ac over Ln but requires high nitrate and low proton concentration CYANEX 301 mixture consisting of mainly bis(2.4.4. trimethylpentyl) dithiophosphinic acid, requires relatively high pH (3.5-4.0), often is used synergistically with TBP SESAME electrochemical method used to oxidize Am to either the +6 or +5 state in nitrate media but because of difficulty keeping Am oxidized in aqueous media, use of a complexant to reduce the apparent redox potential is needed. The cage-like heteropolyion, potassium phosphotungstate is used. Oxidized species is then separated by extraction. SREX Sr Extraction uses dicyclohexano 18crown-6 ether to selectively extract Sr from acidic liquid waste
non-aqueous processes being evaluated as separation technologies for treatment of nuclear wastes are reviewed. 10.7.1. Volatility Processes Uranium hexafluoride has been used for uranium isotopic enrichment in the gaseous diffusion process. Plutonium and neptunium also form volatile hexafluoro compounds. The radiolytic decomposition of PuF6 to PuF4 and F2 in the volatilization process is a disadvantage of the method, since PuF4 is less volatile and deposits on the surfaces of the equipment. Some -diketone ligands form relatively volatile compounds with trivalent lanthanides, indicating the volatility can be expected for trivalent actinides although uranium and plutonium tetravalent and hexavalent -diketones have much lower volatilities. For diketonates such as fod (6,6,7,7,8,8,8-hepta-fluoro-2,2-dimethyl-3.5-octanedione), separation factors greater than or equal to 104 for uranium and plutonium from Am can be expected. Fod has the desirable properties of stability to air and water at temperatures 100C and can be recovered by extraction with an organic solvent. Processing of large volumes of aqueous waste by extraction with -diketones followed by volatilization of the -diketonate complexes may have engineering problems to overcome before use of these volatile compounds could be considered as a viable separation option for the large volumes of defense wastes. 10.7.2. Molten Salt Processes
An important advantage of the molten inorganic salts as well as of molten metals for spent fuel processing is their inherent resistance to radiation damage. For example, pyrochemical systems allow processing reactor fuels after minimum cooling time even through they have very high concentrations of fission products, high decay-heat output and intense radiation emission. In fact, the decay heat can be an advantage since it can be used to maintain the pyrochemical fluid at the process temperatures of 500 to 800C. The Salt Transport Process is a sophisticated pyrochemical method for recovering U and Pu from residues of fast reactor fuels. In this process, plutonium and uranium are separated from fission product residues and other spent reagents. The basis of the separation is the transport of actinide metals between two molten alloys of magnesium, one containing copper and the other containing zinc. The alloys are chemically connected by an ionic molten salt solvent which allows movement of ions between the alloys. Equilibrium is established rapidly at the operating temperature (800C) and plutonium can be separated from uranium by a factor of about 10 and the fission
Two basic types of molten salt systems have been used in separations: (1) a mixed fluoride salt which was used both as the coolant and as the fuel and blanket system in the Molten Salt Reactor Experiment (MSRE) and (2) the chloride eutectic salts which have been used as an ionic solvent in pyrochemical spent fuel reprocessing systems proposed for use with highly irradiated metallic reactor fuels.
products are isolated from the actinide elements. The noble element fission products are retained in the copper-magnesium alloy, and the more reactive products (Cs, Sr, and the rare earth elements) remain as ionic species in the transport salt phase. No external electrical potential is needed in this process as the separation is accomplished by oxidation of the plutonium by the chloride solvent salt at the copper-magnesium interface, and reduction of the plutonium chloride by the magnesium alloy at the magnesium-zinc interface. 10.7.3. Electrochemical Separations using Non-Aqueous Processes The electrochemical technique known as electrorefining was developed to purify plutonium metal alloys to be used in the LAMPRE reactor project (Los Alamos Molten Plutonium Reactor Experiment). LAMPRE never operated but the separations technique was adapted to purification of plutonium and uranium metals for both weapons and breeder reactor fuels. Electrorefining is classified as a pyrochemical process since it uses a molten ionic salt as a transfer medium of pure Pu/U metal to the cathode. The process somewhat resembles the Salt Transport Process described above, but the driving potential is provided electrically and can be controlled very precisely to provide a cathode product that is extremely pure. Spent driver fuel and blanket fuel used to breed plutonium from the Experimental Breeder Reactor (EBR II) has been successfully reprocessed by the electrometallurgical process developed by Argonne National Laboratory (ANL). EBR-II driver fuel consists of highly enriched uranium metal alloyed with about 10% Zr and clad in stainless steel. The blanket fuel (depleted uranium metal) also uses stainless steel cladding. Briefly, the electrometallurgical treatment (shown schematically in Figure 9) involves chopping the spent fuel into small pieces and placing it in an anode basket inside an electrorefiner vessel containing a LiCl/KCl salt mixture heated to about 500C. Prior to electrolysis, an oxidant such as CdCl2 or UCl3 is added to the salt. Upon passage of a constant electrolysis current between the anode basket and a steel cathode, elements that form very stable chloride compounds (e.g., actinides, alkali, alkaline earth and rare earth elements) dissolve into the salt leaving the less stable chloride compounds (e.g., Cd, Fe, Nb, Mo, noble metals) with the cladding hulls in the anode basket. The electrolysis is carried out under controlled current conditions such that principally U3+ is reduced to the metal at the cathode. After a period of time the cathode is removed from the electrorefiner and the U metal is recovered after the adhering salt is removed by volatilization in a vacuum furnace. The uranium is then cast into an ingot in a high-temperature furnace and stored.
Figure 9: Flow diagram of the non-aqueous electrometallurgical process developed and used to reprocess EBR II spent fuel. Courtesy: (NAS 2002) Electrometallurgical Techniques for DOE Spent Fuel Final Report, National Academy Press, p. 21, Fig. 2.2. ANL also demonstrated a variation to this flowsheet that uses a liquid Cd cathode in addition to the steel cathode, as shown in Figure 10. The Cd cathode permitted the separation of Pu, the transuranium elements, and some rare earth fission products from the salt. Without the Cd cathode, these elements remained along with most of the fission products in the salt. The salt was subsequently processed by adding zeolite, heating to adsorb the salt into the zeolite, adding glass and then hot isostatically press the mixture to form a glass bonded sodalite ceramic waste form. The cladding hulls, noble metal fission products, and any unoxidized material that remained in the anode basket were subjected to removal of adherent salt by volatilization and converted to a metallic waste form by adding more Zr and cast into an ingot in a furnace. By changing the head end treatment steps, other types of fuel can be accommodated in this non-aqueous process. For example, an initial Li/Li2O step can be added to convert oxide fuel to the metallic form. To be compatible with the electrometallurgical treatment just described, the electrorefiner requires the spent fuel be in a metallic form.
Figure 10: Modified flow diagram of the non-aqueous electrometallurgical process that used a liquid Cd electrode to separate the TRU elements from the majority of the fission products. Courtesy: (NAS 2002) Electrometallurgical Techniques for DOE Spent Fuel Final Report, National Academy Press, p. 21, Fig. 2.3. This electrometallurgical process with some modifications and additional development could be used in transmutation schemes involving other fuel types such as metaloxides and nitrides and in situations where cooling periods as short as 35 months are required. ANL has already developed an electrochemical head end process to convert the oxide fuel to the metallic form by reducing the oxide in a LiCl/Li2O molten salt bath. The resulting metal fuel could then be electrorefined using the process described for EBR-II fuel. 11. Advanced Fuel Cycle Concepts and Partitioning and Transmutation (P&T)
The Advanced Fuel Cycle (AFC) is an option that not only closes the fuel cycle but also allows significant reduction of the inventory of long-lived radionuclides in the waste. This option is viewed favorably because (1) unused uranium and plutonium in the spent fuel is recovered for future use to generate energy (economic issue); (2) the associated radiological hazard is greatly reduced because long-lived actinide isotopes are removed (public health and safety issue; (3) the volume, heat load, containment times, and repository requirements are significantly decreased (cost issue). The AFC requires coupling and integration of all of the processes and steps in the fuel cycle from fuel fabrication through disposal. It differs from the RFC in that, in addition to the removal of uranium and plutonium, the minor actinides (neptunium, americium, and curium, and small amounts of the heavier actinides) and some of the long-lived fission products (principally, technetium, and iodine) are partitioned from the waste stream and transmuted prior to vitrification and final disposal in the HLW. Partitioning involves a
Figure 11 shows the relative ingestion toxicity of HLW from spent fuel as a function of time after discharge from the reactor by various scenarios of partitioning and transmutation (P&T). If no attempt is made to remove the MA, it takes on the order of 105 years for the spent fuel to decay to the level of 1 ton of natural uranium. However, if 99.9% or a ten-fold decrease in the MA content is achieved by P&T, it takes only about 500-700 years to reach the same level. Although not shown on the graph, a partitioning scheme that includes only the partitioning of plutonium for recycle and not the minor actinides for transmutation, reduces the long-term radiotoxicity of the waste by only about a factor of five. Therefore, plutonium and the minor actinides have to be considered together for any transmutation scheme to be beneficial. It should be further recognized that any fuel cycle strategy involving partition and transmutation that does not include breeding of plutonium addresses only long-term waste issues but does nothing to improve the resource utilization of uranium. If reducing the MA content 100fold requires isolation of HLW for only 500-700 years to reach the level of natural uranium, containers designed to enclose the HLW would fulfill this safety requirement.
complex series of aqueous chemical and/or non-aqueous metallurgical operations to selectively remove or partition the minor actinides (MAs) and long-lived fission products (LLFPs). Transmutation involves the transformation of a minor actinide or long-lived fission product into another nuclide that is either stable or has a shorter halflife and thus, is less of a problem than the original radionuclide. Transmutation involves using nuclear reactions and processes such as neutron capture followed by radioactive decay, (n, 2n) reactions with energetic neutrons, or neutron induced fission (thermal or fast) to achieve the desired transformation. Transmutation, sometimes referred to as incineration, can be accomplished through a combination of LWRs, fast reactors (configured either as breeders or as minor actinide or transuranic [TRU] burners), and subcritical, accelerator-based transmutation devices. The AFC option is the least developed of the fuel cycles although many of the technologies that are needed are well understood and, in some cases, quite mature. Because of concerns about greenhouse gases and global warming, many countries are moving toward increasing the amount of energy produced by nuclear reactors and closing the fuel cycle with various adaptations of AFC.
11.1. Transmutation of Minor Actinides
For the purpose of transmutation, the minor actinides of concern in spent fuel are neptunium, americium and curium although small amounts of the higher actinides, berkelium, californium, einsteinium, and fermium can be made under the right conditions. The reaction pathways leading to the production of the transuranium elements are given in Figure 12. For the minor actinides, the transmutation process consists in the capture of one or more neutrons until a more fissionable isotope is formed. For the actinides, the most important transmutation reaction is fission because it results in the removal of the isotope from the minor actinide inventory and replaces it with two typically shorter lived, less toxic fission fragments. With more energetic neutrons, the (n, 2n) reaction is also useful because this reaction transforms fertile actinides with low fission
Figure 11: Relative ingestion toxicity of representative fission products and some actinides in spent fuel as a function of time after discharge from a PWR. Note reduction in toxicity resulting from P&T under various scenarios of MA and LLFP removal.
probabilities to actinides with higher fission probabilities. Neutron capture reactions that produce less fissionable isotopes add to the inventory of minor actinides.
Figure 12: Neutron capture pathways of importance for the production of actinides. Courtesy: (NAS 1996) Nuclear Wastes, Technologies for Separations and Transmutation, National Academy Press, p. 22, Fig. 2-1. Because thermal neutrons are not as effective for inducing fission reactions as more energetic neutrons, conventional LWRs alone cannot be used to transmute minor actinides. Thermal reactors tend to preferentially produce minor actinides which (especially, non-fissile even A isotopes of plutonium) increase in amount as a function of time. Fast reactors or fast neutron spectrum devices more effectively destroy the minor actinides because the probability of fission is considerably higher with fast neutrons compared to thermal neutrons for both even and odd A isotopes of plutonium fission. Thus, fast neutron devices are much preferred for the recycle of plutonium and the ultimate complete destruction of all of the minor actinides. The transmutation yield in reactors using either thermal or fast neutrons is not the only factor that must be taken into account when developing transmutation scenarios for the minor actinides. Of equal or greater importance is the impact of loading of MAs on the stability of the reactor during normal operations. For example, the addition of minor actinides can result in transients or local spikes of the neutron flux within the reactor volume effecting the overall reactivity and stability of the reactor core. Transmutation of 237 Np (with half-life of about 2 million years) is possible in both thermal and fast reactors. For reactor transmutation, neptunium can be incorporated in either LWR UO2 or MOX fuel and transmuted homogeneously with UO2 or heterogeneously as a mixture of UO2 and PuO 2 . Neither approach presents any significant problems with respect to reactor operation at small loadings (a few percent). Fuel fabrication involving neptunium however is a bit more difficult because 237Np decays to 233Pa which emits a number of energetic -rays, requiring additional shielding. As a result, the alpha activity and gamma radiation levels are significantly higher when neptunium is added to the mix during conventional UO2 fuel fabrication. For MOX fuel
fabrication, the impact is much less. In this case, the presence of neptunium is inconsequential with respect to alpha activity but the gamma radiation level is significantly increased. This situation changes, however, upon multiple recycling of MOX fuel. Neutron capture by 237Np leads to an increase of the short-lived 238 Pu isotope ( T1/ 2 = 88 y) which decays by alpha emission with a high decay energy. As a result the alpha activity increases significantly as well as does the heat load during processing. The (, n) reaction of light elements also becomes important as a result of the high alpha energy associated with the decay of 238 Pu . Neutrons emitted from (, n) reactions complicate not only fuel fabrication but also the transportation and storage of the fuel.
7900 a) produced by the beta decay of 241 Pu and 243 Pu respectively. The 152 a 242m Am isotope, formed by the (n,) reaction of 241 Am is also of importance because its decay leads to 242 Cm . This nuclide, with its very short 163 d half-life, is the most intense -emitter in spent fuel. Successive neutron captures by 243 Am , followed by beta decay, leads to the production of curium with masses of 244, 245, and 246. The ability to transmute 241 Am is particularly advantageous because it is the parent of long-lived 237 Np . Thus, if 241 Am can be removed from the HLW stream and destroyed by fission, a major source of 237 Np can be eliminated. However, transmutation of 241 Am is complicated due to its emission of a 60 keV -ray. Because of this gammaray, fuel fabrication involving significant quantities of americium requires shielded facilities with equipment modified with remote operation. For these reasons, blending americium to form MOX fuel (homogeneous recycle) is difficult and the preferred method of transmutation is by using specially prepared targets (heterogeneous recycle).
Because curium isotopes have both shorter half-lives and higher spontaneous fission branches compared with neptunium and americium, their transmutation in reactors poses another set of problems. In spent fuel, 242 Cm ( T1/ 2 = 163 d) is, by mass, about 100
times less abundant than the 18 a 244 Cm isotope but its specific activity is about six times higher. Both the high specific activity and the neutron intensity associated with curium makes handling operations and fuel fabrication much more difficult than even americium. Any transmutation scheme involving curium is complicated by the fact that curium decays primarily by -emission to produce isotopes of plutonium. Specifically, 242 Cm -decays to 238 Pu , 243 Cm to 239 Pu , 244 Cm to 240 Pu and 245 Cm to 241 Pu , etc. For the case of transmuting the most abundant curium isotope by mass in spent fuel, 244 Cm , the in-growth of 240 Pu causes problems because of its low thermal fission cross section. As a result, transmuting 244 Cm in a LWR is not practical. However, this is a case where using the delay and decay can be advantageous. For example, if 244 Cm is stored for about 100 years, it will decay to ~2% of its original value and the 240 Pu that has grown
Figure 12 shows the transmutation pathways for the production and destruction of Am isotopes. For americium, there are primarily two isotopes of concern in developing any transmutation scheme. They are 241 Am ( T1/ 2 = 460 a) and the longer-lived 243 Am ( T1/ 2 =
in could be separated and transmuted in a fast reactor along with normal plutonium recycling operations. 11.2. Transmutation of the Long-lived Fission Products In addition to removing the MA, there are a few long-lived fission products that, if they could be partitioned and transmuted as well, would further reduce the radiotoxicity of HLW by about another factor of ten. (See Figure 11.) The most important fission products associated with long-term risks are technetium (existing only as 99 Tc ), iodine, and possibly cesium. The transmutation process for fission products is basically the capture of a neutron (or several neutrons) followed by beta decay until a less toxic (shorter-lived) or stable nuclide is formed. For technetium and iodine, the transmutation can be accomplished in thermal reactors through the following pathways:
99
Tc (T1/2 = 2.13105 a)
99Tc + n 100 Tc
129
I (T1/2 = 1.6107 a)
129
127
I (stable)
127
For both technetium and iodine, capture of a single neutron followed by decay results in the production of stable isotopes of ruthenium and xenon respectively. Further, as the irradiation proceeds additional neutrons can be captured but these products are also stable. In practice, the transmutation of technetium and iodine in conventional thermal reactors is difficult for several reasons. First, because these isotopes are major fission products, they are produced in high yield and, over time, result in large inventories that must be separated from the HLW and transmuted. Second, the thermal neutron capture cross sections are not particularly large so much higher neutron fluxes are required to reduce significantly the inventory in a reasonable amount of time. Third, the available neutron flux from conventional LWRs is too small (1013 n cm-2 s-1) to achieve the required level of transmutation in a reasonable length of time. For cesium, the long-lived fission product of concern is 135 Cs . However 135 Cs constitutes only about 15% of isotopes of cesium that are produced in fission. The relatively short-lived 137 Cs ( T1/ 2 = 30 a) and stable 133 Cs are present in amounts similar or greater than
135

100
Ru + n
101
Ru + n 102 Ru
(T1/2 = 16 s)
(stable)
(stable)
(stable)
I+n
130
130
Xe + n 131 Xe + n 132 Xe (stable)
(T1/2 = 12.4 h)
(stable)
(stable)
I+n
128
128
Xe + n
129 Xe + n 130 Xe (stable)
(T1/2 = 25 min)
(stable)
(stable)
Cs. Cs-134 ( T1/ 2 = 2 a) is also present at about the percent level.
Although 135 Cs can be converted to stable 136Ba by neutron capture followed by beta decay, this is not practical because the highly radioactive 137 Cs isotope would make handling the material extremely difficult. In addition, neutron capture by the other cesium isotopes, 133 Cs and 134 Cs , would produce more 135 Cs than would be transmuted. The only way around these problems would be to remove 135 Cs by isotope separation prior to transmutation. Since isotope separation is a very costly process, transmuting 135 Cs may no be cost effective. Similar situations exist for transmuting the long-lived isotopes of zirconium ( 93 Zr ), selenium ( 79 Se ), and tin ( 126 Sn ). Although some of the long-lived fission products have thermal neutron capture cross sections suitable for transmutation in reasonable irradiation times, others do not and would require reactors with very high neutron fluxes to significantly reduce inventories. For such reduction, dedicated reactors with large thermal fluxes and/or dedicated accelerator-driven systems (ADS) with thermal neutron fluxes of the order of 1016 n cm2 -1 s are being considered. Fast neutron capture cross sections for most long-lived fission products are several orders of magnitude smaller than those for thermal neutrons, making transmutation by fast reactors very difficult. Because of the relatively low transmutation rates for long-lived fission products, transmutation of these radionuclides is expected to be very expensive unless new, cost-effective technologies are developed. In general, transmutation of long-lived fission products, although theoretically possible, is very difficult and would require significant development to be successful. Fission products under transmutation conditions are only consumers of neutrons and, unlike the actinides, do not produce additional neutrons useful for further transmutation. Consequently, the product of the capture cross section and the neutron flux must be higher than the decay constant of the isotope for it to be a realistic candidate for transmutation. Without prior isotopic separation, the transmutation of only a few longlived fission products, namely iodine and technetium and, possibly 107 Pd , are feasible. Thus, the best way to minimize the long-term radiological impact of most long-lived fission products is to separate and immobilize them in specially designed, stable waste forms. 11.3. Partitioning Schemes for the Minor Actinides and Long-lived Fission Products
In order to realize the AFC and significantly reduce the inventories of minor actinides and possibly, of some long-lived fission products, advances are required in the chemical processes used to separate or partition these elements from spent fuel. A number of aqueous processes have been studied that are either variations or extensions of the conventional PUREX process. In addition to separating uranium and plutonium for recycle as fuel, aqueous processes could be used for the initial, first cycle separation of selected long-lived fission products, the minor actinides, and possible cesium and strontium from spent fuel. Because aqueous processes undergo radiolysis in intense radiation fields from fresh spent fuel, non-aqueous processes are required, particularly in multiple recycle situations where minimizing the time between fuel discharge and fuel reprocessing is critical. In addition to developing new chemical separation
12. Aqueous Chemical Processing
12.1. Improved PUREX Process Removal of Np, I, and Tc
Neptunium can be effectively separated by a relatively simple modification to the conventional PUREX process. Neptunium can be oxidized to the VI state by nitrous acid and extracted into the organic phase with U and Pu in the first cycle and, later, separated during the second purification cycle of uranium. Neptunium can be transmuted by blending with MOX fuel (homogeneous recycle) or fabricated into special targets (heterogeneous recycle) for irradiation. Unlike neptunium, the other minor actinides, americium and curium cannot be separated by modifying the PUREX process. Processes such as the TRUEX process, described previously, must be designed specifically to remove americium and curium (trivalent actinides) from HLW. Technetium and iodine can also be separated by reasonable modifications to the traditional PUREX process. During dissolution, 1020% of the technetium remains as an insoluble residue with the noble metals Ru, Rh, and Pd with the cladding hulls. The technetium that does dissolve in the nitric acid is Tc(VII) as TcO4 which can be extracted by TBP. Iodine is released as a gas in the dissolution step and is separated by trapping it from the off-gas. A flow diagram showing the removal of Np, I, and Tc from such a modified PUREX process is shown in Figure 13.
processes, a significant amount of development is needed on fabrication of targets of minor actinides and long-lived fission products compatible with transmutation devices. The reprocessing of conventional LWRMOX fuel for recycling the transuranium elements (TRU) and burning them in fast reactors or in dedicated transmutation devices is conceptually possible in present PUREX reprocessing plants. The same PUREX process used for the removal of transuranium elements from HLW from the reprocessing of once through LWR UO2 fuel from conventional nuclear power plants can be used for MOX. However, reprocessing of MOX fuel is more difficult because the radiotoxicity is about eight times greater for MOX compared with once through spent LWR UO2 fuel. Subsequent reprocessing of recycled MOX fuel would require dedicated facilities with more shielding and remote handling capabilities and new, nonaqueous processes.
Figure 13: The PUREX process modified for the separation of Np, I, and Tc. 12.2. UREX and UREX+ Processes
A variation of the PUREX process that has been proposed as a possible alternative partitioning scheme for the transmutation of wastes is the UREX process. In this aqueous based process, shown schematically in Figure 14, uranium and technetium are co-extracted from a nitric acid solution containing the dissolved spent commercial LWR fuel with plutonium in the HLW stream with the other minor actinides and fission products. UREX, like the PUREX process, uses tri-butyl phosphate (TBP) as the extractant. However, in the UREX process, uranium is extracted at a high separation factor in one extraction cycle. The distinguishing feature of the UREX process is the addition of a reductant/complexant, acetohydroxamic acid (AHA), to the dissolver solution. The addition of AHA results in the suppression of plutonium extraction and in the retention of certain fission products (e.g., Mo, Zr, and Ru) that would otherwise contaminate the organic phase. Technetium is back-extracted into a high acidity aqueous phase, yielding a relatively pure technetium stream. Uranium can then be stripped from the organic phase. The UREX liquid waste stream or raffinate contains all of the transuranic elements and all of the fission products except technetium, iodine, xenon and krypton. The separation requirements for the UREX process development include recoveries of uranium and technetium at greater than 99.9% and 95% respectively. (Note: Iodine is released as a gas in the dissolution step and is separated by trapping it from the off-gas line.)
U
o o o o
N
Uranium
The UREX+ process is a series of five solvent-extraction flowsheets that perform the following operations: (1) recovery of Tc and U (UREX), (2) recovery of Cs and Sr (CCD-PEG), (3) recovery of Pu and Np (NPEX), (4) recovery of Am, Cm, and rareearth fission products (TRUEX), and; (5) separation of Am and Cm from the rare earth fission products (Cyanex 301). The goals of the separation process development for UREX+ include:
Technetium o Recovery 95% o Purity only important for use as transmutation target Cesium/Strontium o Recovery 97%
Figure 14: Flow diagram for the UREX process.
Recovery 90% Purity to allow disposal as low-level waste Fission products to meet regulatory limits and TRU < 100 nCi/g (3700 Bq g-1) If U is to be recycled, additional separations would be required to increase the purity to the acceptable standard
o Contribution to the heat load in the repository equal to that of all other fission products o Purity to allow ultimate disposal as low-level waste after decay storage Plutonium/Neptunium o Recovery 99% to allow 100-fold reduction of heat load to repository o Purity to meet mixed-oxide (MOX) fuel specifications Americium/Curium o Recovery 99.5% to allow 100-fold reduction of heat load to the repository o Purity to meet fast-spectrum reactor lanthanide specification of < 20 mg/g Uranium plus TRU Raffinates from the UREX+ process
o TRUEX, all soluble fission products but Cs, Sr, Tc, I, and REEs o Cyanex 301, RE elements o Purity requirements are basis for recoveries in other streams
The flow diagrams for steps 2 and 3, and steps 4 and 5, in the UREX+ process are shown in Figures 15 and 16 respectively.
Figure 15: The flow diagram for Step 2 (recovery of Cs and Sr using CDC-PEG, a mixture of chlorinated cobalt dicarbollide (CCD) for cesium extraction and
polyethylene glycol (PEG) for strontium extraction diluted by phenyltrifluoromethyl sulfone) and Step 3 (for recovery of a pure Pu/Np product) using the NPEX process.
Figure 16: The flow diagram for Step 4 (recovery of Am, Cm, and rare-earth fission products using TRUEX) and Step 5 (separation of Am and Cm from the rare earths using Cyanex 301). If UREX+ can be successfully used, it has the advantage that iodine and technetium are captured for safe disposal, uranium is recovered as U 3O8 for recycle or disposal as LLW Class C waste, Np and Pu are recovered together for blending into MOX fuel for thermal reactors, Am and Cu are separated together and can be transmuted in a fast reactor, Cs and Sr are removed from the waste stream going to a repository, greatly reducing the heat load in the waste form, and, finally, the remaining fission products are stored in the repository. 13. Non-Aqueous Chemical Processing
One of the most challenging R&D areas impacting waste management for the advanced fuel cycle is the development of non-aqueous processes. Because of the higher burn-up needed for transmutation as well as the need for multiple recycling with minimum cooling time between fuel discharge and reprocessing, non-aqueous processes offer important advantages. Non-aqueous processes are much more radiation resistant than aqueous processes and can be used to reprocess spent fuel after considerably shorter cooling periods. Other advantages include the potential to produce much smaller quantities of secondary waste and waste forms suitable for long-term disposal, the ease
of recycling of reagents used in separations, and finally, the compactness of equipment which reduces the physical size of the plant needed. However, the separation factors are usually smaller, requiring multiple stages to achieve relatively high levels of decontamination. Also, the processes must be conducted under highly controlled atmospheres (e.g., dry argon) to avoid hydrolysis and precipitation reactions. Nonaqueous systems typically have a rather limited throughput as they are usually operated in batch rather than continuous processes. However, this is not a severe limitation in a transmutation scenario as after the initial processing of the spent fuel, the volume of material to be processed in the transmutation cycle is only a fraction of the initial fuel volume. Currently, non-aqueous separation schemes are under investigation in several countries including the US, Russia, and Japan. However, the most advanced non-aqueous processing scheme that has been demonstrated on an engineering scale is the electrometallurgical process developed by Argonne National Laboratory (ANL). This process, developed for metallic fuels, is described in detail in the earlier section entitled Electrochemical Separations using Non-aqueous Processes. However, by changing the head end treatment steps, the ANL electrometallurgical process can be modified to accommodate other fuel types such as oxides and nitrides. For example, an initial Li/Li 2 O reduction step can be used to convert oxide fuel used in LWRs to the metallic form. Other such modifications could be made to allow this process to be used in situations where cooling periods as short as 35 months are required. 14. Transmutation Devices for the Advanced Fuel Cycle
For the AFC to be most effective in reducing the inventory of minor actinides at a reasonable rate, dedicated devices that produce a fast neutron spectrum are required. Such devices include the advanced liquid metal reactors (ALMR), a fast reactor configured to operate as an actinide incinerator rather than as a breeder and accelerator-driven systems (ADS). Fast reactor technology, discussed earlier in this chapter, is relatively mature whereas the development of ADS is not. Accelerator-based waste transmutation programs are being developed in France, Japan, USA, and by CERN. An ADS facility shown in Figure 17 consists of (1) a high power proton accelerator; (2) a subcritical target that produces a high neutron flux upon bombardment with high-energy protons; (3) a blanket system that utilizes this intense source-driven neutron flux to fission actinides and transmute fission products; and (4) a chemical processing plant to support the ADS operations.
Figure 17: Schematic of and Accelerator-Driven System (ADS) for transmutation of waste. Courtesy: World Nuclear Association (http://world.nucelar.org/sym/1999/venneri.html) The Uranium Institute, Twenty Fourth Annual International Symposium 1999, Disposition of Nucelar Wastes Using Subcritical Accelerator-Driven Systems by F. Venneri, M. Williamson, N. Li, M. Houts, R. Morley, D. Beller, W. Sailor, and G. Lawrence The central part of the system is the subcritical target where an intense (> 100 mA), high-energy (1-2 GeV) proton beam impinges on a high Z target to produce neutrons in a process called spallation. The effectiveness of an ADS target is usually given by the number of neutrons produced per incident proton and is linearly proportional to both the atomic number and density of the target. For this reason targets such as molten lead, or lead/bismuth eutectic are being proposed as the spallation source. Accelerator-driven systems producing 40 or more neutrons per incident proton are also being proposed. The waste material is loaded into the blanket where it is incinerated by capture of neutrons causing it either to fission or to be converted to short-lived or stable isotopes. This process, therefore, reduces the radiotoxic inventory of the waste material. The heat produced from the transmuter, Figure 18, (the combination of the target and blanket) can then be used to generate power, ~10% of which can be used to run the accelerator and the remaining 90% can be put on the power grid. Unlike fast reactors that operate on the criticality principle (at least one of the neutrons emitted during a fission event goes on to cause another atom to fission) to sustain nuclear reaction, ADS systems are subcritical. When the proton beam is off in an ADS, no neutrons are created and no nuclear reaction occurs.
Figure 18: Schematic of a transmuter for an ADS. Courtesy: World Nuclear Association (http://world.nucelar.org/sym/1999/venneri.html) The Uranium Institute, Twenty Fourth Annual International Symposium 1999, Disposition of Nucelar Wastes Using Subcritical Accelerator-Driven Systems by F. Venneri, M. Williamson, N. Li, M. Houts, R. Morley, D. Beller, W. Sailor, and G. Lawrence
An often overlooked but key component of an ADS is the chemical processing plant needed to support the operations. Within the plant, separation processes are used to partition the spent fuel to obtain the waste material that is introduced into the ADS and also to support multiple recycle, fuel fabrication, and finally, the production of the final waste forms acceptable for disposal in a geologic repository. Figure 19 shows a flow diagram for chemical processing plant designed to support transmutation with an ADS. All of these activities are crucial to the success of transmutation using ADS and considerable R&D is needed to make this a reality.
Figure 19: Flow diagram for a chemical processing plant for an ADS. Courtesy: World Nuclear Association (http://world.nucelar.org/sym/1999/venneri.html) The Uranium Institute, Twenty Fourth Annual International Symposium 1999, Disposition of Nucelar Wastes Using Subcritical Accelerator-Driven Systems by F. Venneri, M. Williamson, N. Li, M. Houts, R. Morley, D. Beller, W. Sailor, and G. Lawrence 15. Strategies for Implementation of an Advanced Fuel Cycle
In general, the different strategies for implementation of AFC concepts depend on tradeoffs between the effectiveness of the partitioning steps (chemical yields and acceptable losses of the desired elements), the degree of transmutation that can be achieved by various types of devices (burnup rates, neutron spectra and fluxes available), and the potential for proliferation of the associated fissile material. However, the two main approaches differ in how the plutonium is managed. In the first, plutonium is separated and used to create energy and the minor actinides, neptunium and above, are treated and managed as waste products. In the second, the transuranium elements, plutonium and the minor actinides are managed as a single unit. Where plutonium is separated from LWR spent fuel, the utilization of plutonium as an energy source and the management of the minor actinides as a waste product is a relatively simple process and the fuel cycle is closed in an evolutionary way. This is shown schematically in Figure 20. Initially, plutonium is recycled in a light water reactor as a mixed oxide fuel, LWRMOX, and later, in fast reactors as FR-MOX fuel. In this scenario, the fuel cycle is optimized for the production of energy from
plutonium, especially if the fast reactor is a breeder reactor, but does not reduce the burden of the MAs and LLFPs on the repository.
Figure 20: Schematic of an advanced fuel cycle scenario where Pu is separated and recycled to optimize the production of energy from plutonium. The second approach which does not separate plutonium and the minor actinides during the processing of LWR fuel has as its principal driver reduction of the risk of proliferation of plutonium. To accomplish the transmutation of this waste stream, a TRU burner is required that operates in a closed cycle where the wastes are recycled multiple times. Further, to be effective, non-aqueous chemical processing is necessary to minimize the time between irradiations and to shorten the overall recycle time. The main difference between the two approaches is that, in the former, plutonium would be removed by conventional wet chemical processing and only the minor actinides are reprocessed using non-aqueous methods. The options for burning TRU include both thermal and fast critical reactors and thermal and special, fast-spectrum subcritical accelerator-driven systems (ADS). Figure 21 is a schematic of one of many possible P&T schemes that involves both aqueous and non-aqueous partitioning that has as an ultimate goal, removal of Pu, the MAs, and selected LLFPs from the waste going to a repository.
Figure 21: One of several Partitioning and Transmutation (P&T) strategies being considered to substantially reduce minor actinides produced by conventional LWR power reactors. 16. Generation IV Nuclear Energy Systems
Nuclear energy is expected to grow considerably over the next 50 years for several reasons: the demand for energy exceeds the supply even though significant improvements in energy efficiency and conservation have been made. The demand is increasing exponentially in Asia; energy resource availability is a growing concern; decline in air quality and climate change due to global warming caused by greenhouse gases produced by the burning of fossil fuels for energy continue; the need for countries for energy security requires a sustainable nuclear energy component that is acceptable to the public.
For nuclear energy to become a larger part of an overall energy strategy, other issues such as reactor safety, economics, and non-proliferation must be considered. These issues, as well as the waste issue, are being addressed in an initiative of the US by Department of Energys (DOE) Office of Nuclear Energy called the Generation IV International Forum for Nuclear Energy Cooperation (GIF). Charter nations, in addition to the US, include Argentina, Brazil, Canada, France, Japan, Republic of Korea, and the United Kingdom. Figure 22 shows the evolution of nuclear reactor technology starting with the early prototype reactors in the 1950s through the proposed Generation IV energy systems that are under design. The Generation IV nuclear
systems are to be ready for deployment by 2030 with standardized designs to expedite licensing, reduce capital costs and allow rapid construction with simpler and more robust designs that incorporate passive or inherently safe features such as no active controls or controls that rely on gravity or natural convective cooling; higher availability and longer operating life, and higher, more efficient fuel burnup with greater minimization of waste.
A roadmap has been developed that defines the next generation nuclear energy systems to achieve the required safety performance, waste reduction, and proliferation resistance, demanded by the public at an economically competitive cost. The six most promising energy systems that have been identified for further development include: Thermal-spectrum systems
Very-high temperature reactor (VHTR) Supercritical-water-cooled reactor (SCWR) Fast-spectrum systems
Gas-cooled fast reactor (GFR) Lead-cooled fast reactor (LFR) Sodium-cooled fast reactor (SFR) Liquid-fuel system Molten salt reactor (MSR)
Figure 22: Time line showing the evolution of nuclear energy systems. Courtesy: US Dept. of Energy, Office of Nuclear Energy (http://nuclear.energy.gov/genIV/neGenIV1.html)
In the US, the Generation IV program is being coupled to the Nuclear Hydrogen Initiative to develop hydrogen production technologies compatible with nuclear energy systems of the future. 16.1. Advanced Fuel Cycle Development to Support Generation IV Energy Systems For an energy strategy involving significant growth in nuclear energy to be successful, advances must be made in all areas of the fuel cycle. For the deployment of Generation IV reactors, fuel cycle technologies must be developed that include new fuels, cladding, and fuel fabrication, improved separation and fuel fabrication processes that support P&T, better and more robust waste forms and disposal technologies. These technologies must be: economical, having a financial risk comparable to other energy sources, inherently reliable, safe, and resistant to proliferation, significantly reduce the toxicity of the waste destined for geologic storage by removal of the transuranic elements, and, reclaim the valuable energy remaining in spent nuclear fuel. 16.2. The Advanced Fuel Cycle Initiative (AFCI)
The US is pursuing a national energy policy which, over time, will significantly increase reliance on nuclear energy. The US nuclear energy enterprise will transition from the current once-through fuel option to a fuel cycle based on sustained actinide recycle that (1) reduces repository burdens for storing nuclear waste, (2) employs advanced treatment technologies that are more resistant to proliferation, and, (3) more effectively utilizes nuclear fuel resources. The US through its Advanced Fuel Cycle Initiative (AFCI) program is developing separation processes that do not produce pure plutonium. This phased approach, shown in Table 9, includes extending the life of the current fleet of primarily LWRs while introducing successive generations of more advanced light water reactors and ultra-high burnup fuels. This approach also includes the introduction of Generation IV thermal reactors, more proliferation-resistant technologies for Pu recycle, and then Generation IV fast reactors requiring new fuel systems and even more advanced separation technologies for destruction of actinides and long-lived fission products via transmutation.
Implementation: approx. time period Now 2010-2015
2020-2025
Fuel Cycle Phase Disposition Actions Once through fuel option Limited closed fuel cycle Spent fuel stored at reactor sites Geologic repositories open High burn up fuels implemented Limited fuel recycling Recycling of weapons useable material begins Cs/Sr removal: allowed to decay
2030-2035
2040-2050
2050
~ 2100
Table 9: Phased strategy for implementation of Advanced Nuclear Fuel Cycles in the U.S. Times are only approximate and durations of the phases or the extent of their overlap are subject to evolution of nuclear future. Courtesy: US Dept. of Energy, Office of Nuclear Energy, Advanced Fuel Cycle Program Plan, May 2005, p.5-3. (http://www.ne.doe.gov/AFCI/neAFCI.html)
Chemical separations technology development for advanced fuel cycle applications using the AFCI Program as an example are focused on separations processes that facilitate removal of those constituents of spent fuel that contribute most to the heat load and waste volume imposed on the disposal of high-level waste in the repository. Processes requirements include:
2035-2040
Geologic disposal of: U as low level waste TRU and remaining FPs as HLW Selected TRU recovery for recycle in thermal reactors Thermal recycle Cs/Sr removal: allowed to decay of TRU Geologic disposal of: U as low level waste Remaining MAs and FPs as HLW U recovery for reuse or storage Cs/Sr removal: allowed to decay Dedicated burners TRU recovery and recycle in for TRU dedicated fast burner reactors Geologic disposal of: Remaining FPs and HLW U recovery for reuse or storage Cs/Sr removal: allowed to decay Gen IV closed fuel TRU recovery and recycle in Gen IV cycle reactors Geologic disposal of: Remaining FPs and HLW Spent fuel continually recycled Cs/Sr removal: allowed to decay Transitional Geologic disposal of: Recycle Only remaining FP disposed as HLW Recovered U routinely used for fuel Cs/Sr removal: allowed to decay Sustainable Geologic disposal of: Recycle Only remaining FP disposed as HLW
removal of over 90% of the uranium in sufficiently pure form that it can be disposed as low-level waste or re-enriched for recycle to LWRs; removal of over 99% of the cesium and strontium present in spent fuel, thereby greatly reducing the short-term heat load; separation of the transuranic elements (plutonium, neptunium, americium and curium) for storage or recycle to LWRs or future advanced reactors for fissioning, thereby greatly reducing the long-term heat load. 16.3. Areas of Scientific Concerns in the AFCI Single-Tier System Front-end fuels separations UREX Dual-Tier System UREX Long-Term Options Advanced processes Advanced light water reactor, very high temperature reactor Inert matrix fuel (IMF)
Thermal reactor for recycle
Fuel for thermal reactors Separations for fast reactor fuel
Fast reactor fuel
Fast reactor
Table 10: Proposed research areas for the advanced fuel cycle program. Courtesy: US Dept. of Energy, Office of Nuclear Energy, Path to Sustainable Nuclear Energy, Basic and Applied Research Opportunities for Advanced Fuel Cycles, Sept. 2005, p. 8. (http://www.science.doe.gov/bes/reports/list.html) Science areas important in the development of advanced fuel cycles are materials, separations, modeling and simulation and proliferation resistance of the fuel cycle. The major challenges in the material science area are maximization of the efficiency in use of nuclear fuels, minimization of the effects and amounts of wastes that are
LWR, ALWR Mixed oxide (MOX) With UREX Non-aqueous pyroprocessin g or advanced aqueous Non-aqueous Advanced pyroprocessing or processes advanced aqueous Metal or MOX metal or MOX Sodium-cooled Sodium-cooled Nitrides, carbides, composites Lead-cooled or gas cooled fast reactors; Advanced systems (fusion-fission; accelerator driven system, molten salt reactors)
disposed, and reduction of the risks of proliferation of potential weapons materials from the fuel cycles. The main scientific challenges in materials development for AFCI are in these areas: data on relevant thermodynamic and thermophysical properties which require theoretical systems to predict such data from alloys, chemical complexes, colloids, etc., at relevant temperatures of reactor operation, of conditions in waste storage facilities, and in operations in separations plants; solid/solid and solid/liquid interface interactions in reactor operation, and in separations and waste disposal; radiation effects in all these systems.
a valid understanding of the ionic and molecular behavior of the multicomponent fluids; design, synthesis and study of the materials (i.e., complexants, etc.) for highly selective reagents; sufficient understanding of the effects of radiation and interfacial phenomena in the separation systems. Critical needs in modeling and simulation are methods to deal with the chemistry and physics by different models. These must involve widely varying temporal and spatial scales, and methods to deal with uncertainties including propagation of errors in the data and in models. The scientific challenges facing modeling and simulation for AFCI can be placed in the following areas: improve nuclear data covariance matrices and determine precise actinide cross sections, develop modeling for materials in extreme environments such as high radiation fields and elevated temperatures, develop models for advanced separations of spent fuels which minimize waste, model the entire fuel cycle with uncertainties in the data and the models.
Nuclear fuel management systems in present use have certain proliferation risks. The growth, internationally, of spent nuclear fuel and of separated plutonium is of growing global concern in this area. A definite and workable program is needed in global management of nuclear materials. A number of factors can be cited as targets for improvement which are several top level goals and require application of new science and technology. strengthening safeguards technology by improving means of reducing the risk of diversion by advanced radiation monitoring detection systems, specific sensors to monitor chemical process conditions and chemical effluents,
The separation systems require much fundamental research to achieve an adequate knowledge of the important factors to ensure success in their use. These include:
decreasing the purity of nuclear materials in fuels and bulk materials (isotopic and chemical composition). 17. Future of P&T Japan, France and the US are the most active pursuers of partitioning and transmutation technologies. In addition, several international groups (NEA, IAEA, and the EC) are engaged in such studies. Each organization regularly publishes their progress, status and future activities. Many of these reports are available on the respective websites. Appendix
ADVANCED FUEL CYCLE INITIATIVE (AFCI) PROGRAM PLAN, May 1, 2005 available from http://www.afci.sandia.gov/downloads/2005_afci_program_plan.pdf ALBRIGHT, D., 1993, World Inventory of Plutonium and Highly Enriched Uranium, 1992, (New York: Oxford University Press). ALBRIGHT, D., BERKHOUT, F., and WALKER, W., 1997, Plutonium and Highly Enriched Uranium 1996: World Inventories, Capabilities, and Policies (New York: Oxford University Press) ANL-99/15, September 1999, A Technology Roadmap for Developing ATW Technology, Separations and Waste Form Technology, Argonne National Lab (ANL) BELLER D. and RHODES R., 2000, The Need for Nuclear Power, (Foreign Affairs, 79, 30) BENEDICT, M., PIGFORD, T., LEVI, H.W., 1981, Nuclear Chemical Engineering, 2nd Ed., McGraw Hill, NY CARSON, P.H., PIERCE, G.D.BRUCHER, E. and MORTON, R.L., 1990, Sources of Waste, Radioactive Waste Management and the Nuclear Fuel Cycle, 14 (1-2), pp 27-44TOTH, I., 1991, Carbonate Exchange for the Complex U02(CO3)34+ in Aqueous Solution as Studied by 13C NMR Spectroscopy, Inorg. Chem., 30, 2239. CHEN, J., ZHU, Y., JIAO, R., 1996, The Separation of Am from the Lanthanides by Purified CYANEX 301 Extraction, Sep. Sci. Technology 31, 2723 CHOPPIN, G.R, 1991, Redox Speciation of Plutonium in Natural Waste, J. Radioanal. Nucl. Chem, Art. 147, 109. CHOPPIN, G.R, 1992, The Role of Natural Organics in Radionuclide Migration in Natural Aquifer Systems, Radiochim Acta, 58/59, 113. CHOPPIN, G.R., RYDBERG, J., LILJENZIN, J.O., 1995, Radiochemistry and Nuclear Chemistry, Theory and Applications, Butterworth-Heinemann Ltd, Great Britain. COOPS, M.M., J.B. KNIGHTON, L.J. MULLINS, 1983, Pyrochemical Processing of Plutonium, ACS Symposium Series 216, Plutonium Chemistry, edited by W.T. Carnall, G.R. Choppin, (Washington DC, American Chemical Society) pp 381-400. DOE/RW-0519, 1999, A Roadmap for Developing Accelerator Transmutation of Waste (ATW) Technology, A Report to Congress , October 1999 CHARTIER, D., DONNET L., ADNET J.M., 1998 Electrochemical Oxidation of Am(III) with Lacunary Heteropolyanions and Silver Nitrate, Radiochim. Acta 83 (3): 129-134. CULLER, F.L., 1956, Reprocessing of Reactor Fuel in Blanket Materials by Solvent Extraction, Progress in Nucl. Energy, Series III. Process Chemistry, Vol. 1., edited by F.R. Bruce, I.M. Flecther, H.H. Hyman and K.J. Katz (New York, McGraw Hill) pp 172-194. CUILLERDIER, C., MUSIKAS, C., HOEL, P., NIGOND, L., VITART, X., 1991, Separation Sci. Technol., Vol 26(9), pp 1229-1244. DOE, 2001. United States Department of Energy, Office of Nuclear Energy, Science and Technology and Coordinated with the National Nuclear Security Administration. Report to Congress The Advanced Accelerator Applications Program Plan, Washington, DC. , USA: US Government Printing Office.
Appendix: Additional Bibliography
DOE Order 5820.2 (1984) and replaced by 5820.2A in 1988, both titled Radioactive Waste Management. DOE Office of Nuclear Energy, Science and Technology, Office of Advanced Nuclear Research. Generation IV Nuclear Energy Systems, Ten-year Program Plan, Fiscal Year 2005, March 2005, available from http://nuclear.energy.gov/genIV/neGenIV1.html DOE, Basic Energy Sciences Workshop, 2005, The Path to Sustainable Nuclear Energy Basic and Applied Research Opportunities for Advanced Fuel Cycles, September 2005, available from http://www.er.doe.gov/bes/reports/files/PSNE_rpt.pdf DONNET, L., ADNET, J.M, FAURE N., BROS P., BROSSARD Ph., and JOSSO F., 1999, The Development of the SESAME Process, Proceedings of the Fifth OECD/NEA Information Exchange Meeting on Actinide and Fission Product Partitioning and Transmutation, Mol, Belgium, 25-27 November 1998. DOZOL J.F., DOZOL M., MACIAS R.M., 2000, Extraction of Strontium and Cesium by Dicarbollides, Crown Ethers and Functionalized Calixarenes, Journal of Inclusion Phenomena and Macrocyclic Chemistry 38 (1-4): 1-22. DUNLOP, R.E., ROSA, E.A., and KRAFT, M.E., Editors, 1993, Public Reactions to Nuclear Waste, edited by, Duke University Press. ENSOR, D.D., JARVINEN, G.D., SMITH, B.F., 1988, The Use of Soft Donor Ligands, 4-benzoyl-2,4dihydro-5-methyl-2-phenyl-3H-pyrazole-3-thione and 4,7-diphenyl-1,10-phenanthroline, for Improved Separation of Trivalent Americium and Europium, Solv. Extr. Ion Exch., 6 439. ESIMANTOVSKII, V.M., GALKIN, B.Y., LAZAREV, L.N., LYUBTSEV, R.I., ROMANOVSKI, V.N., SHISHKIN, D.N., 1992, Technological Tests of HAW Partitioning with the Use of Chlorinated Cobalt Dicarbolyde (CHCODIC); Management of Secondary Wastes, Proc. of the Symposium on Waste Management, edited by R.G. Post (Tucson: Ariz. Board of Regents) pp 801804 Federal Register: July 21, 1995 (Volume 60, Number 140) Page 37556-37565FUGER, J., 1992, Thermodynamic Properties of Actinide Aqueous Species Relevant to Geochemical Problems, Radiochim Acta, 58/59, 81. HIROSE, K., and SUGIMURA, Y., 1993, Chemical Speciation of Particulate 238U, 239-240Pu and Th Isotopes in Seawater, Sci. Total Environ., 130/131, 517. HORWITZ, E.P., DIETZ, M.L., FISHER, D.E., 1990, Extraction of Strontium from Nitric Acid Solutions Using Dicyclohexano-18-crown-6 and its Derivatives, Solv. Extr. Ion Exch., 8, 557. HORWITZ, E.P., SCHULZ, W.W., 1999, Solvent Extraction in the Treatment of Acidic High-Level Liquid Waste: Where Do We Stand?, In Metal Ion Separation and Preconcentration: Progress and Opportunities, ACS Symposium Series 716, Editors A.H. Bond, M.L. Dietz, R.D. Rogers, (Washington DC), pp 20-50. HORWITZ, E.P., DIETZ, M.L. and FISHER, D.E., 1991, SREX: A New Process for the Extraction and Recovery of Strontium from Acidic Nuclear Waste Streams, Solv. Extr. Ion Exch., 9, pp. 1-25. HORWITZ, E.P., SCHULZ, W.W., 1985, The TRUEX Process A Process for the Extraction of Transuranic Elements from Nitric Acid Wastes Utilizing Modified PUREX Process, Solv. Extr. Ion Exch., 3, p. 75 INTERNATIONAL ATOMIC ENERGY AGENCY (IAEA), 1977, Regional Nuclear Fuel Cycle Centres, Vienna, Austria. JAIN, S., RAMASWAMY, M., THEYYUNNI, T. K., 1995, Removal of strontium from low level waste using zeolite 4A, NUCAR 95: Proceedings of the Nuclear and Radiochemistry Symposium, Kalpakkam, India, Feb. 21-24, 1995. JARVINEN, G.D., MARSH, S.F., SMITH, B.F., YARBRO, S.L., YATES, M., WALKER, R.B. 1992, Baseline Actinide Blanket Processing Flowsheet for the ATW Program, LA-UR-92-63, (Los Alamos, NM), Los Alamos National Laboratory (LANL). KIM, J.I., BUCKAU, G., and KLENZE, R., 1987, Natural Colloids and Generation of Actinide Pseudocolloids in Ground Waters in Analogues in Radioactive Waste Disposal, Cornel, B. and Chapman, N.A. Editors, Graham and Trotman, New York, pp289. KLENZE, R., KIM, J.I., and WIMMER, H., 1991, Speciation of Aquatic Actinide Ions by Pulse Laser Spectroscopy, Radiochim. Acta, 52/53, 97. KOLARIK, E., KOCH, G., KUESEL, H.H., FRITSCH, J., 1972, Separation of Americium and Curium from Highly Radioactive Waste Solution, KFK-1553, Karlsruhe, Germany, Karlsruhe Nuclear Research Center.
KUMAR, A., MOHAPATRA, P.K., PATHAK, P.N. and MANCHANDA, V.K., 1997, Dicyclohexano 18 Crown 6 in Butanol-Octanol Mixture: A Promising Extractant of Sr(II) from Nitric Acid Medium, Talanta 4, 387. LANL (Los Alamos National Laboratory) 1999, Roadmap for the Development of Accelerator Transmutation of Waste: Target and Blanket System LILJENZIN, J.O., PERSSON, G., SVANTESSON, I., WINGEFORS, S., 1984, The CTH-Process for HLLW Treatment Part 1 General Description and Process Design, Radiochim. Acta, 35, pp 155162. LOWENTHAL, M. D. , 1997, Radioactive Classification in the United States: History and Current Predicaments, UCRL-CR-128127 S/C # B332804 MADIC, C., HUDSON, M.J., LILJENZIN, J.O., GLATZ, J.P., NANNICINI, R., FACCHINI, A., KOLARIK, Z., ODOJ, R., 2000, New Partitioning Techniques for Minor Actinides, Final Report, EUR 19149. MADIC, C., 2000, Overview of the Hydrometallurigcal and Pyro-metallurgical Processes Studied Worldwide for the Partitioning of High Active Nuclear Wastes in Actinide and Fission Partitioning and Transmutation, Madrid, OECD/NEA. MATHUR, J.N., MURALI, M.S., IYER, R.H., RAMUNUJAM, A., DHAMI, P.S., GOPALAKRISHNAN, V., RAO, M.K., BADHEKA, L.P., BANERJI, A., 1995, Extraction Chromatographic Separation of Minor Actinides from PUREX High-Level Wastes Using CMPO, Nucl. Technol., Vol. 109, 219-225 MATHUR, J.N., MURALI, M.S., NASH, K.L., 2001, Actinide Partitioning A Review, Solvent Extr. Ion Exch., 19 (3), 357-390 MORITA, Y., TANI, S., KUBOTA, M., 1991, Separation of Transuranic Elements from High-Level Waste by Extraction with Diisodecyl Phosphoric Acid, The Third International Conf. on Nucl. Fuel Reprocessing and Waste Management, Recod91 Vol. 1, Sendai, Japan MORSE, J.W., and CHOPPIN, G. R., 1991, The Chemistry of the Transuranium Elements in Natural Waters, Rev. Aquat. Sci. 4, 1. MUSIKAS, C., 1984, Actinide-Lanthanide Group Separation Using Sulfur and Nitrogen Donor Extractants Intl. Chemistry Congress of Pacific Basin Societies, (Honolulu) CEA-Conf-7706. MUSIKAS, C., 1985a, Actinide/Lanthanide Group Separation Using Sulphur, and Nitrogen Donor Extractants, Editors G.R. Choppin, J.D. Navratil, and W.W. Shulz, Actinide/Lanthanide Separations, (Philidelphia, World Scientific Press), pp 19-30 MUSIKAS, C., HUBERT, H., 1987, Extraction by N,N-tetraalkylmalonamides, II Extraction of Metallic Ions, Solv. Extr. Ion. Exch. 5 877 MUSIKAS, C., 1999, Review of Possible Technologies for Actinide Separations Using Other Extractants than TBP, NATO SCI. Ser., Ser. 2 53, (Chemical Separation Technologies and Related Methods of Nuclear Waste Management) pp 99-122 NIFENECKER, H., DAVID, S., LOISEAUX, J.M., and MEPLAN, O., 2001, Basics of Accelerator Driven Subcritical Reactors, Nucl. Instr. Meth. A463, 428. NAS 1957: The Disposal of Radioactive Waste on Land, (National Academy Press). NAS 1994: Management and Disposal of Excess Weapons Plutonium, National Academy of Sciences. Committee on International Security and Arms Control, Washington, D.C., (National Academy Press) p.34. NAS 1996, Nuclear Wastes, Technologies for Separations and Transmutation, (National Academy Press) NAS 2000, Electrometallurgical Techniques for DOE Spent Fuel Final Report, (National Academy Press). NUCLEAR WASTE MANAGEMENT ORGANIZATION of Canada website: http://www.nwmo.ca/ [Information on the strategy being used by Canada to handle radioactive waste from nuclear power generation] ORGANIZATION for ECONOMIC CO-OPERATON and DEVELOPMENT, NUCLEAR ENERGY AGENCY (OECD/NEA) website: http://www.nea.fr/welcome.html NASH, K.L., CLEVELAND, J.M., and REES, T.F., 1988, Speciation Patterns of Actinides in Natural Water: A Laboratory Investigation, J. Environ. Radioact., 7, 131. OCED/NEA 1998, Status and Assessment Report of Actinide and Fission Product Partitioning and Transmutation, OECD Report NEA/PTS/DOC. OCED/NEA, 1999, Actinide and Fission Product Partitioning and Transmutation Proceedings of the Fifth International Information Exchange Meeting, Mol, Belgium, 25-27 November 1998.
OECD/NEA, 2000, Nuclear Energy Agency, Organisation for Economic Co-operation and Development. Actinide and Fission Product Partitioning and Transmutation, Paris, France: NEA Press, 2000. OCED/NEA, 2001, Actinide and Fission Product Partitioning and Transmutation Sixth International Information Exchange Meeting, Madrid, Spain. OECD/NEA, 2002, Actinide and Fission Product Partitioning and Transmutation, Seventh Information Exchange Meeting, Jeju, Republic of Korea. OECD/NEA, 2002, Accelerator-driven Systems (ADS) and Fast Reactors (FR) in Advanced Nuclear Fuel Cycles A Comparative Study, Paris, France: NEA Press, 2002. OECD/NEA, 2004, Actinide and Fission Product Partitioning and Transmutation, Eighth Information Exchange Meeting, Las Vegas, USA. OECD/NEA, 2006, Actinide and Fission Product Partitioning and Transmutation, Ninth Information Exchange Meeting, Nmes, France. PERSSON, G., WINGEFORS, S., LILJENZIN, J.O., SVANTESSON, I., 1984, The CTH-Process for HLLW Treatment- Part II Hot Test, Radiochim. Acta 35, pp 163-172. PERSSON, G.E., SVANTESSON, S., WINGEFORS, S., LILJENZIN, J.O., 1986, Hot Test of a Talspeak Procedure for Separation of Actinides and Lanthanides Using Recirculating DTPA-lactic Acid Solution, Solv. Extr. Ion Exch., 2, 89. PLENDL, H.S., Editor, 1994, Special Issue on Nuclear Transmutation Methods and Technologies for Disposition of Long-lived Radioactive Materials, Nuclear Instruments and Methods A, Vol.414, 1126. PLENDL, H.S., Editor, 2001 Special Issue on Accelerator Driven Systems, Nuclear Instruments and Methods A, Vol. 463, 425-666. RAISBECK, G.M., YIOU, F., ZHOU, Z.Q., KILIUS L.R., 1995, I-129 From Nuclear Fuel Reprocessing Facilities At Sellafield (UK) And La Hague (France) - Potential As An Oceanographic Tracer, Journal Of Marine Systems, NOV, 1995, V6 (N5-6):561-570. RAISBECK, G.M., YIOU, F., ZHOU, Z.Q., KILIUS L.R., 1995. I-129 From Nuclear Fuel Reprocessing Facilities At Sellafield (UK) And La Hague (France) - Potential As An Oceanographic Tracer, Journal Of Marine Systems, NOV, 1995, V6 (N5-6):561-570. RIZKALLA, E.N., and CHOPPIN, G.R., 1994, Lanthanides and Actinides Hydration and Hydrolysis and Solution Chemistry of Actinides and Lanthanides in Gschneider, Jr., K.A., Erying, L., Choppin, G.R., and Lander, G.H. Editors, Handbook on the Physics and Chemistry of the Rare Earths, 18, 529. SCHULZ, W.W., HORWITZ, E.P., 1988, The TRUEX Process and the Management of Liquid TRU Wastes, Sepn. Sci. Technol, 23, 1191 SELUCKY, P.; RAIS, J.; KYRS, M., 1979, Study of the possibility of using dicarbollides to extract cesium and strontium from waste radioactive solutions, Ustav Jad. Vyzk., [Rep.] (1979), (UJV 5069), 58 pp. SHANBHAG, P.M., and MORSE, J.W., 1982, Americium Interaction with Calcite and Aragonite Surfaces in Seawater, Geochim. Cosmochim. Acta, 46, 241. SHANNON, R.D., 1976, Revised Effective Ionic-Radii and Systematic Studies of Interatomic Distances in Halides and Chalcogenides, Acta Cryst., A32, 751. SHANNON, R.D., and PREWITT, C.T., 1969, Effective Ionic Radii in Oxides and Fluorides, Acta Cryst., B25, 925. SHANNON, R.D., and PREWITT, C.T., 1970, Revised Values of Effective Ionic Radii, Acta Cryst., 1970, B26, 1046. SILVA, R.J. 1995, Chemical Thermodynamics of Americium, Elsever, Amsterdam SILVA, R.J. and NITSCHE, H., 1995, Actinide Environmental Chemistry, Radiochim. Acta, 70/71, 377. STRUMM, W., and MORGAN, J.J., 1996, Aquatic Chemistry: An Introduction Emphaszing Chemical Equilibria in Natural Waters, John Wiley, New York. SULLIVAN, J.C., 1983, Reaction of Plutonium Ions with the Products of Water Radiolysis in Carnall, W.T., and Choppin, G.R., Editors, Plutonium Chemistry, ACS Symposium Series, 216, 241. TACHIMORI, S., SATO, A., NAKAMURA, H., 1979 Separation of transplutonium and rare earth elements by extraction with diisodecyl phosphoric acid from DTPA solution, J. Nucl. Sci. Technol. 16(6), pp 434-40. TACHIMORI, S., NAKAMURA, H. 1982a, Extraction of some elements by a mixture of DIDPA-TBP and its application to actinide partitioning process. J. Nucl. Sci. Technol. 19(4), pp 326-33
U
A:
Glossary
ADS: AFC: AFCI: AHA: ALMR: ANL: Bq:
BRC:
TACHIMORI, S., NAKAMURA, H., 1982b,Extraction of some elements by a mixture of DIDPA-TBP and its application to actinide partitioning process, J. Nucl. Sci. Technol., 19(4), pp 326-33 The League of Women Voters Education Fund, The Nuclear Waste Primer 1993 Revised Edition, Lyons & Burford, New York (1993): pp 25-26. United States Code, title 42, section 10101 (42 U.S.C. 10101) U.S. Code of Federal Regulations, Title 10, Part 60.2 (10 C.F.R. 60.2) United States Code, title 42, section 2014 (42 U.S.C. 2014) United States Code, title 42, section 2021 (42 U.S.C. 2021) VANDEGRIFT, G. F., REGALBUTO, M.C., AASE, S.B., ARAFAT, H.A., BAKEL, A.J., BOWERS, D.L., BYRNES, J.P., CLARK, M.A., EMERY, J.W., FALKENBERG, J.R., GELIS, A.V., HAFENRICHTER, L.D., LEONARD, R.A., PEREIRA, C., QUIGLEY, K.J., TSAI, Y., VANDER POL, M.H., and LAIDLER, J.J., 2004, Lab-Scale Demonstration of the UREX+ Process, Waste Management 04 Conference, Tucson, AZ VITORGE, P.,1984, Lanthanides and Trivalent Actinides Complexation by Tripyridyl, Triazine, Applications to Liquid-Liquid Extraction, CEA-R-5270 WANNER, H., Forest, I. Editors, 1992, Chemical Thermodynamics of Uranium, North Holland, Amsterdam. WEAVER, B., F.A. KAPPELMANN, 1964, Talspeak: A New Method of Separating Americium and Curium from Lanthanides by Extraction from an Aqueous Solution of Aminopolyacetic Acid Complex with a Monoacidic Phosphate or Phosphonate, ORNL-3559, Oak Ridge, Tenn, Oak Ridge National Laboratory. WEIGL, M., GEIST, A.,M GOMPPER, K., KIM, J.I., 2001, Kinetics of Lanthanide/Actinide Coextraction with N,N-dimethyl, N,N-dibutyltetradecylmalonic diamide (DMDBTDMA). Solvent Extr., Ion Exch, 19(2) pp 215-229. YAKOVLEV, G.N., GORBENKO-GERMANOV, D.S., 1956, Coprecipitation of Americium (V) with Double Carbonates Uranium (VI) or Platinum (vi) with Potassium, Proc. 1st United Nations International Conference on Peaceful Uses of Atomic Energy, Vol. 7, Vienna, International Atomic Energy Agency. YOUNG, W. A., 1994, Hazard-Based Classification of Nuclear Waste A Wiser Arrangement, Nuclear Guardianship Forum, #3. ZHU, Y., SONG, C., XU, J., YANG, D., LUI, B., CHEN, J., 1989, The Removal of Actinides from High Level Radioactive Waste by TRPO Extraction. The Extraction of Americium and Some Lanthanides, Chinese J. Nucl. Sci. Eng., Vol . 9, pp 141-150. ZHU, Y., 1995, The Separation of Americium from Light Lanthanides by Cyanex-301 Extraction, Radiochim. Acta, 68, pp 95-98.
Mass number, sum of the number of protons and neutrons in the nucleus. Accelerator-driven system. Advanced Fuel Cycle. Advanced Fuel Cycle Initiative. Acetohydroxamic acid, complexing agent used in the UREX process to suppress the extraction of plutonium. Advanced Liquid Metal Reactor. Argonne National Laboratory. Abbreviation for Becquerel, the SI derived unit for radioactivity defined as the activity of a quantity of radioactive material in which one atom decays per second (s-1). Below regulatory concern or de minimis refers to material containing very low concentrations of radioactivity such that the associated radiological hazards are generally considered to be
Breeder reactor: BWR: CERN:
CSEX: Cooling time:
Decommissioning of a nuclear reactor:
DIAMEX: EBR-II: EC: eV: EW:
Fissile nuclear fuel: FBRs:
FR-MOX: GFR: GIF:
Greenhouse Gas: GWe: HLW: Incineration: IAEA: ILW: Isotopics: keV: LAMPRE: LANL: LFR: LLFP: LLW:
negligible since they are less than for naturally-occurring radioactivity. A nuclear reactor that produces more fissile nuclear fuel that it consumes. Boiling water reactor. Organisation Europenne pour la Recherche Nuclaire (European Organization for Nuclear Research) - Worlds largest particle physics laboratory located near Geneva on the border between France and Switzerland. Chemical process designed to selectively extract cesium. The amount of time spent nuclear fuel is allowed to decay in pools of water before handling for the purpose of chemical reprocessing or dry storage. Involves removing the spent fuel (the fuel that has been in the reactor vessel), dismantling any systems or components containing activation products (such as the reactor vessel and primary loop), and cleaning up or dismantling contaminated materials from the facility. Extraction process for improved separation of actinide from acidic solutions using bifunctional diamides. Experimental Breeder Reactor II. European Community. Electron volt. Exempt waste waste that is identified as below regulatory concern or de minimis. Fuel that can be easily made to undergo the nuclear fission reaction. Fast Breeder Reactors reactors that breed new fuel using fast neutrons. Fast reactor mixed oxide fuel. Gas-cooled fast reactor. Generation IV International Forum for Nuclear Energy Cooperation. Gases in the atmosphere that absorb light radiated from the earths surface and lead to global warming. Gigawatts of electrical energy. High-level waste. Term used interchangeably with transmutation. International Atomic Energy Agency. Intermediate level waste. Distribution of isotopes such as in spent nuclear fuel. Kiloelectron volts. Los Alamos Molten Plutonium Reactor Experiment. Los Alamos National Laboratory. Lead-cooled fast reactor. Long-lived fission products. Low-level waste.
LWR: LWR:MOX: MA: MeV: MOX: MSR: MWth: MWe: NEA: NORM/NARM: NPEX: Partitioning:
P&T: PUREX:
PWR: Pyrochemical: Radiotoxicity: Raffinate:
REEs: RFC: SCWR: SFR: SNF: Spallation:
SREX: Subcritical reactor:
TALSPEAK: Transmutation:
TRAMEX:
Light water reactors. Light water reactor mixed oxide fuel. Minor actinides, i.e. actinides other than U and Pu. Million electron volts. Mixed oxide fuel. Molten salt reactor. Megawatts of thermal energy. Megawatts of electrical energy. Nuclear Energy Agency (France). Naturally Occurring and Accelerator produced Radioactive Material. Neptunium extraction chemical process designed to selectively extract neptunium. A complex series of aqueous chemical and/or non-aqueous metallurgical operations used to selectively remove or partition the minor actinide and long-lived fission products from highlevel waste. Partitioning and Transmutation. Plutonium Redox Extraction chemical process designed to selectively extract plutonium by changing its oxidation state. Pressurized water reactor. Pertaining to chemical reactions carried out at high temperatures such as in a molten salt. A measure of the toxicity or the harmful potential of a quantity radioactive material assess in terms of dose received. In the PUREX process, the raffinate is the solution containing the dissolved spent nuclear fuel that remains after the extraction of plutonium and uranium. Rare earth elements also known as the lanthanides. Reprocessing Fuel Cycle. Supercritical-water-cooled reactor. Sodium-cooled fast reactor. Spent Nuclear Fuel. Process by which a heavy nucleus emits a large number of nucleons (primarily neutrons and protons) as a result of being hit by a high-energy (several 100s of MeV or greater) proton. Chemical process designed to selectively extract strontium. A reactor in which a self-sustaining nuclear reaction can not be maintained; thus, when the source of neutrons is removed the reactor shuts down. Trivalent Actinide Lanthanide Separation by Phosphorus Extractants and Aqueous Komplexes. The transformation of a minor actinide or long-lived fission product into another nuclide that is either stable or has a shorter half-life and thus, is less of a problem than the original radionuclide. Process for separating tri- and tetravalent actinides from
TRU: TRU burner: TRUEX:
Bibliography
Interactive Chart of the Nuclides from the National Nuclear Data Center at the Brookhaven National Laboratory. Website address: nndc.bnl.gov/chart [This site provides quick and easy access to nuclear data for known isotopes such a half-life, decay modes, etc]. International Atomic Energy Agency (IAEA). Web site address: www.iaea.org [This United Nations site is a comprehensive source of detailed, high quality international nuclear and radiation related information. Search this site for articles and reports on a wide variety of nuclear related topics such as nuclear waste management, transportation of nuclear materials, nuclear power world-wide, issues related to nuclear non-proliferation, etc]. Nuclear Energy Institute (NEI). Web site address: www.nei.org. [This site provides a general overview of nuclear energy information in an easily understood format].
Nuclear Instruments and Methods (A) Journal. Plendl, H.S., Editor, 1994, Special Issue on Nuclear Transmutation Methods and Technologies for Disposition of Long-lived Radioactive Materials, , Vol.414, 1-126 and Plendl, H.S., Editor, 2001 Special Issue on Accelerator Driven Systems, Vol. 463, 425-666. [These two dedicate issues of this journal contain a number of excellent articles containing technical information on methods and technologies for disposition of long-lived nuclear waste]. Organization for Economic Co-operation and Development, Nuclear Energy Agency (OECD/NEA). Web site address: nea.fr. [This site is a valuable resource for technical information covering research and development in the area of nuclear waste disposal. See especially proceedings from annual International Information Exchange Meetings on Actinide and Fission Product Partitioning and Transmutation].
U.S. Department of Energy (DOE). Web site address: www.eia.doe.gov [This very large site provides comprehensive data on energy use throughout the U.S. with links to numerous sites for specific energy information. Also see DOE Office of Civilian Radioactive Waste Management at web site ocrwm.doe.gov/; DOE, Basic Energy Sciences Workshop, 2005, The Path to Sustainable Nuclear Energy Basic and Applied Research Opportunities for Advanced Fuel Cycles, September 2005, available from http://www.er.doe.gov/bes/reports/files/PSNE_rpt.pdf; DOE Office of Nuclear Energy, Science and Technology, Office of Advanced Nuclear Research. Generation IV Nuclear Energy Systems, Ten-year Program Plan, Fiscal Year 2005, March 2005, available from http://nuclear.energy.gov/genIV/neGenIV1.html].
Nuclear Waste Management Organization of Canada (NWMOC). Web site address: nwmo.ca [Information on the strategy being used by Canada to handle radioactive waste from nuclear power generation].
UREX: UREX+: US NRC: USDOE: VHTR: Vitrification:
lanthanides and most other fission products using liquid cation exchangers, such as trialkylamines and tetraalkylammonium salts dissolved in organic solvents. Transuranium elements. A reactor or accelerator-driven device designed to efficiently reduce the inventory of transuranium elements by fissioning. Transuranium element extraction separation scheme to recover the trivalent actinides and trivalent rare-earth (lanthanide) fission products. Uranium extraction. Uranium extraction plus addition separation steps. United State Nuclear Regulatory Commission. United State Department of Energy. Very-high temperature reactor. Process by which nuclear waste is incorporated into a noncrystalline or glass-like matrix.
Uranium Information Center (UIC). Web site: uic.com [This site, maintained by the Australian Uranium Association, contains a wide variety of briefing materials and educational resources on nuclear energy topics]. US Nuclear Regulatory Commission (NRC). Web site address: nrc.gov/waste [This site provides information about types of regulated waste and activities, responsibilities and related information]. Wastelink and Radwaste.org. Website address: radwaste.org/ [Site are maintained by Herne Data Systems Ltd includes more than 10,000 links to radwaste, nuclear, radiation and environmental related companies, research centers, regulatory agencies, government organizations, non-governmental organizations, etc.]. Wikipedia Encyclopedia. Website address: en.wikipedia.org [A wide variety of nuclear topics can be accessed by searching this site by topic]. World Nuclear Association. Web site address: world-nuclear.org. [This site provides comprehensive and factual information covering a wide variety of nuclear-related topics from around the world. The information is easily understood and updated frequently]. Biographical Sketches
Patricia Ann Baisden received her BS degree (with honors) in 1971 and her Ph.D. in chemistry in 1975 under the direction of Prof. Gregory R. Choppin at the Florida State University. After completing her graduate degree, Dr. Baisden accepted a postdoctoral appointment with Nobel Laureate, Glenn T. Seaborg at the Lawrence Berkeley Laboratory. Since 1978, she has worked for the Lawrence Livermore National Laboratory in California holding a number of technical and management positions including Deputy Director of the Glenn T. Seaborg Institute for Transactinium Science and Division Leader, Materials Program Leader, Chief Scientist, and Deputy Associate Director in the Chemistry & Materials Science Directorate. Her expertise is in nuclear and radiochemistry; actinide chemistry, and lasers and optical materials and over her career she has authored or co-authored over 50 journal papers. Dr. Baisden has also held a number of professional positions including serving as Chairman of the American Chemical Societys Division of the Nuclear Chemistry and Technology, as a member of the Department of Energy (DOE)/National Science Foundation (NSF) Nuclear Science Advisory Committee, and as an editor of Radiochimica Acta, the International Journal for the Chemical Aspects of Nuclear Science and Technology. Additionally, she has been appointed to a number of National Academy of Sciences/National Resource Council study committees including the Committee on Environmental. Technologies for Decontamination and Decommissioning, Committee on Electrometallurgical Techniques for DOE Spent Fuel and Excess Weapons Plutonium Disposition; Committee on the Assessment of the National Institutes of Standards and Technology (NIST) Physics Laboratory, and the Chemical Sciences Roundtable. Dr. Baisden is also credited with starting in 1983 the "Summer School in Nuclear Chemistry," an Undergraduate Fellowship Program for DOE. This program, which will be held for its 25th consecutive year in 2007, has to date, introduced over 550 undergraduate students to the field of nuclear and radiochemistry. Currently Dr. Baisden holds the position of Assistant Associate Director in the National Ignition Facility (NIF) Programs Directorate at LLNL and is on special assignment to the Office of Inertial Confinement Fusion with the DOE/National Nuclear Security Administration in Washington, DC. Gregory R. Choppin received a Maxima Cum Laude Bachelor of Science degree for Chemistry from Loyola University, New Orleans, Louisiana, in 1949 and a Ph.D. from the University of Texas, Austin, in1953. He then began postdoctoral research with Glenn T. Seaborg in the new element research group at the Lawrence Radiation Laboratory, University of California-Berkeley. In 1955, he accepted a permanent position in the Lawrence Laboratory and was one of the four co-discovers of element 101, Mendelevium. These experiments were the first on single atoms as only one atom of Mendelevium was made per hour of irradiation in the cyclotron. In 1956, he moved to Florida State University as an Assistant Professor of Chemistry. At FSU, he initiated a research program in f-element chemistry, studying both lanthanide (4f) and actinide (5f) behavior. He spent sabbatical years at the Belgian Nuclear Center (Mol) in 1962-63 and at the German Nuclear Center (Karlsruhe) in 1979-80. He has spent shorter periods for research in nuclear laboratories in France, Portugal, Sweden, and Japan. His research has resulted in over 400 journal publications and 8 books. A major focus of his research has been the thermodynamics and kinetics of f-
element complexation reactions. Since 1975, he has focused attention increasingly on the environmental behavior of the actinide elements. Recognition of Professor Choppins research is reflected in a number of awards among which are American Chemical Society Award in Nuclear Chemistry; Presidential Citation Award, American Nuclear Society; Chemical Pioneer Award, American Institute of Chemistry; Award in Chemical Education, Manufacturing Chemists Association; Award in Rare Earth Chemistry, Rare Earth Society, Japan; Becquerel Medal in Radiochemistry, British Royal Society of Chemistry; Honorary Doctor of Science, Loyola University, New Orleans; Honorary Doctor of Technology, Chalmers University, Sweden; Alexander von Humboldt Prize, Germany; Hevesy Medal for Nuclear Research, Hungary. In 1969, he was given the honor of becoming an R.O. Lawton Distinguished Professor at Florida State University. In 2001, Professor Choppin became a Professor Emeritus.
To cite this chapter Patricia. A. Baisden and Gregory R. Choppin,(2007),NUCLEAR WASTE MANAGEMENT AND THE NUCLEAR FUEL CYCLE, in Radiochemistry and Nuclear Chemistry, [Ed. Sndor Nagy], in Encyclopedia of Life Support Systems (EOLSS), Developed under the Auspices of the UNESCO, Eolss Publishers, Oxford ,UK, [http://www.eolss.net]

Nuclear Fuel Cycle

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Nuclear Fuel Cycle

Uploaded by

Copyright:

Available Formats

RADIOCHEMISTRY AND NUCLEAR CHEMISTRY Nuclear Waste Management and the Nuclear Fuel Cycle - Patricia. A.

. Baisden, Gregory R. Choppin

NUCLEAR WASTE MANAGEMENT AND THE NUCLEAR FUEL CYCLE

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Greater than Class C

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

separated and fissioned using fast neutrons

Encyclopedia of Life Support Systems (EOLSS)

Pu ( T1/ 2 = 24 000 a). Using this logic, the net loss

Z > 94 (transplutonium elements) FP = Fission Products

* 1000 MWe LWR, discharge plus 150 d

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

6. Nature of HLW as a Function of Time

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

10. Separations Technologies for the Nuclear Fuel Cycle

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

10.4. TRAMEX Process

Encyclopedia of Life Support Systems (EOLSS)

Phosphoric acid based DIDPA, HDEHP, TBP

Encyclopedia of Life Support Systems (EOLSS)

Pyridine and Amides

Thio-phosphinic acid based

Encyclopedia of Life Support Systems (EOLSS)

Electrochemical redox with heteropolyions

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

11.1. Transmutation of Minor Actinides

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Xe + n 131 Xe + n 132 Xe (stable)

129 Xe + n 130 Xe (stable)

Cs. Cs-134 ( T1/ 2 = 2 a) is also present at about the percent level.

Encyclopedia of Life Support Systems (EOLSS)

12. Aqueous Chemical Processing

12.1. Improved PUREX Process Removal of Np, I, and Tc

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)

Very-high temperature reactor (VHTR) Supercritical-water-cooled reactor (SCWR) Fast-spectrum systems

Encyclopedia of Life Support Systems (EOLSS)

Implementation: approx. time period Now 2010-2015

Encyclopedia of Life Support Systems (EOLSS)

Encyclopedia of Life Support Systems (EOLSS)