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Clark, Hobart, and Neu 1995 Waste Isolation Pilot Plant Compliance Certification Application Reference 135 Clark, D.L., D.E. Hobart, and M.P. Neu. 1995. Actinide Carbonate Complexes and Their Importance in Actinide Environmental Chemistry, Chem Revs. Vol. 95; 25-48. Submitted in accordance with 40 CFR $194.13, Submission of Reference Materials. Carera, ;., Neurcan. 3.p.. - 986 "Est~rncaonoi ?x:ier Parcrneters L'nae; Panslent anc' S:eadu Sco:z ~oi~icions,2. Unlacaness, Stc;z.:ird, and solucion ftiqo:ithrns." 9. Clark, D.L.. Floba~.D.E., Neu, M.P.. 1995 '9ctinicz Carbonate Complexes ana Thslr Irnporcccca in Ect;nide Environmencai G,~mrsny."=?em Revs. ',Jot. 05, 25-48. ON ' ; x 28.C3 398.00 Cleveland, J.M.. i 9* nGit:calRevleu of Plutonium Eov~lbrioof Environrnencal Concern. In Moueirng in Equmus S;lstms: Smrct:on, So~ubrlrtuanu tlnq of t9e Emencan Chernrcc~Societu, Pdiarnr Beacn, Fi, Series: 3521 -336. Cti~- ; x CLO.CC 220.30 . - , I. 2av1s.G.B.. Jcnnsco i 984 'Ccxxenc on Cmcamincnc Tianspor: :n fracturad PONS Media: fcr s Sjscern cS ~rciielFrcc:vres" 5y SLG~C~U,C.A., and Fmd, E.O.,' Rasc~rcesRzsecrcn, \jot. 23,i\.'o. 9. s?. : 321 - 1 322, Szpt. ., -- ? 984. 1 Qtl; I i x i 3.:: ' 48.50 , , -. - 4 Actinide Carbonate Complexes and Their Importance in Actinide Environmental Chemistry I David L. Clark,'~~~David E. Hobart,lb and Mary P. Neda Chemical Science and Technology Division, Los Alamas National Laboratory, Los Alamos, Mw Me& 87545, l?eThe Sciems DMm, Lawrence Berkeley Laboratory, BeBerky, California 94720, and UE G. T. Seabog imWe for Transactinium Scienae, I Livemre, California 94551 I Received May 16, 1994 (Revised Manuscript ReceM September 16, 1994) Table 1. Oxidation States of Light Actinide I Contents Element@ 1. Introduction Pa U Np Pu Am Cm 1 .I. Complexation Equilibria I11 I11 I11 I11 (111) (III*) (III*) 1.2. Hydrolysis (IV*) IV (M (N) (IV*) N TV 1.3. The CarbonateBicarbonate Ligand System (V*) V (V*) (V) V 2. Carbonate Complexes of the Actinide Elements (VI*) (VI) (VI) VI VII VII VII 2.1. Hexavalent Actinide Carbonate Complexes 2.1.1. Solid State and Structural Studies a An asterisk indicates the most common oxidation states, 2.1.2. Solution Chemistry and environmentally important states are in parentheses. 2.1.3. Species Distribution in Aqueous Solutions 2.2. to approximately 38000 tons in 1985, and was Pentavalent Actinide Carbonate Complexes predicted to reach 88500 tons in 1990.' For the 2.2.1. Solid State and Structural Studies United States alone, it is estimated that by the year 2.2.2. Solution Chemistry 2000 the accumulation of spent nuclear fuel will 2.2.3. Species Distribution in Aqueous Solutions reach 40000 metric tons.5 The majority of this spent 2.3. Tetravalent Actinide Carbonate Complexes fuel and its decay products is expected to be stored 2.3.1. Solid State and Structural Studies in deep geologic rep~sitories.~Each repository site 2.3.2. Solution Chemistry has its own unique conditions and intrinsic barrier 2.3.3. Species Distribution in Aqueous Solutions properties; and the characteristics of these sites is 2.4. Trivalent Actinide Cahnate Complexes under intense study in many countries. 2.4.1. Solid State and Structural Studies The principle transport mechanism for migration 2.4.2. Solution Chemistry of transuranic elements away from a repository is 2.4.3. expected to be by action of water, and therefore the Species Distribution in Aqueous Solutions chemistry of transuranic elements under natural 3. Concluding Remarks aquatic conditions is receiving a considerable amount 4. Acknowledgments of study. In order to understand the chemical 5. References behavior of transuranic elements in natural aquatic systems, one must consider a wide variety of complex geochemical processes such as ~orption,6-ll-~~pre- 1. Introduction cipitationldissolution and redox equilibria? solu- bility,12-l9 radioly~is,2O-~~hydr~lysis,~~.~~ humic acid In the last decade we have dramatically increased c~mplexation,~~-~~colloid generati0n,4~.~~."-~~ and the our understanding of the chemistry of actinide ele- effects of other metal ions and other potential ligands ments with a potent emphasis on relevance to the on actinide ~peciation.~.~.~-~~Each of these topics is environment. This flourishing chemistry of the 5f an active area of research and to describe them all elements was stimulated by many factors, including is beyond the scope of this paper. There are many inorganic chemists' interest in structural diversity, reviews which provide an overview of the chemical new synthetic methods, new chemical separations, behavior of transuranic elements in natural aquatic and a need to understand the fate and transport ~ystems.~,~*~-~' properties of actinides in natural aquifer systems. Of the 14 5f elements following actinium in the The purpose of this review is to present the motiva- periodic table, thorium, protactinium, and uranium tion behind environmentally important actinide car- occur naturally.75 On the basis of nuclear properties, bonate research and to provide a modem reference availability, and distribution, only six of the 14 in the area of actinide carbonate chemistry that actinide elements (thorium, uranium, neptunium, reflects the developments and achievements in the plutonium, americium, and curium) are of long-term field since Newton and Sullivan's thorough review environmental concern.@' The known oxidation states of actinide carbonate solution ~hernistry.~ of these elements are listed in Table with the The vast majority of transuranic elements are most common oxidation state in aqueous solution produced in commercial nuclear reactors from ura- denoted with an asterisk, and environmentally im- nium-based fuels.3 It was estimated that cumulative portant oxidation states are in parentheses. The spent nuclear fuel from western nations amounted variety of accessible oxidation states for these ac- 0 1995 American Chemical Sodety I al. i6 ~henkxlReviews, 1995, Vd. 95, No. 1 Clark et Actinide Carbc actinide sc tion. The I effectively coordinatic are "hard" plexes wit carbonate actinides 1 trend: An Complex variety of stants it i: literature 1 their equil David L. Clark received a B.S. in chemistry in 1982 from the University Mary P. Neu received her B.S. in chemistry and mathematics from the of Washington, and a Ph.D. in inorganic chemistry in 1986 from Indiana University of Ahska, Fairbanks, in 1986 and her Ph.D. from the University University under the direction of Distinguished Professor Malcolm H. of California, Berkeley, in 1993 under the direction of Professors Darleane Chisholm. He spent a year as an SERC postdoctoral fellow at the C. Hoffman, and Kenneth N. Raymond. She is currently a University of University of Oxford with Malcolm L. H. Green before joining LANL as a California President's Postdoctoral Fellow, working with David L Clark at J. Robert Oppenheimer Fellow in 1988 with Alfred P. Sattelberger. He Los Alamos National Laboratory. Her research interests are in the areas became a staff member in the Isotope and Nuclear Chemistry Division at of inorganic, environmental, and radiochemistry of heavy metals, including Los Alamos National Laboratory in 1989. He is presently a secthn leader the actinides. of the Inorganic and Structural Chemistry Group at Los Alamos National Laboratory. He is a research affiliate at the Glenn T. Seaborg lnsttute they are released to the environment. It is conve- for Transactinium Science, Livermore, CA. His research interests are in the areas of inorganic, environmental, and radiochemistry of heavy metals, nient to divide actinide environmental contamination including the actinides. into categories of short- and long-term concerns for exposure andlor groundwater contamination. Short- term concerns involve actinide isotopes which have relatively short half-lives. Dilution and natural Equilibr; decay will effectively ease these kinds of actinide ; the presen contamination problems. Long-term environmental 1 make up t concerns involve long-lived actinide isotopes (half- lives greater than hundreds of years) produced in large quantities which require extreme precautions and zero in handling, isolation, and disposal. formation 8 Actinide elements released to the environment will - zero ionic E eventually come into contact with water. Carbonate and bicarbonate are present in significant concentra- tions in many natural waters, and are exceptionally strong complexing agents for actinide ions. There- fore, carbonate complexes of actinide ions may play David E. Hobart received his 0.A degree in chemistry from Rollins College an important role in migration from a nuclear waste in 1971. In 1981 he received his Ph.D. in chemistry from the Universtty repository or in accidental site contamination. The of Tennessee, Knoxville, under the direction of Professor Joseph R. potential for aquatic transport of actinides as a result Peterson. David then held the position of postdoctoral research associate of carbonate complexation is reflected in the forma- at the Transuranium Research Laboratory, Oak Ridge National Laboratory, tion of naturally occurring uranyl carbonate minerals Oak Ridge, TN. He was a staff member in the Isotope and Nuclear such as rutherfordine, U02(C03),78liebigite, CazlJJO2- / Chemistry Division. Los Alamos National Mratory, Los Ahmos. NM (C03)31'10- 1 lH20,'9 and andersonite, Na2CaWO2- I from 1983 to 1993. He is presently the group leader of the Actinide Geochemistry Group, Earth Sciences Division, Lawrence Berkeley (C03)33.6H20.80It is our responsibility to understand Laboratory, Berkeley, Ck He is a guest scientist at the Glenn T. Seaborg and predict the fate bf industrial and research Institute for Transactinium Science, Livermore, CA. His research interests byproducts, whether they originate at mines, nuclear indude actinide element aqueous solution and did state chemistries; reactor sites, or within long-term repositories of speciah, solubility, spectroscopy, redox behavior, thermodynamics, highly radioactive waste. To gain an understanding complexation, etc. His work is focused on actinide chemistry relevant to nudear waste isolation and the environment of the complex geochemical behavior of these materi- als, we must begin with a fundamental knowledge of actinide carbonate chemistry.
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