(h- -f(*S ORNL-5050
DIVISION
Annual Progress Report
PERIOD ENDING MARCH 31.1975 JBBSk
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This rapon MM pimmml m an account of work ipomwd by rtw UnHotf Stmt (•rovornfoant. Naioiar tno UMM Stows nor 010 Enanjy ftaaujrcfi and Davolooaaant AdniMtstiation, nor any of ttwir ainptoyaas, nor any of tnaw contractors, subcontractors, or ttttir atnafcoYaas* nofcas any warranty, axpnjss or ttnpkad, or aavurnts any lajaf fcabinty or rasponsvbrMy for ina accuracy, conojilofanass or uavfuloaas of any •nforviujtton, apparatus, product or procass ovactoaad*. or roprosants that its uaa would not mfrinpt pnuasaly oumod nplrts. uc-w-
CHBMCAL TECHNOLOGY WVUttM ANNUAL rwoowni REPORT I 31,1975
0. E. Ferguson — Division Director R. 6. Wymer — Associate Division Director K. B. Brown — Aiiirteru Divuior. Director A. P. Msjfntuskcs — Chemical Development Section Chief C. D. Scott — Experimental Engineering Section Chief D. E. Ferguson — OCTOBER 1975 OAK RIDOE NATIONAL LABORATORY Oe*Btdoe.Tewneee«e 37130 operated by UNION CARBIDE CORPORATION torflw ENERGY RESEARCH AfU>De3rEU>PJva£NTAC«ttl«^^ WeporapnwHOiiitri»ediwdii>earie»are»lbluiM ORNL-2392 tend Endfeaj Aupm 31.1967 ORNL-2576 Period Endinff Aupm 31. <959 ORNL-27K Period Endng AupM 31. H» OftNL 2993 Period Endeej AupM 31.1M0 ORNL-31S3 Period EndniNhv 31.1M1 ORNL-3314 Period End** May 31.1992 ORNL-34S2 Period EieJuMj Mo> 31. WW ORNL-3t27 Period Endwaj May 31.19— ORNL-3B30 Period Eodnf Nay 31.19ft ORNL-3M6 Period EndmgMoy 31.199* ORNL4145 Period End** May 31,1997 OFML4Z72 Period Endoej May 31. 1961 ORNL-4422 Period Enden May 31. Ht» ORNL-457? Period End** May 31. 1970 0RNL4H2 Period Endmf MHtk 31,1971 ORNL-4794 Period Endinf March 31.1972 0RNL49B3 Period Emftni Man* 31,1973 ORNL49S9 Period En*ne March 31.1974 Preface This piopes report is * »Mwy of the research sod dcwtefffurf iffatu conducted io the Chemical Technology Dmskm doring the period April I, 1974-ltoch 31, r9V. ftanher Mfonaalic: rcprding work n the varans programs caa be obtained from the topicalreports ah d tosnei «3da eitei m the references. ii: Cbutents PREFACE - 1. DEVElXJPIIEPfT OF AQUEOUS PROCESSES FOR LMFWFUEL5 I 2. HTCR FUEL RECYCLE DEVELOPMENT PROGRAM 2 3. MOLTEN-SALT REACTOR PROGRAM 3 4. WASTE MANAGEMENT 4 4.1 Geologic Disposal Evaluation Program 4 42 Processing Modifications for Improved Waste .ianigrmenl 6 4 J Leaching of Radionuclides from Waste Solids II 4.4 Methods for Management of ORNL Liquid Wastes 14 43 Projections of Radioactive Wastes from the Nuclear Fuel Cycle 19 5. TRANSURANIUM-ELEMENT PROCESSING 20 5.1 TRU Operations 20 5.2 Special Projects 21 6. HTGR TECHNOLOGY AND SAFETY PROGRAMS 24 7. PREPARATION OF "3UO, 25 7.1 Recovery of233U from Waste UOj and Scrap UOi-ThO, Pellets 25 7.2 "'U Purification Systems 25 7 J Conversion of" 3U from Nitrate Solution to Ceramic-Grade Dioxide Powder 26 8. SEPARATIONS CHEMISTRY RESEARCH AND DEVELOPMENT 27 8.1 New Separations Agents 27 8.2 Separation of Radium from Uranium OreTaitngt 28 8J Separation of Alpha Emitters from Fuel R«procesting Wastes 30 8.4 Waste Stream Processing Studies 31 8J DistrmutimEquih1>ria,IUrieti(»,andMechafusrm 33 9. BIOMEDICAL TECHNOLOGY 36 9.1 Advanced Analytical Techniques 36 9.2 Centrifugal Fast Analyzer Development 42 v •BBBBBSHB BLANK PAGE L VI 10 BCVWrOWMTItTALSlUnB ** MA niiwilil ltarf>w«fftifci«ii .... 49 11. MOCHBMCALBKMEEUNG 57 I I.I faiyMtOtaJyarthtte-iiaBofHjiiura .... 57 II J? fcowactgrft [Infill 59 IIJ •Jtpimfftiilyfui 61 12. CQALTKHNOUlCYnKKKAM 65 12.2 Ttp• n ti i•• Xr i TinliMji «. i2j n» »•!•!< r«*i i ijM.Tm rf»i»storiBiii nin Tmx* « 13. ATnMDCOXfDCS.NmtBCS.Ara>CAltm)ES ID 13.1 FifwntwofTtriM ijMwi pan 70 13.2 HuMi Hw [fMii 70 14. STUDKSmCHBVALBIiaNEBUNGSCIBeCE 72 14.1 Ma«TwfcfRjMtaiOpainsbUcCalMMB 72 14.2 ft ii •lnwOpfctewi Slwte» 72 143 n nfc^Sf*e»Co>—iFarfwi^CooJocfiida^ 74 CaMactarUM«Vai««4Mac«y 75 143 nipwili in uf'ijrwlnli Imfciii 75 I4J6 Ifc^iiicCiwwiiiliwofCnpliiie 77 15. COKntOUEDTKHMIUClEARrROGItAM 79 1*1 Stu|ii^S»w*t»otaTniiBwlfc«<^Syrtn»fo>»E«yeiiMirtjiFwio«PwmlUic^ 79 ISJ rtwpmminmfar Tew * ofCijuwiptiiw tWfwgfar Fwiwi Inctort 81 1SJ TriliMiSoiMJMSiMm SI I*. KJOeeSTUMB S2 16.1 loAMSafplio«oiiClMcodlfMI(MiMiD(9Drpli(M 82 16.2 Reaction of OinoJc ndWtt win Hypcnuotrooic Nitric Kot 84 !7. REACTOR SAFETY RESEARCH 86 17.1 fiHtoPtofcctRclcMfroMLimFMl 86 17.2 Tf—Hm Mam fnm UtfK fad 87 vu 18 NULLA*REGULATORYCOMMISSIONPROGRAMS 91 IS. I Ik ulupauat nf "As Low as PracOcaMe" < ALAPl Gaatcs for the Nwdear Fad Cyde 91 1SJ Safety Review of Nudear Facatiie* 91 1SJ Safety Review of Tnasport Casks 92 l«». DIFFUSION OF ADSORKD SPECIES IN rOROUSMEDU 93 30. MISCELLANEOUS PROGRAMS 96 20.1 RCIMKC States 96 202 Studies lavofciai Tests of Obsolete Casks 96 20J PiipMHi of ORNL Radioactive Waste by Hyataafc Fractarif, 97 20.4 Storage. FanfkafMi. aarf Datfributioa of "*U 96 20.5 CnesMcal Apajjutioas of !vacfear Exatosran 99 20.6 Preparatina of Tnasiag Gvajes for Nadear Facility Peunaarl 99 20.7 tamuanuiiial hapact Stateavcat on the US. Nvcttar Power Export Program 100 PUBLICATIONS SPEECHES. AND SEMINARS 101 1. Development of Aqueous Processes for LMFBR Fueb Tim woAeameumti with the fciflapajnii of aaae- Plla*IIR«> 8 a^PaT •™a^™a^^a» *J" *^P*aw 9W^Pa^H*w ^BBT*^» v^^a^vHi aaaaa^B^avJH^ OK PIDCOKS far LMFHt fiMb it MM sepofMi ho« dm rieei • theLMFMT faaf iterrdr /lugi— HIMJUJI Hepnef jfar rtr /awJorf Ap* I fi> Dutmttr SI, 1974 (ORNL ThMt36> Soae Meat cf the work have aho the category UC-79 - Liaajj Metal Fan Breeder 1 1 BLANK PAGE 2. HTGR Fuel Recycle Development Program The Chemical Technology Division's activities under information must be distributed solely under the the HTGR Fuel Recycle Development Program, which category UC-77 Gas-Cooled Reactor Technology. The is part of the overall Thorium Utilization Program, work has been reported separately in monthly GCR include develupir.-nt work in head-end reprocessing and documents and will be summarized in the Gas-Cooled fuel fabrication, off-gas cleanup, and conceptual and Reactor Programs Progress Report for the Period cost studies. This work is not reported here this year, in January 1.1974, to June 30,1975 (to be published). compliance with regulations which stipulate that such 2 »-*«•*•- r."1 ""— •• -^*'* nrrur-"*nm»-r^*^^*arew.,^>**fr3*sr*c5reer:'*»^ xunsHiwawnnaR*~**»* 3. Molten-Salt Reactor Program The Chemical Technology Division's activities under 1. MSR Prognm Semiennu. Progr. Rep. Aug. 31. 1974. the Molten-Salt Reactor Program are concerned with ORNL-5011.p.99. the development of on-site fuel processing methods for 2. MSR Program Semmnnu. Progr. Rep. Feb. 28. 1975. Molten-Salt Breeder Reactors and with the production ORNL-5047 (in preparation) of the various molten salt mixtures required for the 3. J. R. Hightower. It., ex al.. Engineering Development MSR Program's research ami development activities. Studies for Molten Sell Breeder Reactor Processing No. 18. ORNL-TO-4698 (March 1975). This work is not reported here this year, in compliance 4. J. R. Hifhtower. Jr., ei al.. Engineering Development with regulations 'vhich stipulate that such information Studies for tMten-Sell Breeder Reactor Processing No. 19. be distributed solely under the category UC-76 ORNL TM-4S63 (July 1975). Molten-Salt Reactor Technology. The work has been 5. J. R. H^htower. Jr.. et al.. Engineering Development reported separately in MSR monthly documents, in the Studies for Molten-Salt Breeder Reactor Processing No. 20. ORNL-TM-4870 (in preparation) Molten-Salt Reactor Program semiannual progress 6. J. R. HightowcT, Jr., et al.. Engineering Development 1 2 reports. * and in Chemical Technology Division quar Studies for Molten-Salt Breeder Reactor Processing No. 21. terly progress reports.3-* ORNL-TO-4S94 (in preparation). 3 4. Waste Management 4.1 GEOLOGIC DISPOSAL tics to be examined for this purpose relate to stability EVALUATION PROGRAM (both short-term mechanical stability for the operations and long-term stability for preservation of waste con The Geologic Disposal Evaluation (GDE) Program, as tainment) and tightness (i.e., notation from the circulat now constituted, has two objectives: first, to evaluate ing waters of the biosphere). This wil be accomplished the suitability of all potential geologic formations and largely through the study of mines and other under rock types in the continental United States as perma ground openings constructed in the various rock types nent receptacles or repositories for any category of throughout the country. The geologic formations or radioactive waste, using any appropriate emplacement rock types under investigation include: (1) rock salt technique; second, for those promising geologic forma (interior salt domes of the Gulf Coast area; Salt Valley tion-waste-type-empbeement technique systems, to anticline and other structures in the northwest portion carry out the research and development activities that of the Paradox Basin; and deep bedded salt deposits of could eventually lead to the establishment of actual the Williston. Sapai. and Salina Basins); (2) argillaceous waste repositories using one or more of these systems. rocks (shales and especially the Pierre Shale formation); During the current report period, emphasis has been (3) carbonate rocks (limestones in northern Ohio and focused on (I) geologic and hydrologk stvlies of a Kansas City areas, and the Sdnu Chalk in Alabama and number of •ock types, to evaluate their fundamental Mississippi); (4) volcanic rock (basalts and tuffs); (5) suitability for u.e as waste receptacles, and (2) develop crystalline rocks (granitic intrusives and high metamor- mental studies, in particular those concerned with rock phics); and (6) porous and permeable formations for mechanics, rock properties, and radiation effects on disposal of fluids. rocks and borehne plugging. Bedded salt, srit dome, aid srit anticlines The Major chanra have occurred in the GDE engineering stratigraphy of the southeastern New Mexico repository program Hiring the past year. The Bedded-Salt In-Situ site developed from cores taken from exploratory Experimental Program to support the high-level waste boreholes AEC 7 and 8 indicates that marginal commtr repository design effort at the New Mexico site was cial potash ore zones occur in the McNutt potash zone terminated in late August 1974. With the assignment of of the Salado Formation that overlies the three candi primary responsibility for the design, construction, and date salt horizons which are at depths of 1900,2100. operation of an alpha repository to Sandia Laboratories and ~ 2700 ft. A single-unit seismograph operating at in February 1975, all ORNL engineering efforts direc the site since January I, 1974. sensed one significant ted toward the design of an alpha repository at the New seismic event which is being studied to determine Mexico site were terminated (or will be by the end of whether it might have been a small earthquake or a rock FY-1975). Engineering efforts are new directed solely fall in a nearby potash mine. Based on geologic and toward evaluating and assessing promising waste dis engineering studies, it was concluded that no economi posal systems developed by the GDE Program. cally significant oil and gas fields are likely to be discovered in or around the site. Several studies are Geology and Hydrology under way to determine tectonic stability, hydroiogic The objective of the geologic and hydroiogic studies is stability, and location of salt domes suitable for waste to investigate the general characteristics, features, and storage facilities. Preliminary analysis of the data occurrence of a number of rock types so that their indicates that several domes appear to be suitable. A fundamental suitability for use as radioactive-waste preliminary geologic investigation of the salt anticlines receptacles can be evaluated. The principal characteris in Paradox Valley, Utah, indicated that the deposits at 4 5 the northernmost portion of the Salt Valley antidote Reck prauerty sacamanwaems. The coefficient of have the greatest potential for a waste repository site. thermal expansion (CTE) for pure KaCI crystals and Argauceous rock. A survey study was completed natural rack salt from the Lyons mine has been which explains and illustrates the critical geologic and measured. The CTE of the pu»e crystal agreed weB jrith hydrologic characteristics of several rock types, such as the reported literature values and fits the expression shale and mudstones, which would be instrumental in their containment of radioactive wastes. Since the most CTE = aX I0-* *C~' = 41J03 - 2.9*4 X 10*/r2 affirmative evidence of hydrologic tightness and me l • 1.015X Vi't*1352X HTV. chanical stablity of rock exists in subsurface excava tion, a survey was conducted of rhe tnert tfsai SO Natural rock salt CTE measurements differed greatly n svems that have been constructed tor > •<*> .. f liquid that the sample expanded rapidly and irreversMy on petroleum gas. Those regions of the Uni-ea States dial first heating to 140*C; this was probably due to the appeared most favorable for a waste storage cavern were expansion of the brine inclusions exceeding the plastic delineated. Studies were initiated to evaluate the limit of the salt lattice, thereby causing plastic strain or suitability of the Pierre shale formation and the Green deformation. Thus, the results obtained on beating the River ofl shak formations as waste repositories. sample are only valid for tins particular tinve-tempera- Carbonate rack. Studies are in progress to evaluate ture history. The results obtained on cooling, however, the suitabiity of the essentially dry limestone forma show that the true CTE of natural rock salt is tions near Barberton. Ohio, and Kansas City, Kansas, as essentially that of pure NaCI after the induced stress is waste repositories. -•-• • » rcneveo. Vckawk rack. Studies are under way to provide A device, the "plane probe," for rapidly measuring, information about the geologic and hydrologic factors the thermal conductivity and thermal dnTusivity of affecting the utility of basaltic rocks and tuff for waste rock samples has been developed and tested and is now disposal. Specifically, infomiation about the rock operational. The results wil be used in thermal analyses underlying the Hanford Plant Site and Nevada Test Site studied to determine the effect that heat released from is being evaluated. radioactive waste wB have on various waste disposal CtysfaMne rack. A study was initiated to evaluate the systems of interest to the GDE Program. information available from geologic studies at the Rock aMdumks. The rock mechanics analysis effort Savannah River Reservation and to extrapolate it to is divided into two parts: a finite-element analysis other areas in the eastern coastal plains with the same technique using both thermoeustk-plastic and thermo- type of rocks. A similar study was initiated of the rock riscodastk laws to model the stability of nunc excava in the Minnesota. Michigan, Wisconsin, and neighboring tions, and a complementary semiemprrical model to Canadian areas to establish the geologic and hydrologic simulate a ful-sized repository. Both models are being conditions that cause mines in this zrea to be dry* or validated using appropriate actual mine stabiity data. wet. SteeeaVenergy studies. The stored-energy studies on Arenaceous rack. Studies are under way to evaluate salt and solidified wastes were essentialy completed. It small and "enclosed" basins containing rock formations was concluded that the storage of radiation energy in of adequate porosity and permeability to receive liquid salt will not present any barrier to the safe operation of waste. a salt mine repository. Data obtained with sohdified wastes in a cooperative program with Pacific Northwest Develouujw^KBl studies Laboratory are stil being analyzed. A review of the general aspects of radiation damage and energy storage Various studies are in progress to provide the experi in solids, and of pertinent physical and chemical mental and developmental information necessary to properties of rocks (in particular, silicate minerals and support both the geologic and hydrotogic studies and limestone), does not indicate any significant amounts of the engineering assessment studies, in particular, and to stored energy or any significant radiation-induced evaluate the impact of the waste disposal operations per chemical effects at the gamma dose and the fast- se and other works of man on the long-term contain neutron fluences «10*7. > 3.4 keV) that will prevail ment provided by any geologic formation. These studies in the rock immediately adjacent to buried waste. This include the development of borehole plugging tech program is being redirected into a broad study of niques, mine stability and rock mechanics analysis, rock rock-waste interactions to obtain information, such as property measurements, and rock-waste interactions. the migration of radionuclides from waste through the 6 geologic formation: the effects of radiation on physical deep rock disposal concept for high-level waste, and a and chemical properties of rock: chemical mtenctioas generalized stti-ly of the emplacement of heat-generat between waste and rock: the effects of high tempera ing encapsulated waste in a mined cavity. tures, including melting (on both waste and rock): and Studies of the IVddedSaH Mat rnw*. To document methods for effectively isolating waste packages from the Bedded-Salt Not Plant (BSrT) design effort, a the rock and the circulating groundwater. Conceptual Facility Design Description report was assembled and given limited distribution m May 1974. boreholes that haw been or wil be drilled at afl This report is a file compilation of the work done by prospective waste repository sites must be plugged, it is Kaiser Engineers. Inc.. under the technical supervision necessary, particularly for a salt mine repository, not of ORNl; the work was terminated m November 1972. only to study the dissolution of soluble rock histori Some updated information and design alternatives were cally and theoretically but also to develop materials anoco- and techniques for emptacing and testing the borehole The BSIT in situ experimental program was termi plugs. Studies are under way (I) to determine the nated in August 1973. A report deewnenting the history of salt dissolution around boreholes in the planned experiments, the prdiminary equipment Hutchinson salt formation in Kansas;(2) to develop and design, the mine layouts, and the initial contacts with validate a mathematical model of salt dissolution potash mine operators in the southeastern New Mexico around a borehole in a salt bed which would predict the potash field was placed in ORNL Central Fifes size and shape of the cavity that would develop if fresh Alpha iip injury it f n In July 1974 the GDE water enters the top of the formation with brine Program was directed to develop "m-house" concepts removal at the bottom: and (3) to develop and validate and mine arrangements for the disposal of alpha waste a mathematical model of conveuive-diflFushe fiow in a and spent-fuel bulb in a suitable geologic formation. static-water column in an open borehole. Further guidance in August 1974 specified that the fn addition, several ongoing programs are in progress: conceptual designs developed for the Lyons. Kansas, (I) to develop methods for mechanically forming a repository and the BSFP should be reviewed, evaluated, borehole plug with natural materials, such as shales.(2) and. based on current alpha repository design criteria, to chemically empbee a borehole plug by hydrothermal used to develop a concept for the surface facilities by transport (usually by aqueous solutions at temperature "fitting'* them to the New Mexico site. This study was and pressures different from the ambient), and (3) for completed, and 15 drawings showing the location of the rock salt, to grow a molten-salt plug in situ. Civil facilities on the site, as well as their conceptual design engineering grouting techniques and commercial bore features, were prepared. hole plugging programs were also reviewed. and a survey Straiigraphic data for the New Mexico site indicate of the literature pertaining to naturally occurring that potential salt horizons exist at 1900. 2100. and borehole plugs was carried out. — 2700 ft below the surface. Engineering studies are in Most of these studies will be completed early in progress for the preliminary analysts of: (I) the FY-197o. The information obtained will be evaluated stability of a mine layout in each of the three horizons: and used in developing a program (o field-test promising (2) the methods and equipment required for drilling materials and emplacement techniques in situ. spent-fuel hull canister emplacement holes: and (3) the various methods for excavating storage rooms, etc.. and for transporting excavated salt to the hoisting facility. The studies will be completed by the end of FY-1975. Engineering studies and analyses .-re needed to assess Early in February 1975. Sandia laboratories was the technological feasibility of the many potential given the overall direction for the design, construction, waste disposal systems so that promising concepts can and operation of the alpha repository, and ORNL was be identified and developed into viable waste disposal directed to provide Sandia with all pertinent informa systems. These engineering assessment studies are tion. Any further alpha repository design effort at carried out under five broadly defined programs: (I) ORNL will be at the request of Sandia Laboratories analyses of techniques for emptacing gaseous, liquid, or solid wastes in a geologic formation: (2) waste charac 42 rllOCTESSING MODIFICATIONS FOR terization: (3) waste disposal system evaluation: (4) IMPROVED WASTE MANAGtMBTT development of promising waste disposal systems: and (5) repository design. Emplacement techniques being This program for the improvement of waste manage analyzed include the rock-melt capsule concept, the ment by additional removal of actmides. using modified 7 reprocessing methods, replaces the Waste Fractionation recycle of the aqueous wastes from the actinide Program, for which we reported activities and progress purification cycles. Secondary (irnrruing of the high- las: year. In the latter program, only the fractionation level waste is used to remove aaneridnm. tnnwm, and (or partitioning) of actinidci from the high-kitl waste any residual plmomnm. Insoluble residaes from fuel stream from a conventional Purex plant was toasideied. However, the investigation quickly revealed that the separated in feed clarification steps and treated, where program needed to be expanded in scope.'*2 In necessary, to reclaim the actmide values. An important addition to the atiiluymtnt of processes to partition requncmtni is the capabdity for removing the actinides the high level waste, it was concluded that significant without significantly increasing the volumtj of high-, advantages could be attained by improvements and low-, and mtetmediate-level wastes. Tins leqairement modifications of present-day reprocessing methods. prohibits the use of processes that discharge large The objective of this program is to determine the Quantities of rtirmk-il reagents m the wastes. If technical feaesbiity of removing actinides from aD the processes that depend on luge Quantities of reagents are radioactive wastes generated during the comnanciai to be used - and they are probatory necessary for the reprocessing of nuclear reactor fuck. During this report removal of americium and carimn - reagents that can period we investigated the possibility of iccovwing be recycled or converted to acceptable nonradioactive UtmnUIUII, ptutOtHlRII* IWDtltflNRIl, drnfflCfBClDflt* 3Mi i,htmkjl wastes awst be chosen. curium from spent i"ueb to such a degree that the The studies tomwiiing this program have not yet calculated radiological toxicity of wastes after about piugiessed to the point where the feasibility (or 1000 years of storage would be comparable to the mfeasMHy) of chemical flowsheets for the satisfactory toxicities of naturaly occurring uranium -mncrab. The removal of actinides from reprocessing wastes can be recovered actinides would receive special treatment for determined. On the basis of tracer-level studies with disposal, and might be recycled to power reactors where synthetic wastes and conceptual nuteiial-balance flow they would be burned to form fission products. The sheet studies, the cbemistry leqoired for the actinide study was routed to The development of methods lor separations (with the possMe exception of phnonwan) itmoving actinides from light-water tractor (LWR) appears to be theoretically possmie. However, a vast fuck. Removal of 99.99* of the piutomum. 95% of the amount of work remains to be done in order to select neptunium, and 99.9% of the inamum.amerkium.and the best combination of chemical steps and to prove curium firm LWR fuel (witfc phiioniurn recycle) would thai the desired chemistry can be carried out in reduce the potential hazard of high-level waste at 1000 workable, integrated processes under conditions involv years to about 5% of that for pitchbfcnde (asswmng ing high levels of radiation. Our work strongly suggests that 99.9% of the "'I is ako removed during repro that recycle methods might be developed for Purex cessing and is nvinagrd as a separate waste).1 At these plants which would substantially reduce the quantities levels of actinide and l2'l removal, the actinide of the misceBaneous low- and Mtermednte-lcvcl wastes. contribution to the lonf-tcrm hazard potential would The actnude-bearing wastes currently require relatively be comparable to that from the long-lived fissioa large-area sites for disposal or storage. Such wastes products. appear to be amtivablt to recycle if appropriate The concept of actinide removal is based on a chemical reagents are used for treating used solvent and combination of modified Purex processing and second for adjusting the neptunium and pmtonmm valences in ary processing of the high-ievei waste. According to this the Purex separations. concept, the necessary removal of uranium and nep The most troublesome chemical problems encoun tunium and most of the ptotonhim is accomplished by tered m aclamte removal ate associate-! with pMtoahaa extra extraction stages in the Purex process and by and amenemm-curium. The chief difficulty with Plu tonium lies in the need to maartaia it ip an extractaMe form at a very low coaccntratio *. Sroutmg experiments 1. W. D. goaf and R. E- Lewr. fiainiirj Snafcs of the showed that about OJ0I% of the |)lslumam was AmtihimimfofComimnmlH&-l.eTrttfMn la das process the certain of the fasten product! (| i) arc loaded oa catkM rcsia from mo, (of waste, selectively win 35 M HNO, We I W.TrJ* rCCOVCry • aad erbium tracts m thetie waste. Aside from ion is the caty cheautal reagent Ccmstmg oxalate be an attractive alternative to process for ia Ibis process has beca drmunilrated ia oW bbon.*ory, i process. synthetic wastes. A smfle oxalate pscco'xt'ia We ia a lint step toremove aboa t 95% of the for the recovery of aho to complex the aad for by step to .we tori of the tioa step. Considerably less ioa verification at fafJ required in these opcratioas dn ia the a to perfocmaace of recycle SVDCCSw* anvCmurofffflttCSMS WlOl fwMwOtlwKCVS ShOwt*tv AVC91CT than 99.9$ recovery of the trivakat rltmtats. The to be done to confirm the separatioa of oxalate precipitate aeed aot be accoai conceptualflowsheets for the pished ia the first step to be quantitative, siace aay ia figs- 4.1 and 42. residual precipitate waj be retaiaed by the ioa < oa the lughlrH column aad wil be deaorved whea die asetrk toa of LWR fad denicats are elated from the icsia cohaaa with 35 M 33J0O0 laWd/atelric ton. HNO,. A question yet lobe resohet) with icgard to the oxalate precipitatioa step is whether the precipitatioa and solids removal step is feasible ia remote opeiatkms. Tribvtyl phosphate extraction from heavily salted Studies arc beiag carried out to identify the i somtiom may be a viable method for the recovery of present ia waste sohrtioas and, uftuaately. to t the trrcaleut elements.4 If satisfactory methods can be developed for recycling the r&w% agents. Furex-type synthetic waste solutions; however, we teccady ob- technology might be extended toremove . - from the dissolution of irradiated curium and iraascarivm defeats along with the heavy LWR fuel (burnup. 33J00O MWd/metrk toa). Syathctic bnihaaides at the taae of reel irpmeisiag. In nitrate- waste jufutions coatam a smsi amount of solas when salted systems, the light laathanidei (abovt 80 mole % they am prepared- These soSds consist anaaruy of of the lanthanide fission prodacts) can be partitioacd tm. saver, hawJcs, and some ssmwmm. On from the trivaknt actaudes aad heavy hathmidn. Laboratory studies with synthetic wastes have shown that about 95% of the ssitiaj agent. AlTNOiH. can be recovered for recycle by precipilatiag it from IS M HNOj solution. The extra acid required to precipitate the salting agent could tbea be leumied by dbtlbtion and reused. 4. J.M. McKwUoi ct at.. Prtimmmtof U0H i pom AatmUet by SohrM Extrmttttm w*» HP, DM 3*1 (Aunuf 1*74). by synsfsetk waste soHdt is dhvumvd ia Sutt.SA 10 ¥%. 4.1. CMMftMl MriMtan K3r li fa.«iT*a 7:ks- wm ltf£ BLPUQL -in rJLn &uU<* i&A«i MM I rm fc. base «S' SS&L T tS9L Ffc.4J. CMH|»II ********* 11 Tiaasmatatna • coaajKrdal powerreactors i s owe of dK potcatol waste •wynf aJtemtncs for rcdac- ra; the bag-term hazard of the actmafrr removed fn 4J LEMommzoFAAuamKimei foci irpnn.miaf, «Bts. Darvag tar past year, studies have bee* peifouacd to deteraaae some of the Croats saaaar to poteatol anpacts oa the comaKrdd feel cycle miastiy Facmty at ORNL were made by dot aujhl retail from the inasKatatioa of these wane coatammg "Sr. acUamcs. and to citjpfcdi the treads ia iiaaiamuttua '"Cs. "*rV or ,44C, a day meuare of rates that remit from variali jas of both die type of oaferiab m days, aad me reactor piodaciag the wast' actaades ard the type of ofdaaeavtopcsB reactor inmaratiac rbe waste actaades. AM of the Apscy (IAEA) type i owe stadies arc amie at coadfeams of leach tests.5-* The Atactica of notope steady-state axydc of dK waste MM* of time if dam oocc perdcjr.bat spent-fad basis, dm were rti.yUed for ti mnaatjlioa if cJsmjed less oftea. were as folows: ap to 2S days ia aaaad air dK jMJaai Irarhcd from the U*m fad: 0.4% U:0.4*% Fa;9S%Np;aad99.9% AM. day (for ccsraa reteatioa) CavK.Cf.aadEs. the isotope leach rates foEowed dK order: U-Th fad: 0.49% U;0.4% Ta;0.49% Pa. 95% Np aad Cs > Sr > CM > hi. with overaf results awkatmt dot Pa.aad 99.9% AM. CM. Bk. CI. aad Es. caa pre teach rates coamaobte lo daae ob- Some of the Most import ml resaks cbtaiaed fa for wastes iacarporated arto buronajcjie tjanes these studies are as I (Re.4Jaad4.4i. 1. The arena* aaaat' traasmatauaa rates of die waste To obum data more rat***. dK proposed IAEA actnwdcj m dK foar types of Iran—laiioa reactors bach test was sacccssfaly mnmHei by i are: PWR-Ta. 32%; LMFBft. 4J%; PWR4.. 4.9%; with a smmto vahmw. a awch brper svfeu. «• tiTGR.7.**. ratio, aad a bran vohaae of hade water per vohaaeof specaaea. aad by natnaa; kadi water anre fre- 2. The recyckw waste actmides beiag trwM—nd ojatady. The kadi rate .or < occapy. OR the average, apptoxaaatefy 0.7% of a of CnaaJite. pottery day. or < PWR-U or PWR-Ta core. 1.4% of aa LMFBft core, These aamtives. as Bated, are ia dK oaier of i aad 2JV% of an rlTGR core. 3. The iafaate weatroa mdiyavaliua fiKtor (*,) of the waste actaades napes from 0.7 to 0.9 for day aad comammg oae. two. aad foar tams the Ihenaai traasmatatioa reactors aad from 0.9 to 14 le mks{6 wt %)dwred ami for aa LMFBR traanaatjlioa reactor. Siace the recycle waste actaaacs represeat oaty a sMafl frac- lioN of dK reactor core, dK overaf reactivity of aay of the reactor types Bcaaaged oaJ 4. The atatroa activity of fresh thermal it reactor fad. coataawaj actaades to be »r dae to dw presence of "*Cf; typical from 10" to 10" aeatroMMc'1 (metric tour' The aeatroa activity of fresh ^9* bv* aawaw^awaj^ mmm) m** ap* ^"J/» traaaajatatioa reactor fad » much tower. fm aW tmtmpmmtm «/ 10* lo 10* aeatroas sec "' (metric loa)'1 0KHL-49U IA«li nVat oaeof the aj. by E. D. cycle Kibe fori Iff-J»7 (1*71). 12 WftSTE PRODUCTS •mi i in— i in— nnymwyntwi i in— i i HI— I HIM CALCMES CERAMICS stt _ _. GLASSES LKME. errviMCNS. CEMENTS.. GROUTS.... ill i 11—^ I.Iill ©"• 10"* »"T »"* O"* 10* OJ © * I0H 10 LEACH RATE, q Km? toy) f%.*3. kti«—**MMi—in>—MtpMAac*. 0—L PaS *-11*04*1 CERIUM CERIUM AND TERBIUM PLUTOflMUM ANO AMERKWM YWKSTE PW00UCT& PLUTONIUM ANO CURUM 11 ii—i i mi in—i i HUM i "il I HUM I MR CALCINES CERAMICS iff . GLASSES BITUMENS CEMENTS GROUTS m IIIWM in—t 7 tar* »"* o' «r* ©"* IO* *>*• lO"* «0- 10 LEACH RATE. «****«•*) 13 for the 2S-day-cared pouts wbea the BOSS prodact thaa froai the groat; aatialy replaced twice per day (Fig. 4 J), la coatnst. loager taae period*, a sautter fractkm of cesaaa is the aamaMs leached froai anay bororihrate leached froai the sroat prodact that fhan the glass. r to be exphaaed by diffaskm and Unag the owdified effective dtfrasmties (Dr) derived i processes. The predicted aantiatT of < froai the data, rnaanairnai were wade of the aaoantt leached froai a groat luaijaiiag Coaa leached froai a S5-gal dnaa of pout, assaaaag two caaapared with those for a borosakate glass in Fig. 4.6. dwTcrcat fonas for the dnaa - a staawfaate medium The theoretkai lelatioasiaps vied in these cakahtioas . These calcvbtioas show that the aregnca ia ief. 7. The coBaparisoa of fractions leached (Fa> 4A> shows that, dariag short *aae periods, a years if the De is approxaaatcJy I X iC cat*/sec aad diehdy saaber fractioa of ccsaaa is leached froai the for awre thaa 3Q0O years if the De a appronraatefy 6 X I0'1* cai'/sec. They abo show that the projected anoaats kacbed froai a waste prodact that bassaoKd to approxaaate a scau-iafaatc awdaaa are conservative 7. H.W. J.C A- H- KJwJwMT* ID$.)»f. (oa the side of safety), saace they are cqaai to or greater Graatsl at the 77taj A—I Iwiiam OaWL OWC T9-4MI 0.2* 0.22 - 0.20 • X , o 0.1t- X u a UJ 0.18- _1 § • CO 0.l«- • J • CJ r fc 0.12 - g • »•* 0.10- •— ¥ r Ik 0.00 UJ > r- 0.01 a 0.01 - o.oe 0.0 T0TAI TI«tfWT5) 14 io-«- o 10 -»r u a to-* o 3C 10 "• r*- GROUT , Da « 7.61 »-* cnT/sec BOROSiLICATE GLASS k. 0.*8.4x«0-ecMystc O k*M»tO-Ts#c-« z 80ROSILICATE GLASS O 10-* 0,M.7«tO-»*airVsec <_> y*0.57 d «c •*- »o-«b o X u £ to-* I 11111. i i i i nil, i i i i nil, i.i HI IO-H » I0" ^sHM s irjT- to » w TOTAL TIME (YEARS) of the 137.d ('i/j = 30 yean) teacM Am a boiDsilicate j*a» aad a cruKnlitioas groat as •Redacted by 4.4 METHODS FOR MANAGEMENT OF obvious advantages, may be discontinued in the future. ORNL LIQUID WASTES Should this occur, an alternative method for handling the waste solution generated at ORNL will be required The shale fracturing process is a proven, economical - a method that can utilize largely existing technology method for the permanent disposal of intermediate- to convert the waste solution into a solid, noncombusti- level waste (ILW) solution at ORNL; over the past eight ble material with low teachability, suitably packaged for years, about 1,000000 gal of waste solution containing storage until some method of disposil is selected. 500,000 Ci of radionuclides has been mixed with A study is being made to determine the most cement and injected into the impermeable shale beds promising processfes) for the conversion of various that underlie the ORNL area. Recent national emphasis ORNL waste streams to suitable forms for temporary in waste disposal technology, however, has been to on-site storage and for ultimate shipment off-site for store wastes in retrievable forms, thereby maintaining disposal by whatever means is chosen. The desirable the maximum flexibility in the choice of future disposal characteristics of the waste forms include low teachabil options. The waste disposed of by the shale fracturing ity, structural strength, minimum volume, and noncom- process is essentially nonretrievable as a matter of bustibility. Since these wastes have low heal generation deliberate choice; for this reason, this process is in rates, heat dissipation is not a problem and good conflict with the current philosophy and, despite its thermal conductivity is not required. The desirable 15 characteristics of the process include operational sim The most promising of these methods are summarized plicity, compatibility with alkaline nitrate solutions, for reference "»the flow diagrams in Fig. 4.7. Processes low operating cost, and a minimum of required develop for the treatment of ILW. ILW sludge, and effluents ment. A qualitative estimate of the 'Tit" of selected from the Process Waste Treatment (rVT) facility arc processes and product waste forms with the desired included. AH processes are based on the same weekly characteristics is given in Tabic 4.1. None of the known load (KXft load factor), and all storage volumes are waste forms or processes meets all criteria: therefore, given in terms of 55-gal drums so that comparison of some desirable characteristics must be sacrificed M different processes wifl be simplified. compromised so that other, more desirable characteris An average composition and annual volume have been tics can be achieved. assumed for each of the several waste streams of JUL ^ i«oo «•/« ^ »J» r"— ^>M|w« CLASS 'III I J ST9«e : 2*0' ,." CHKOnBtf WOUtOKS W C»Tfi ' T^ '• T^\ am rp i 1—-» e^l »» —Till JTlOW I «n«W*«CT«() S-*-f (OUT 1 9-Mtm $» '•» riMa*rc* Fig. 4.7. forwatefiuaoa. Table 4.1. Qualilalive evaluation of various waite proveuei Waste lorm characteristics Process characteristics Proce» Radiation Operational Required Compatibility with teach rate Structural strength Vc'ume I'lammability damage complexity development nitrate alkaline wastes Shale cement Very low Low to moderate High None Very low Low Low Yei Glass Very low Moderate Mu'ierate None Very low Very high Very high Ye Aqueous silicate Moderate Low u> moderate High None Very low Moderate Moderate Yes Cesium snipping a a Low* 0 a High High Yes Scavenging a a Low* 0 a High High Yes Calcining High None Moderate None Very low Low Low No Asphalt Low Moderate Moderate Yes Appreciable Low Low Doubtful Polyethylene Low Moderate Moderate Yes Very low Low Moderate Yes Titanate f »• V <• c c r c Urea-formaldehyde High Low Moderate c t' Low Moderate No VR-JO* c V Moderate *• r Low Moderate Doubtful "Not applicable. *Not including separated nitrate waste. 'Unknown; insufficient information. ''Commercially available process from the Aerojet Energy Conversion Company. 17 concern to this study - the ILW. the PWT waste, the fracturing process. The cement fixation process is a currently generated ILW sludge, and the ILW sludge in simple low-temperature operation that produces a inventory. These values are listed in T^We 42. The waste form ot high durability and excellent leach sludges will have to be diluted by a factor of 4 or 5 resistance. It is probably also the least expensive of before they can be resuspended and transported the alternatives considered. through the waste handling system; however, the 2. The glass formation process is complex and involves volumes of sludges given in Table 4.2 are for undiluted the use of high temperatures; therefore, its suitabil material. A ten-year processing period is assumed for ity could »e established only by carrying out J major the 400,000 gal of sludge presently in inventory. development program. The off-gas padlems and Of the II processes given in Table 4.1 for ILW disposal of by-product waste streams would require fixation, only four - shale cement fixation, glass particular attention. formation, aqueous silicate (cancrinite). and cesium 3. The cesium strip process is a complicated process stripping have suitable final waste forms and have that offers the possible advantage of a major been studied m sufficient detail for most of the reduction in waste volume. significant process parameters to be known. The calcin 4. The aqueous silicate process provides no obvious ing, asphalt, and polyethylene fixation processes advantage over cement fixation and results in a produce inferior waste forms. The urea-formaldehyde product that is apparently much more leachaMe. and the VR-20 processes yield waste forms that have not yet been sufficiently evaluated: in addition, the 5. The cement fixation process appears to be clearly compatibility of these processes with nitrate waste superior for the processing of sludges. TV volume of solutions has not been demonstrated. The scavenging waste that would be produced is somewhat smaller and titanate fixation processes need further develop than that required for glass formation; i.i addition, ment work before serious study is attempted. the complexities inherent in high-temper; ture opera A brief investigation was made of the suitability of tion are avoided. the four processes for handling ORNL waste solution An engineering study of cement fixation, glass forma and sludge. Several tentative conclusions were reached: tion, and cesium stripping processes has been started. The results of this study will be used to prepare comparative cost estimates that will be used in the The fixation of ORNL waste in shale cement grout is selection of one process for more-detailed future probably the best of the alternatives to the shale consideration. TaHe4.2. Coiiyaiibon and volume of Waste stream ILW Current Inventory PWT concentrate sludge sludge Volume, gal/year 80.000 16.000 10.000 40.000 Salt concentration M 1.2 3.5 Suspended solids. wt % 0.5 40 50 Radionuclide content. Ci/pl 90Sr 0.1 6X I0"5 1.6 2.0 ,37Cs 1.0 2x I0"4 0.16 0.2 144Cm 1 x |0"3 None 2.4 x 10^ 3x I0"2 *°Co 2X I0"3 8x 10"* 0.08 0.1 »9Pu 2x I0"5 None 6.4 x 10"* 8X I0"4 l06Ru 0.035 !.5 X I0"5 0.04 0.05 2x 10"* TaMe 4.3. l-'uel cycle wastes projected for the year 2000 Annual generation Ac 'uiuulaicd invent >ry in the United Slates Category Volume Activity Annual Volume Activity Thermal Metric tons Toxicity (m3 at RCC.)" High-level waste, solidified 36 4.1,000 220*r 109 14.000 63.000 330 2.4 X I0JI H.HX Id" Transuranium wastes Cladding hulls 39 130 38l)'d 370 560 6,000 77 I.8X lO1*1 3.1 x I0n Miscellaneous a, if. y solids 230 5.5 2,800«*r 2,400 22 84 0.5 3.5 x K)1* 8.8 X 10" Alpha solid-. 810 22 6404-J 6,600 121 160 14 9,6 X lO19 1.6X |013 Beta-gamma wastes Noble liases l.l> 190 I70«d 11/ 1,200 2,00(1 0 4.0 X Id" Iodine 0.06 0.0007 I6«*-' 0.6 0.006 ~() 0 3.0 x I0'4 1.0 X Id" I.WR tritium 1.900 0.26 3.400*' 21,000 1.9 0.07 0 9.7 X I0,: 6.5 X 10* lission product tritium 7.5 11 JO** 70 75 2.6 0 3.7 X I01* 2.5 x I010 Miscellaneous d, -> solids 2.6(H) 3 49. (KM)*' 2.400 15 180 ~0 3.8 X K)"" 4.7 x lo" Ore lulling* 1.200,000 0.4 1.7 x 107 5.4 120 77,000 7.6 x lO1" 2.3 x 10" "Cubic meters ol air or water required lor dilution to Radiation Concentration (iuides (KCC) values (Appendix H, Table II, of 10 ( !R 20), ^Solidified immediately and shipped ten years afler generation. 'Rail shipments are assumed. ''Shipped one year after generation. Truck shipments are assumed. 'Number of cylinders pr-ssurucd at 22(H) psi. 19 4 5 PROJECTIONS OF RADIOACTIVE WASTES caused an increase in the projected volume of ore FROM THE NUCLEAR FUEL CYCLE tailings in the year 2000. In order to obtain waste management data that are ORNL tMG 7VO09 more realbtic in light of current knowledge, new projections were made of the volumes and nuclear characteristics of wastes to be shipped and stored through the year 2000. The new projections were based on a recent projection of nuclear power growth in the * United States.' The conservative estimate (case A) was modified to delay commercial I MFBRs until 1993. The resulting contribution of t Nuciem fbwrr Growth 1974 2000. WASH! 139(74) (February 1974). 1990 2000 9. M. I. Bel. ORICEN - The ORNL Isotope Gcnentioa aad CALENOAR YEAR ENDING Depletion Code. ORNL-462S (May 1*73) 10. Cham. TtthmoL Dm. Atom. fnp. Rax Mr. 31. 1974. Fij\ 4.8. tVojtcaBd ORNL-4966. pp. 11.12. States (c»e A. 1993 LMFMU- 5. Transuranium-Element Processing The Transuranium Phirriang PfaM tTRUt and the The purposes of this section ate to report the ruga Fhsx Isotope Reactor (HFUOwerc bait at ORNL VgXuVM danmvMES wal Ota? WtQGCWKti uMuf CvflunSn^aMvM OflwaV research. At TRU. urfet rods •ladiatrd' at the HHR used in TRU. More denied mfuimatnm is presented in are processed for the separatum, recovery, and pun- a series of senuanuaal reports on production, status. fkauon of the heavy atlaaidr, cksntuts. which, in tan. — J • • 1.2 are distributed to labor atoiki rtuuugaoul the country for research work win these dements. TRU is the production, storage, and distribution center lor the bcavy-ekmcut research program in the United Slates, ft During the first four years that TRU was in operation. Inactions integraty with the researchers and not merely as a sappier. Products are usuaty NgMy purified prior naasV for the TRU program at the Savannah River Plant to shipment and are frequently provided in special (SRD and at the HFIR. and af recovered tranmranium fhemscai forms and/or in special devices required by the elenatats (pnMonium onrough fiimianO were dn> experimenter. In addition to the nornssl prodnction trihuttd to rcjtjrchtis. During the next three years, functions, various programs are pursued in cooperative operations at TRU were expanded to htdude the ventures with other research laboratories to assist them processing of ntaterisb irradiated at SRP as part of the in their work. Special isotopes are provided upon CaMfninhim I (Cf-ll nmsinji. This was an itradlatkin request, and hot 5.1 TRU OPERATIONS 1. L 3. Km. J. E. Harfov/. tM E. D.Colm*. Wwiaoiitwii The functions of TRU are to recover targe quantities FbOCtWiHt rWttt StHtitKOtOm KtfOTt Of frOmKttOM, StOtOt, vMnf c/ the transuranium elements and distribute them to /ami for frrtod Cmnv/ AMT 30. 1974. ORNL-4991 iFcanwy researchers. Since it began operation in 1966. TRU has l»75K 2. L i. King. J. E. lajrinw. mi E. P. Comw. fwwjwuiwjw been the only source of significant quantities of woct$&9f rmttt StwAtrWHm Report of rht&lKttOH, Stotos. OJm berkebum, californium, einsteinium, and fermhjm in Man for **>4 E**m Drttmttr 31. 1974. ORNL-S0J4 (in the United States. 20 21 mi a Mrf of 23 HFWt «lw« taajrtt aaat avoonaml Tan** of I CM amtmm. Kqr oil pn to ta» !ia Tatar S.I. It*, : Of liajMl flH l «*# ^ha* 9*«BJfejW4f^BBBBm^l^B«*BBBBo aWka^aV**"* atalaVaBBBBBBf ^^—^^^j^^^^a ^ rf^i^BBaffe si BBA B^OBBB?* BBo BBBBB> 49JJjfl ABBTA. Aftkto. V)T CMPCfSBH Of law 9CHRMff CMNMs to ••£ mttf MM* •! SK C«lMflV MMMM fTTWB HW iSpBCBS* IwQ tmrnUm mmm HF1R wpfs. Ta» yar w, ot**m,miukmt»mcmmmmr>i lof aasortafe aa4aif»a»x aaaoact >t*blniM4iMopa|ilJ»|ar>**E»,Mi»WwiOLS of pgof "»rm Oaa#Mr aroaWt* faamaaJ mi -WW taMaa" IJVjajofavtookaBy paw "'Eaaaattmj of "'f« 134 Mf niiMMB OJOW7? J"c«. a*i s» ,w mw» lawn oaatty •mi Hit iMain4S CaH HFtHaaa ofTa ifltaMtMMlM "'0 Twraty-m tarpm *m faataaaal at onto to wcfdr Soaar of ih* at HtU it wow- avion to thr HF1IL Of fear tarptu. IS maliiari poraMrf oHo mm JKU nodi. 5 co«a*M« CM bo»N to itawrdam. Bat anwm maialaon from 0.9 » miaiaam nwiaw ncwwrffloatami- *ajio 13 a* of *"CT«*m fabricated ttfayaar.tlaee of lofmcvrioaiiatlirHFIIL ifccar wrr ooow> <»ijpihir< ia type J04L stmku S.I. ojaaaaai afiaawji -»•" aatTi aaaaftoojaaaj M974. JI.I97S foul 47 'Amtnaum «mt mmnw jft urn —i»a> wp-*ai«J from caca Table 5.2. YuMsnulsvoncrncsof' "a Sample A Sample B Sample I" Dale of analyse* May 10. 1974 May 15. 1974 March 26. 1975 Itotopk analyst Atom 7 Atom'* Atom'? 24*o 4.22 17.24 3.62 250cf 88.86 81.85 89.22 "•cr 6.22 0.850 6.48 2"cr 0.6S9 ao59 0.678 M3cf <0.003 <0.005 <0.002 «4Cf <0.003 <0.005 <0.002 2,0 Total Cf 204 MK 79 n 1.14 n* Percent of spontaneous 59.r> 12.1% 59.3/ fission activity due to 2"ff 23 The other rabbit (sample Bl was irradoted at the uct mnninmg 0.4Mg of "2Cf. and a curiam product 244 same neutron flax bM lor only 43 hr. Tins uiadined rmwrwrng 2.6 m;of Cm.6.7lujof "'Cm.and I2S target was protested by the same tedmifue. Approxi pg of 2SVm were obtained. mator? 10 mg of *4*wV awttinof 25,CT were A series of rorajutrr raWwhnruM wa> made, using the mow ltd and purified. The natoon oompossnon of exact nimmriun history of the capsules and the dm lawfornimn is afau shown • Tahk 5.2. The shorter nu-ajwid product mmpumaoa. to determine the best •i idiiiawi time n mhrd in a significant redaction in the value foe the 24»Cm capture cross section. Moat of the conusVutian to the spontaneous fisaon activity from "*Cm decays to 24*ufc with a 64-mm Imfrme Oury a the heavier cahfonuum isotope. * * 2Cf. snml tnctkm (about 5x 10"*) captures a neutron and becomes loae-feved 2**Cm. Spedw HFUt Tamtto The destruction of the 2S*Cm by absorption of a A series of catenations has been made for the pnrpose 2,*Cm varying from 2 to 200 •. The Ike woifc Rhnc to met NdMhv aai afety in napii n kawt fcw upoiid in IWIIIMJ GC1 a»*ats • am iryortfi keat d« year. •» aaapaaacc asaaaaaci aai aal be aaaaaarianl at aar GaCotdai Mb ngalataMM aaath flapwaed m sack iafonaatwi JtwriMr Jaoaajan Jkaaiu Jbjnrr /far «tr Aaaaf aaM ae *Mriaa«c4 a**/ aaato *r caNfory UC-77 - laawrj 1974-Jmm 1975 (to ae pataaaaij. GatCooM tractor Tcdawloty Ike aaafe «f oar 24 7. Prcpauatioc of 2iU"UO 2 (MfDto i«f"*U f) at me rate of fc«aC1"Unci««ck.<2» UOi 2* kg of ">U per UO,toBAflfo* .pearls, and <4> "'UD, scrap painted at OtML and d ThOj sen* geaesated « BAH. lie K»tme 50 to 250 kg of mused ansae, and a of UOj powder at a aba* capacity of of she HI nnim 12 M HNO,-OJ04 M F-0.1 M ANNO,*, was am*. The < 7.1 BKOVEBY OF "'UHMM WASTE %ol2M TteiimhiaisohuaoswvjmiiiiiiiililiitoT UO, ATOftXATUO, ThO, rOXETS urn as wed to the setum extraction system. About 14 kgofkafcedi thai report period, the to recover 78.1 l^of}"U from recycle UO, • 24 drwnmtinvn This to he effective for Al,0,>fi 7.2 1J», Kg furnace (ie.. UO, ); (2) recycle UO, bard from cleanup of the glove boxes after each Twenty runs were conducted in die solvent extraction operation; and (3) one entire lot of product system to recover and to purify 336 kg of i that BAM could not receive because of problems in present in various types of scrap, rrcyde i their faemty In addition, some unused "'UO, (5.2 the ion exchange system, and recycle kg) returned by BAPL and anal accumulations of previous solvent extraction runs. Uranium losses to the analytical samples at ORNL were dissolved. raffinate ranged from OJ to 1%, averaging 0.66*. The AB of the pure UO, was dissolved in saghtry more thorium content of the wjahim product ranged fro* than the stokhiornetnc amount of HNO, at 80'C so 500 to 5000 ppm. that the nitrate solution, after being analyzed for AHMoxinutcly 706 kg of uranium was purified in 31 impurities, could be sent directly lo storage or proc runs made in the ton exchange equipment. Nonrecovcr- essed through the km exchange system for purification. abk losses totaled 0.02%. The effectiveness of the ream The product from the dissolution of ammonium dhva- (200- to 40tHmsh AG-50W-X12) column was observed natc and UO, that had been spiDcd or used m analytical to decrease markedly after a total throughput of 370 kg tests was purified in the solvent extraction system of uranium, which corresponded to approximately 20 before being returned to storage. Four of the dissolu loadings and 20 ehnJons. Thrj loss in effectiveness was tions were essentially "ckanout" operations made in an attributed to the ,24Ra, a thorium decay product, that effort to account for all uranium charged previously. had "grown into" the uranium solution during the five Fight dissolutions of Savannah River oxide (39.1 kg of years it had aged in the storage tanks. We then diluted 25 -X"IHI»IB> a una nil i MA • 27 *a «f I St a«M* art M •_!** Oar hM <2HS kg a* UOJIOTMQCM. a aaaac raa. Tar MA's npf. afta "(H •« Mr *T *t EMpt far car k* ia I2«| «f*r"*la«41yirlla barf far aTaaaaaaa. J «e Hi il aat? J»* U. TJCONVBHONOF"*!) *a« iaufc»*e a.aa n iiJiaiilaa»af to MlaUIE SOUfnOK ID Tat fatter *» of tfavTi . a total «r6T7k«ar 1X^(31 lots) VJr 5S» kg (30 IMS) m naitfiiiil •» fey 8. Separations Chemistry Research and Development of IC fields. The atlm- • cwjeiry cc 9 of the Pewer systems* . w*» placed o* the desuaMhrc CM, try of jepamioeu systems aa MM Descriptive chemistry iachsdes nadir i of the Fa>t.l. AcyaaMpnaBstaaalcaalfmBli icactjnas of sabstaaces to he separated aad of seoara- saflkicM to estaMrdi the coatroiiag bled separations proceaes. aad arvestita twa of the cbeaMsiry of potential MEW separatins extraction characteristics for aatericima aad other agents aad Methods. sufficient to evaluate their aserul- trivaknt actaudes from dilate acids; unfortunately, arav la process dtiriupaicat. a selected aKthod is however, it has Smiled sohanbty |<0J05 AT) m aliphatic developed mto a coeaplete process aad tested at the ddaeats such as Jt-dodeume aad undesirably high scale aeeded to evaluate iu perforatance aad/or eco- aqjueoas sohmmty. We have synthesized two aew aoaHcs aad to predict its huge-teak perron: snee. acylated pyrazolones with more favorable sorubifaiy Although there is considerable interdependence and properties: 1 -phenyl -3-methy1-4-p-ren-butylbenzoy;-2- overlap between descriptive chemistry aad process pyrazobn 5-one (wMBBP) (Fig. 8.1(0)1 and l-pheayl- development. Sects. 8.1. 8.2. aad 8.5 represent pn- 3-methyl-4-decanoyl-2-pyrazolin-5-one (•MDP) JFig. anriry the Unmet, whue Sects. 8J and 8.4 represent 8.1(c)!. When used in synergistic combination with primarily the latter TOPO at the optimum ratio of one mole of acylated pyrazolone to two moles of TOPO. the two new 8.1 NEW SEPARATIONS AGENTS compounds show much higher solubility in n-dodecane; 4MDP is the more soluble, X).2 M. Neither compound A number of reagents have been examined in our shows any measurable distribution to aqueous phases. starch for selective extractants for plutonhim and the All of these compounds. •MBP. •MBBP. and wMDP. tramphrtonium actinides from acidic reprocessing waste have higher solubilities in aromatic diluents such as solutions One class of compounds, the acylated dielhylbenzcne than in n-dodecanc. but give lower pyrazolones in mixture with donor additives such as americium distribution (extraction) coefficients. Even iri-n-ocivlphosphine oxide (TOFO) or tributyl in diethylbenzene. however, the americium coefficient phosphate iTV). has been used in analytical with •MBBP may be high enough to be useful. Table 1 applications. A i "oresentative compound used in our 8.1 contains data on the extraction of americium by studies. I -phenyl-J-A.*thyl-4-benzoyl-2-pyrazolin-5 one •MDPTOPO and •MDBPTOPO mixtures from (•MBP) |Fig. 8I(«)) was found to have excellent Talspeak-process effluent (Sect. 8.3) adjusted to pH I.S. The americium distribution coefficients are much lower than the maximum values thai could be obtained I. B. F. Myasoftfov. N. E. Kocfcn:-on. and M- K. Cnimiton. Zh Am/Hi. KMm. 28.1723 (1973). with higher TOPO concentrations. 27 2S TS-«4ti 1 IJftfroriicjad. R-QO Q fc( ** OjaSMN^DTTA "•• i* I -S> pied by Dr. Craj* ami a (fori Bi functional phosphonates. first investigated by S 2 SEPARATION OF RADIUM FROM URANIUM ORE TAHJNGS fairly strongly from MgMy acid soiutioHS (4 to 6 M HWH) and. when pure, arc easily stripped by duule The objectives of this project to investigate the acids (<1 N). These compounds have potential appfcca- leaching characteristics of radium from wanmu ores bmty to separating americiom. curium, and rare earths and suifate-ieached ore tattings are: (I) to determine if from al of the other fission products in fuel reprocess there is an economically practicable method for remov ing wastes without prior destruction of the UNO) ing the radium (and ol*»er radionuclides), and 12) to (Sect. 8 J). In two commercially prepared compounds. find a means by which he leachabmty of the radium dibutyl-^F^-diethylcarbarnyfmethyknepriosphoittte due to weathering can be significantly reduced. Pre (DBDECMF). IF* 3.2(c)]. and dO*xyl^VjV-d»tthyl- viously reported :«sts'-7 which were directed toward carbamyfcr^hylenephosphoi&te (DHDECMP). [Fig. the determiru ion of the leaching characteristics of the *.2{fc)|. impurities prevented stripping of americium in "slimes solids' fraction of the suffateJeacticd tailings, the desired way. These impurities may be strongly ex indicated thai effective removal of radium was proteMy tracting neutral compounds. Our present efforts relative not practical, since it required the use of fairly to these compounds are directed toward developing concentrated HN0} 'H HCI solutions (3 J#). or exces methods of purification. sively large volumes of selected salt solutions. Cyclic "crown" ethers arc reported to complex many In more recently reported data.* pertinent to possible metal ions, especially alkali metals and alkaline earths, reduction of radium leaching due to weathering, leach presumably with the metal ion within fhe ether ring. ing tests were made on sea sand thai had been ground It has been suggested that the size of the "host" ring to 325 mesh, washed successively with 0.1 M HCI affects the specificity as a function of (he size of the solution and water to prevent adsorption of radium on metal ion. If so, one would hope to be able to the freshly exposed surfaces, and then coated with synthesize compounds that are highly selective for a eilhe' RaS0« alone or RaSO« in combination with specific ion or group of ions - an exciting prospect. An CaSO« and/or BaS04. In an attempt lo further eluci- arrangement has been made with D. J. Cram of UCLA5 to supply certain of these compounds lo us for testing. We are currently investigating several compounds sup- 6. Chrm. Techm.1. Orr. Atom, tto^r. Rep. Mmr. 31. I97J. ORNL-4M3. pp. 57 58 7. S. D. Sharer. "The Leachability of Radhim-226 from 2. T. H. Siddall III./ Inorg. Nucl. Chem. 25. 883 (1763) Uranium Mill Solids and River Sediment." Ph.D. then*. Univer- 3. T. H. Siddall III./, /new* Nucl. Chem. 2*. 1991 (1964). fity of Waconati. Madison. 1962. 4. T. H. Siddill III.US. Patent 3.253.259 T3.««tS IMTIAI. HOLE MHO *J SOUO, Fa> 9.3. Effect V varying nwi of aTaawn mlh ssKstss (AESO4) on the Ufcitwe 5^. AESO4 precipitated onto finely wound sand and liwn leached with I AYNaCI-O.I aYHCI SulaMin (in^wDof AESO»: 5Cj,a0.02,.ts,alO"*.5B,a2x lO"*.*,,., a 2 x IO"V 30 These data suggest the possibility of reducing the the original waste solution containing the americium. leaching of radium from ore tailings by the addition of curium, and fission product rare earths and to the BaSO«: however, such a procedure would probably americium-curium-bearing effluent from the Talspeak require impracticably large quantities of BaS04. process. In the current version of the Talspeak process, the rare earths are separated from the trivalent uctinides 8 J SEPARATION OF ALPHA EMITTERS by preferential extraction with dK2-ethylhexyI)phos- FROM FUEL REPROCESSING WASTES phoric acid (HDEHP) in diethytbenzene from an aque ous solution containing glycolic acid and sodium In support of the program on Process Modifications diethylenetriaminepentaacetate. •or Improved Waste Management (Sect. 4.2). we devised The composition of the feed solution is based on an improved process '•••.. vrheet for removal of ameri- standard values assigned to typical LWR fuel reprocess- crum and curium from reprocessing wastes. The new itig wastes from 1 metric ton of uranium fuel as version (Fig. 8.4) eliminates most of the difficulties modified by the present concept of processing to encountered with a previously published flowdieet that remove uranium, neptunium, and plulonium to accept was based chiefly on solvent extraction.'* Several able levels (Sect. 4.2). The values for distributions of extraction steps are excluded by using conventional americium and curium in the various processing steps oxalate precipitation followed by scavenging of residual are based on results obtained in tracer-level laboratory amounts of americium and curium with small amounts experiments with simulated fuel-reprocessing solutions of rare earths. These operations are applicable both to under a set of conditions which are not necessarily optimum. For example, removing more HNOj would 10. Chan. Technol. D& Annu trogr Rep. Mar. 31. 1974. make possible a decrease in volume, with a consequent ORNl-4%6. pp. >6 27. decrease in cost and improved performance; however, (•n«CT«M I UV9mm • ^ MV "A"l rwwcrneq r- w ; JO I IMIIlffl „ «p JT^ JL 1 1 1 Htl'ti "-T * -1 —•"• '—*4*t worn •ymu»n IM » ot« ; »ic 1PWNSO» sB^l fer •tout TOMKTO* L «t_j«ss. iw a eivcoiic at* fcf » -011 .-«»» « MW « ml Fig. 8 '. Amcricimi-canBM wcovtiy from Pwcx waste by oxalate precipitation of rare earths and actMdes, Tabpcafc partttionmf. rcpreciprtatiM, and calcination. •-.iz — •^•^sz^'-^XKs^-j'ft.zr^-'i—**->.-*£»•« 31 the specific conditions in terms of results expected have into TBP from HNO3 feed solution, experiments were not been detetmined yet. The terms "HNO3 removal," designed to determine the stability of Pu(IV) in HNO3 "solid-liquid separations," and "oxalate decomposi and in synthetic fission product solutions at various tion" designate operations for which various alternative, temperatures and acidities of interest. Some of these feasible methods exist. conditions are conducive to hydrolysis and precipita tion of several of the fission products, and efforts were 8.4 WASTE STREAM PROCESSING STUDIES made to determine the effects of this behavior on piutonium extractabUity. The purpose of (his program is to provide certain To date, we have identified three principal problem fundamental information required for the satisfactory areas that can result in plutonium losses prior to or treatment of waste streams in nuclear fus) reprocessing during Purex processing. These include: (I) a decrease plants. A number of problems have already become in the plutonium distribution coefficients with succes apparent in studies'' of processes for removing long- sive TBP extraction stages, (2) the PuflV) interaction lived actinides from wastes, and certain bask informa with the ruthcruum-rhodium-palladiuin components of tion is required to solve these problems. Additional synthetic feed, and (3) phitonium kisses associated with problems will likely become apparent as process devel precipitates of zirconium and zircormim-moiybdenuni- opment studies continue. The basic mechanisms involved m these reactions have Initially, the program involves only studies related to not, as yet, been determined. removal of actinides from the high-level waste stream A small but significant amount of plutonium does not from fuel reprocessing plants. These studies include: extract into 30% TBP dodecane from a 3 M HNO, 1. an mrestigation of the nature of the plutonium in feed solution. This effect involved about 0.01% of the high-level waste streams that is inextractabie by present plutonium feed concentration and resulted in a TBP. its mechanism of formation, and methods for decrease in plutonium distribution coefficients from its removal: 17.0 to 0.2 in seven consecutive extraction stages. Th; initial plutonium was highly purified, and spectrophoto- 2. control of neptunium valence by the use of reagents metric analysis indicated that it was composed entirely thai are more amenable for recycle of waste streams of ionic PuflV); however, the limits of detection for from the separations process. other species are well above 001%. The nature of this 3. application of fused-salt processing methods for inextractabie plutonium has not yet been identified: treatment of insoluble residues in the wastes. identification will be difficult because of the very low concentration. Last year the principal emphasis was on studies of A second type of reaction observed involves PufiV) inextractabie plutonium in high-level waste. In addition, instability when synthetic feed solutions are aged or an investigation of the kinetics of the reduction of heated. This instability »js found to be due primarily Np(VI) to Np(IV) by ferrous nitrate was carried out. to inteiactkm with the ruthenium component, although Studies on fused-salt methods for dissolution of solid similar effects were observed to a smaller degree with residues were initiated late in the year. rhodium and palladium. At room temperature, PuflV) is not stable in the presence of nithewurn. rhodium, nutoniiun Behavior in Synthetic Wastes and palladium at acid concentrations of 2Mot less. As Difficulties in achieving high plutonium recoveries much as 50% of the PuflV) can convert to other species (99.99%) during reactor fuel reprocessing are antici in about ten days. A significant feature of this pated due to the formation of inexlractable plutonium interaction is that the affected plutontum is slowly lost species. Therefore, studies were inituled to investigate from solution, although visible precipitates are not reactions that can result in plutonium losses =»nd to generally involved. When such solutions are heated, the determine the basic mechanism involved. change occurs very rapidly, and greater than 90% of the Since plutoiiium will be recovered from spent reactor PuflV) can be convened at 80°C even in fairly fuels by the Purex process, in which PuflV) is extracted concentrated acid solution (3 to 7 M). In preliminary efforts to identify the specks to which the .^uflV) is convened, it was determined speclrophotometrically II. WD. Bond and R E. Leur*. Feasibility Studies of th* that the PuflV) was oxidized lo PufVI); HDEHP and Partitioning of Commercial HighLeret Wastes Generated in Spent Nuclear Fuel Reprocessing: Annual Progress Report forTB P extraction behavior also indicated that the species FY 1974. ORNL-5012 (January l??5). was Pu(VI). The principal effect of the ruthenium-plu- 32 ionium interaction on piutonium extraction behavior in determining step was found to be the reduction of the the TBP-HNOj system was the reduction of distribu intermediate species, Np(V). The reduction reaction tion coefficients by a factor of 2 to 3, although in some was first order with respect to Np(V) and Fe(ll) experiments small third-phase losses occurred due to concentrations and about \ order with respect to sohds formation. hydrogen ion concentration. The compiexing of Np(lV) Since piutonium losses can result from the formation with nitrate ion appears to explain the modest increase of solids in feed or waste solutions, the hydrolytic and in rate observed with nitrate ion concentration. The precipitation behavior of zirconyl nitrate is being energy of activation was measured to be 9.8 kcal. We studied at various conditions of aging and heating. At also studied the kinetics of the back reaction of the 60 to 80°C, a consistent trend exists in the dependence reduction [i.e.. oxidation of NpflV) to NpfV) by ferric of zirconium hydrotyik behavior on HNOj concentra km). The reaction rate appears to explain the moderate tion, and this trend was not altered by the presence of slowing of the reduction rate after about 75% of the rVNOjb. At low acid concentrations (1 M or less), reduction has been completed. The oxidation reaction, colloidal solutions of very small zirconia particles (20 to which is first order with respect to NpflV) and Feflll) 40 A) are formed. These colloidal solutions are very concentrations and negative third order with respect to stable, and fonnaticn appears to be irreversible in that hydrogen ion concentration, has an activation energy of the particles do not readily dissolve even in concen 35 kcal. The relative effect of temperature on reaction trated acid solutions. Hydrolysis of ZKXNOsh in rate constants is shown in Fig. 8.5. Based on the results more-concentrated acid media (>2 M) results in the of this study of chetnica! kinetics, a 10- to 20-min formation of zirconia precipitates instead of colloidal holdup time would be required to reduce Np(VI) to solutions. Maximum precipitation occurs at 2 M HNOs, Np(IV) in a partitioning column. and the amount of precipitate that forms decreases with increasing acid concentration. A small amount of precipitate is formed even in 6 M HN03. Although the OSSl-IVt TO-SSVMt nature of such precipitates has not been fully resolved, 1.200 I——VJ 1 1 1 1 electron micrographs show that they contain distinctive rodlike structures that ate typically about 1000 A wide and many thousands of angstroms long. 1.000 - The effect of zirconium hydrolysis on piutonium TBP extraction behavior was evaluated in two experiments. In the first, PufNOjb was heated at 80°C with O.eOO - ZrCHNOsk in 3 M HNOj until precipitation occurred. Some piutonium is undoubtedly associated with the zirconia precipitate, but the amount is too small to be otoo \ X detected by gross alpha analysis of the feed solution. m 1 ^W The effect on piutonium extraction behavior is also - \ \ quite small, although piutonium losses are a factor of 3 «0.400 - \ greater than for solutions of Pu(IV) alone after five extraction stages. In the second experiment, i M HNOj containing both 0.200 - Pu(NOj)4 and ZrO(N0,h was heated at 80°C This gave rise to a major piutonium loss mechanism in which 2% of the piutonium became completely inextractable 0000 - inTBPfrom3MHNO}. Redaction Kinetics of Np( VI) -0.200 I 1 1 1 1 1 1 3.100 3.200 3300 3400 3500 MOO A study of the kinetics of the reduction of NpfVI) tc «0»/T NpflV) in nitric acid solution by ferrous nitrate was. 13 Fif. %S. Effect of temeerttuw oa the specific rate conttMt made using spectrophotometric methods. The rate- ind»rc*e**Mraactkm MfOj * • Fe* • *H* - Nf>* • Fe* • 2H,0. 12. work performed in cofhborafon with J. R. Peterson and Y. Jao of the University of Tennessee, KnoxviBe. A * forward reaction; 0 • backward reaction. 33 Molten-Salt Processes at each potential, a fraction-reduced-vs-potential curve was obtained. From this curve, the half-wave miegarnji- A review of the literature was made to determine the tRm potential from 0.1 M NH«CI was detennined to be feasibility of a molten-salt extraction process for -1.60 ± 0.05 V relative to the standard hydrogen removing actinides from the solid residues that result electrode potential. This is sknttar to the values for from the aqueous dissolution of spent fuels. These calcium (£l/2 = - 1.97 V) and strontium (£l/2 = -1.86 residues consist primarily of plutonium oxides and V), again demonstrating the similarity noted above. noble-metal fission products but may contain trace quantities of other actinides. In principle, the recovery of the actinides should be possMe by dissolving the residues in molten salts and then extracting the acti Outside interest in liquid scintillation alpha spectrom nides into a liquid-metal phase. Studies were initiated etry increased greatly during the past year. This interest regarding the chemical reactions required for dissolu and our own use of this alpha counting method resulted tion of the residues in molten salts and the chemistry of in investigations leading to significant improvements in the molten-salt-liquid-metal transfer process. it and in the related separations methods for arpha-emit- ting nuclides. 85 WSTWUmON EQUILIBRIA. KINETICS, In cooperation with the School of Engineering of AND MECHANISMS Arizona State University, Tempe. a short study of "Smgfe Atom" Chemistry reflector and electronics configurations was made and reported. The abstract follows: The adaptation of separations chemistry techniques ""Some Studies of Reflector Construction and Beet rowan to rapid handling and to small volumes has allowed Configurations for Optimizing Puhc-Heajht and Pube-Shape successful completion, in cooperation with members of Resolution in Alpha Liquid Semination Spectrometry,'' by the Chemistry Division, of three separate studies of the John W. McKhreen, School of Engueering, Arizona State chemistry of nobdium, element 102, using the cyclo University, Tempe, Arizona, and W. J. McDowell, Chemical Technology Division. Oak Ridge National Laboratory, Oak tron-produced isotope 25sNb (l = 223 sec). The t/2 Ridge, Tenn. Abstract: Various sample sizes, reflector sizes and first paper, "Comparative Solution Chemistry, Ionic shapes, and reflector materials were examined to Jriri—inr Radius, and Single-Ion Hydration Energy of Nobel- their effect on pulse-height and pulse-shape resolution m alpha ium," has been published;13 the other two are in liquid scintiBation spectrometry. A section of metal sphere preparation. The abstract of the second paper follows: coated with a diffuse-while reflective material was found to have the best characteristics for both pubc-height and pnuc "Nobdium Chemistry: Aqueous Complexing with Carboxabte shape resolution. Although sample volumes as brge as 10 mJ lota: by W. J. McDowell, O. L. Ketter, P. F Dinner, and J. R. could be tolerated when used with reflectors to accommodate Tarrant. Abstract: The tendency of divalent nobdium to form them, the best results were obtained with I-ml samples and complexes with citrate, oxalate, and acetate ions in an aqueous smaller reflectors. Comparison of two types of pube-sbape medium of 0-5 M NH4NO} has been examined by solvent discrmimatmn circuitry for separating alpha and beta-gamma extraction techniques and compared with the complex-forming pulses indicated that a zero-crossover method was superior to a ability of calcium and strontium under the same conditions. In constant-fraction-timmg method. The combination of these general, for each anion, the complexing tendency of nobdium is improved detectors with solvent extraction methods of incorpo between that of calcium and strontium, being more nearly like rating the sample in the scintillator and pulse-shape discrimina that of strontium. The data aOow the estimation of a tion allows alpha specttometry with a background as low as concentration quotient for the formation of NoHCil and NoOx. 0.01 count/mm and an energy resolution as good as 5.5%. There is some suggestion of a difference in nobeuum chemistry from that of calcium and strontium. Other work was directed toward adapting liquid scintillation alpha spectrometry to a wider range of The paper describing the third study will be entitled applications. A program being carried out in coopera "Determination of Half-Wave Amalgamation Potential tion with the Health Physics Division has the objective of Nobeliurn." In this work, nobelium was placed in a of improving both the instrumentation and the chemi small electrolysis cell and electrolyzed into a mercury cal separations aspects of the system. Efforts in cathode. By analysis of the nolelium solution before instrumentation development are aimed at improving and after electrolysis at each of several selected poten alpha-energy resolution and pulse-shape resolution, that tials anil by repealing the experiment a number of times is, the capability for electronically separating alpha-pro duced pulses from beta-gamma-produced pulses. Chemi 13. R. J. Sit*a. W. J. McDowell. 0 L. Keller. Jr, and I. R. cal systems improvements have included increased light Tarrant, fnorg. Chem. 13,2233-37 (1974). output and stability of the scintillator solution as well 34 as move effective and more dependable methods of and. with |H,0| and |HN0,| approximately constant, extracting the alpha-emitting nuclide into the scmtil- the cquiHbrinm quotient expressed m liquid-phase utor. Progress was made it the development of a concentrations is procedure for stripping the alpha-emitting nuclide from the extractive scmtittator used m a commercial beta liquid scintillation counter and reextracting it into the v high-resolution scmtMator. This procedure could be IU used to scan a large number of samples, selecting only We define the distribution coefficient If as the ratio of those requiring the better energy resolution or the tracer iodine count rate in the liquid to that m the gas. lower background of the high-resolution detector for C /Cc Since HIO, exists oaJy m the liquid stale ami further treatment- L 599-9% of the iodine is in the form HIO, in these tests, CL * |HIOj |. The only species mine gas is l2. so that assuming l2 distribution to foBuw Henry's bw with proportionality constant k gives Cc * 2x|l2|. Equa In the lodox process, concentrated nitric acid is used tion (1k then becomes to scrub or remove volatile iodine from air streams encountered in various parts of a nuclear fuel reprocess C ing facility. The nitric acid serves as an oxidizing agent s v?=2A_L|H,0i, |Nlo4| . 12) to convert the iodine to the nonvolatile pentavaleni form (i.e.. to a form of iodic acid)- The iodic acid or its equivalent form of l205 or HIjO; is then stored or disposedofasradioactivewasfef'311.,7'I).Oxidation log-A • lo- IHIOjJ = 5 log |N,Q,1 + k, of iodine leads to the production of reduced nitrogen in the HNOj. In oxidizing iodine to the pentavalent state, = 5 log |HNO^ ) + *, (->) the use of HNO3 in the 16 to 20 M range b most M important, since at these concentrations the reaction where *, = log [Q!lk\. since the concentration of the rates are much faster and the chemical equilibrium actual predominant reduced hitrogen species. |N204|. favors formation of pentavalent iodine. is equal to the equivalent stoichiometric concentration Previously, we reported studies of the chemical of nitrous acid. |HNOj|„ Further. [HIOjl was held equilibria made by spectrophotochemical methods in approximately constant in these tests (H varied only the HNOj concentration range of 14 to 18 M.'* This when C(; varied), so that Eq. (3) reduces to report summarizes tracer studies of the lodox equilibria in 17 to 20 M HNOj In order to approach the operating conditions to be used in the actual gas tog//=log^U StoglHNO,!,,*^ . <4> scrubbing process, experiments were designed to meas ure the liquid-gas partition of iodine between 17.18.19 where k2 = k, log |HK>j). A plot of tag # vs log and 20 ik HNOj solutions and air. I HNOj I j, would thus be expected lo show a slope of Some understanding of the partition behavior of 5. iodine can be obtained if we assume that we are dealing primarily with a two-species equilibrium (namely. I, and HIO3). Studies made on the HN0,-NOj-N0 14. Chrm. Tethnoi Dn Anm. Frogr. Rep. Mtr. 31. 1974. system indicate that the NOj/NO ra.io becomes large, ORNL-4966.pp.29 31. at least 100. for HNOj concentrations above 17 15. L Ya. Ternhchenko et si.. Zti Prikl. Khim. 41.487 92 7 (1968). M*'"' Thus it appears thai the reduced species will be 16 M E. fbnn ct si.. Zh Prikl. Khim. 36.16 24 (1963). either N0 or its dhner. N 0 . Further, on the basis of 2 2 4 17. L. Ys. Tereshchenko « si.. Zh WW. Khim. 41. 702-9 other work on the N02-N204 equilibrium, the pre (1968). dominant species at high equivalent nitrite concen 18. V. I. Atroshchenko el si.. Kore Tekhnotoflm Sriazon- ,9 ,, no*o Azota. Izd. Khimo. Mono* (1968). trations will probably be f^J0^. ' The correspond ing redox reaction is 19. L H. Mntiina et si., Vestn. Aktd. Bekrusk S.S.R.. Ser. Fiz. Ttkn. Ntruk. 4,23 (1967). 20. R. V. T. Wsyund./ fhys. Chem. 72.1626 (1968). 21. C. MaUna and f Tonca. Btmc Nitrogen Compounds. 3d I] + IOHNOJ * 2HI03 + 5N,0« + 4H,0 . ed.. Owm. Publishing Co.. Inc.. New York. 1973 35 If the predominant reduced nitrogen species were N;0. However, such a reduction would be counter to NO? instead of N20.». the corresponding relation the evidence cited above;' **' * hence it is more likely would be to reflect, for example, changing activity coefficients While the slopes per se thus cannot yet be interpreted with confidence, the close agreement of these tracer lug #7 = lug % l0log|NO | + *, 2 distribution measurements with the spectrophotometrh. measurements gives confidence in the validity of both. * IOIog|HNO:|s(+*4 Consequently, the results allow calculation of the partition coefficients required for practical application Figure * 6 shows the equilibrium iodine distributions of the lodox process to be made in both high and low obtained at the four nitric acid concentrations as a nitrite concentration regions by use of the appropriate function of the stokhioaietric nitrite concentration in apparent concentration dependences. Note from Eq. 121 the system (added nitrite plus nitrite-equivalent pro that the distribution coefficient. H. is inversely propor duced by oxidation of iodinel. The results are similar to tional to the total iodine concentration. *{HIOj|. At those from the spectrophotonKtric work ' * in that the lower IflO) concentrations than used hi these tests (2 X slopes vary between 2.5 and 5 As noted previously, 10 ~y My the distribution coefficient would be cone slope values of 2.5 could suggest reduction to NO and spondingjy higher MM •• T«-i»*>m Tt~ SLOW •-» tfO* MH-il o u \ \ \ ?»S i ** IMf tO* IC"' »* 10 STOCMOMETMC MTKITE, [MNOJ^W n>li Piawlwirr of tfct iodine orttwon toitlkitnt in the lodox pwc— on the nllilli wuii mwt concentration $n mnrtmi taOictmcatmkmiQJ0nMm*4tttn»imuk»&ctmctnintk>m. 9. Biomedical Technology 9.1 ADVANCED ANALYTICAL TECHNIQUES automated high-resolution analytical systems that can identify and quantitate many molecular constituents. Various disease states may give early warning of their New analytical concepts are being developed by the onset or their continuing presence by subtle changes in Biomedical Technology Group: some of these will lead excretion levels of molecular constituents in phy sioiogK to the fabrication of prototype analytical systems for body fluids. Prompt medical treatment based on these use in clinical and biomedical research laboratories. early symptoms may prevent the disease from develop ing: retard the progress of the disease; or. at the very least, minimize its debilitating effects. Detection and monitoring of these early symptoms will require that Three major analytical concepts are undergoing de research and clinical laboratories be equipped with velopment and may be categorized as: high-resolution I CHROMATOGRAPHIC SEPARATION FDR 6 )Mlfi EACH OF a CARBOHYDRATES USM6 A SORC AOO CONCENTRATION 6RMMENT — 90*02 on TEMP. 60*C CRAJMEMT 0.1—0.C7M 80MC MCSO.0H-7X) nOWUTE » mi n» il Fig. 9.1. RapM separation of 13 carbohydrate* by MM cxchaaft thwwanlogiaBliy, Ming a nwtnl boric acM concent danrt. High leinitivily of the cerate oxidbnetrk detector thows the baseline rite due to an increase in borate concentration. 36 37 liquid chromatography, centrifugal efcitnn chroma entent mtroduction, a rotor win up to eight chro- tography, and elation ekctraphoress. aniographic nihimni terminating in flow covets, a stationary hght source and photodetector, and a digital- high-resonibon liquid chromatographic system receiving logic circuit which synchronizes dw cuvet signal win the most developmental attention in the past year was the appropriate recorder trace. die glycoprotein carborydrate analyzer. The applica In operation, dm sorption medium is loaded into dK tion of the cerate oxidimetric detector system to columns dynamkaly in dae form of a slurry. A steady carbohydrate analysis was discussed previously.1 This etnent flow rate is established, and the sample is detector system has been unproved and coupled with a mjecied into dK eJuent stream. The duate roonitormg liquid chromatographic system1 for die analysis of system is operated throughout the ran, and a multi- neutral carbohydrates in serum glycoproteins. The I stno-durt recorder is used for dau display. sensitivity of die cerate oxidunetric system for carbohydrates was increased, and the analysis time for protein-bound carbohydrates in strum was reduced. 1. C D. Soon ct aL. ExjtrimnUal Eugmuui^ Store. Figure 9.1 nwstraies die separation of 13 carbohydrates «ML Au*r. ««•. Sept. /. 1973. to Fck. 28, 1974. ORNL- in 6 br. using the improved glycoprotein carbohydrate llM*02tDcoeiMMr I974K analyzer. 2. S.baanaW.W.t^t,Ji.,~ANewVe«saiKanaScamm Centrifugal dmmn ihi imntignnhir system. A proto WBniiiiiit Svnm for LiaaM ClKoautogranfcy: Cerate Oxnto- Uoa ari Fnomccnoe Uasnaami," AmaL Lett. 5, 177 type centrifugal system was developed to permit photo «I972>. metric monitoring of ehiaie streams from multiple 3LCR Scon, W. W. Rtt. awl W. F. Johnson. "Cmtrrfwpl chromatographic columns.* The major components, Ehrtioa Ckromjunrapny with Ehaic Monitorinc," J. shown in Fig. 9.2. include: a means for sample and Onm-tog. 99, 3$ (1974). onm. owe 74-3733 ELECTRONICS srmr CHART RCCOROER CLUUIT PREPARATION AUO STORACE STATIOUART ILUATf COLLECTION nine PHOTOMUITIPLICR | TO VACUUM •• «- SYNCHRONIZATION SUPPLT SYNCHRONIZATION LI«NTS M* APART DISC 4-PHOTO CONDUCTORS SYNCHRONIZATION CIRCUITS WASTC MOTOR COLLECTION Fig. 9.2. Ceatiifami uinon chroantognpn with thnte tnonttorine. 38 Experiments with simple gel filtration separations gent development system can also be used wherein one have shown that the apparent efficiency of the entire or more reagent streams are contmuousty mixed with system can be represented by about 30 theoretical the eluate stream and the resulting reactioa products plates. The comparable chromatographic peaks from are continuously monitored photoraetricaUy. . each channel had very dose elution times, indicating The entire system, excluding the 5-kV power supply, that the ehient flow rates for the various channels were is enclosed in an acrylic photic housing. DouMe- quite sumlar. •nertocking safety switches are installed at each point Ehjomi thtlruphaitaii system. The usual mgh- of entry to the column area. As a result, electrical rcsohinon electrophoresis for biological macromote- current can be applied only if and when all switche: arc cules requires a series of manual manipulations to dosed. achieve best results. Consequently, the entire operation Ally in • AnphLiliini can require a relatively long time (hours), and die many manual steps result in poor quantitation that can be Analytical separations studies on human phyaologic very operator dependent. A new concept for electro fltuds continue to demonstrate useful applications of phoresis is under development that, hopefully, will high-resolution liquid chromatographic systems and result in a highly automated analytical system which detectors developed by the Biomedical Technology will be accurate, reproducible, and require a short Group. Emphasis is continuing on the separation and analytical time. This concept is that of elution electro analysis of proiein-bound carbohydrates hi serum. phoresis in which the ehiatc stream is continuously Feasibility separations of human serum immuno monitored by a flow photometer or colorimeter. globulin;, using the centrifugal elution chromatograph. The ekibon electrophoresis system utilize* a hori have shown a potential for the development of a zontal glass column < typically 3 mm in diameter by 40 prototype clinical analyzer. Preliminary results obtained cm long) loaded with a packed bed of particulates and with the elution electrophoresis system indicate mat jacketed for forced-liquid cooling (Fig. 9.3). Samples clinical utility includes the separation of serum proteins are introduced at the midpoint through a septum, and with detection by uv photometry, the separation of column entry points are arranged to allow a continuous various hemoglobins in the hemoiysate from red blood flow of eluent sweeping past each electrode chamber cells {RBC) with colorimetric detection, and the separa into the column or column exit. Eluent can be tion of serum isoenzymes of lactic dehydrogenase introduced directly into the system at either electrode (LDH) with reagent development followed by colori- side during or subsequent to the electrophoresis separa metric detection. tion, and the eluate stream progresses through a Analysis of neutral carbohydrates in serum glyco continuous-flow uv photometer or colorimeter. A rea proteins. A sensitive and reproducible chromatographic REAGENT 1BUFFER 1S0LUTBN RESERVOIR ~mSTRP-CHAR T f RECORDER REASENT STBEMLLREAGEMT UPSTREAM r NEEDED PUMP ELUENT PHOTOMETER' OR 5C COLORWETER BUFFER SOLUTION •*E—ff CEBATH SAMPLE ELECTRODE ELECTRODE NTROOUCTION CHAMBER CHAMBER -ELECTRODE ELECTRODE s POROUSrr BEO QC POWER SUPPLY Ffc.9.3. Batten iw< tiopkonm system. 19 procedure was developed for the analysis of neutral The three protein-bound neutral carbohydrates were carbohydrates in glycoproteins. Separation is effected measured in sera from 29 patienu with metastatic by ehttion of a rugn-resowtior anion exchange column breast cancer. Twenty-three of these paticnu had with a pH 7 concentration gradient of boric acid (0.067 fucose values above the range of values found for the to 0.672 M). high-sensitivity detection is provided by a normal female subjects. Levels of the three carbo cerate audknetric system1 which monitors the fluores hydrates were all within normal ranges for the six cence of Ce** produced by the oxidation of eluted ptfientt having normal fucose levels. In general, eleva constituents with Ce4*. Sensitivity to nanomok tion in fucose was accompanied by ekvatkm in the two amounts of the carbohydrates galactose, fucose, and hexoses; however, a proportionately larger increase was mannose was demonstrated. The separation of a refer apparent in the levels of fucose (Table 9.1). ence standard containing 16 neutral carbohydrates is The resulu showing that 79% of the patienu hav«r shown in Fig. 9.4 and is illustrative of the separations elevated fucose are interesting, but the high percentage that can be achieved with this system. of these patienu displaying normal values is somewhat Levels of glycoproteins in human serum were esti disappointing. Additional studies are needed for pa- mated by using hydrolysis and analysis of the protein- bound carbohydrates Elevated levels of serum glyco proteins were observed in human subjects with malig nant diseases and in laboratory animals with induced 4. R. A. L. Macbeth and J. G.Bcfcea.*TbanCrrcopioli 4 in Mangaant Disease,"/*«*. Sure, SB, (33 (19*4). tumors. '* An elevation of serum protein-bound fucose 5. S. Hantiman and G. Bryant. "SeraaMucohiUreb in Rats was reported for patienu with malignant breast Bearing Wake; Careworn 256 and the Effect of Swpol masses.* In general, nonspecific colorimetric procedures Extirpation of the M^apuHt." Oncer Res. 24,1625 (1964*, were used to analyze neutral carbohydrates in serum 6. F. E. Rosato. M. Seltzer, J. Mulct, and E. F. Rosato. glycoproteins even though the methods were shown to "Serum Fucose in the Diagnosis of Breast Cancer," Cancer 28, 1575(1971). be subject to interference.7 ~' ° Chromatographic sepa 7. A. S. Evans. M. F. Dotan, T. Z. Sobocinski, and F. A. ration enables a specific analysis of each of the three Quran. "Utility of Scram Protein-Bound Neutral Hexoses and neutral carbohydrates (mannose, fucose, and galactose) L-Fucosc for Estimation of Mabgnant Tumor Extension and that arc bound to serum glycoproteins. Evaluation of Efficacy of Therapy," Cmctr Res. 34, 53S (1974). Protein-bound mannose, fucose, and galactose were S. P. Z. Sobocimki, W. I. Canterbury, and K. M. Hanky, measured in 12 normal female subjects. Our average Determination of L-Fucose in Glycoproteins, I, Effect of fucose analysis (Table 9.1) was substantially lower than Nonfucose Moieties of Serum Glycoproteins. SR 72-6, Armed the values determined by means of the nonspecific Forces Radiomology Research institute Scientific Report. coiorimeiric procedure and reported in the literature. Bethcsda, Maryland (1972). The latter generally ranged between 8.2 and 9.5 mg/100 9. G. Gyorky and J. C. Houck. "The Determination of Terminal Protein-Bound Fucose." Can. J. Biochrm. 43, 1107 ml."'11 However, Sobocinski et al.,* analyzing the (1965). same pooled normal serum by means of the nonspecific 10. R. J. Wmzlci, "Determination of Serum Glycoproteins,'* colorimetric method and a specific enzymatic pro Methods Biochem. And. 2, 279 (1955). cedure, found that results by the nonspecific method 11. J. J. Barlow and P. H. Oillard, "Serum Protein-Bound were 44% higher than those obtained by the enzymatic Fucose in Patients with Gynecologic Cancers," Obttel. Gynecol 39,727(1972). method (9.5 mg/100 ml vs 6.6 mg/100 ml). Our results 12. A. Safer and S. K. Weimtaub, "Serum Protein-Bound would tend to verify the failure of the colorimetric Fucose Levels in Certain Chronic Diseases: A Oinical-Statisbcal method to measure accurately true fucose levels. Study," din. Chim. Acta 6,174 (1961). Table 9.1 wtmwfwt of pfotn*v*%(Mmnt c«nY%ali*r4n4«v in wtn Horn Type of Average analysis (mg/100 ml) Range (mg/100 ml) No. subject Mannose C.V.* Fucose C.V.- Galactose C.V* Mannose Fucose Galactose Normal 12 44.4 17.6 4,g 25.7 43.6 19.5 34.5 -62* 2.8- 7.6 30.2-57.5 Breast cancer 29» 69.0 26.S 10.0 39.2 73.5 30.9 45.0-107.3 3.9-21.1 39.1 -125.1 "Coelrkitiil of variation rt> %. Six pilients had aB analyses within the range of normal values. 40 ""» '—'—i 1 1—i—rr-r ! ! i * 3 8 I I V 1 1 i 1 i X s 1 I? HL ij li si #1 1 DUMSMnij ^ i. • ^-».i» 41 bents in the latter category to determine if the normal chromatognm is shown in Fig. 9.5. As expected, the levels are maintained. chromatographic pattern had a large peak for all of the GeatiwnpJ elation rhiiinnliyiyhy of am •*• nonsorbed species, foBowed (after (hanging die clucnt •NMngJafcaias. A separation of the protein IgG from to 3 M NaSCN) by a much smaller peak for the specific normal human serum is representative of the affinity protein, lgG. The rotor speed was 400 rpm; monitoring chromatography experiments using the centrifugal elu- was done at a wavelength of 280 nm. tion chromatograph. The eight-place, fixed-column The results of these preliminary experiments led us to rotor previously described was used for this investi believe that the system is capable of performing gation. The cohunns are dynamically loaded with a determinations of several different serum proteins slurry of Sephadex G-25,100- to 30O*i size range, onto simultaneously from a single sample in less dun 10 mm. which antKhumanHgG had been immobilized. When a Proteins of specific interest include the human immuno steady-state flow rate of euent was established, the globulins. sample volume of 25 /d of human serum per column (a total of 200 id for eight column\> was dynamically •i semi isoenzymes of LDH. As many as introduced into the ehient annuius. The resulting !2 eiectrnphoretic peaks, detected by a flow uv photometer operating at 280 nm, were separated from 10 ul or less of human serum. A typical ekctro- phoretogram of human serum shows a separation in ONNL 0«6 73-112 which the normal serum protein pattern (Le., the n—i—r CONSTITUENTS pattern usually observed by cellulose acetate electro OTHER THAN phoresis) is observed but with an indication of addi US tional resolution. The peaks were tentatively identified by edition position and by reclectrophoresis on an analytical gel electrophoresis system. Operation of the same system with a flow colorimeter monitoring a! 410 nm but with othei operating W6 conditions similai to those used with the serum separation gives an indication of seven hemoglobin peaks from I ul of a 4:1 (distilled water: packed RBC) RBC hernorysate. This compares with the usual four to five bands that are more completely isolated with a cellulose acetate separation. Separation of serum LDH isoenzymes was achieved using the same operating conditions as those above; however, a reagent development system was used to detect the separated enzymes. A colorimetric deter mination of isoenzyme activity was made continuously by monitoring the lactate-to-pyiuvate conversion with a flow colorimeter measuring absorbance at 510 rim. 3 4 9 6 7 6 •0 Five major electrophoretic peaks and several smaller ELUTION TIME (mini peaks were evident in the resulting LDH separation ROTOR: 8 COLUMNS (Fig. 9.6). This pattern was in good agreement with the COLUMN OlMCNSlONS: 0 32 em > 10 cm CLUENT ENTRY: RADIUS OF 35 cm typical separation of the five common LDH isoenzymes ROTOR SPEED. 400 rpm SAMPLE: HUMAN SERUM on cellulose acetate. The separated enzymes were SAMPLE VOLUME 0023 ce/column tentatively identified by elution position and cochro- STATIONARY PHASE: ANTl (HUMAN) IgG IMMOBILIZED ON SEPHAOEX G-2S,IOO-3O0p matography of two of the isoenzymes. ELUENT WATER. THEN 3J1 NaSCN An elution electrophoresis that can be applied to Fig. 9J. Affinity chromatagmn for xpanlion of IgG routine clinical analyses has not yet been developed, from nomal haman mm, iumg prototype centrifapl elation but the operating concept for such a system has been CtWOmatOffaph. iWmonstratcd by a first prototype system. 42 ORNL 0W& 7S-C29M literature is now available with over 85 articles or chapters published on the subject. 1 TYPICAL SEPARATION Of, CELLULOSE ACETATE O During the past year, primary efforts inctuJed the continued development of an analytical system based 0.03 — around a miniaturized prototype of a CFA. A system comprised of an automated sampte-reageut loader, an analyzer, a computerized data system, a rotor cleaning IU station, and several rotors has been evaluated and zU routinely operated for the past two years in the clinical < laboratory of the Health Division. To obtain another •ao2 — it independent evaluation, -.wo additional systems were o * — fabricated and are being assessed hi the clinical labora « z M tories of the NASA Johnson Space Center, Houston, Texas, and the National Institutes of Health (NIHX u Bethesda, Mainland. Three additional systems are bong K fabricated for future evaluation in several diverse 3 K laboratories such as a Mood bank laboratory, a small- X QO«r— animal laboratory (National Center for Toxicological jl -1 X X Z a o Research, Jefferson. Arkansas), and a genetic screening J J A " " laboratory (University of Michigan, Ann Arbor). Z • 1 i To broaden the application of CFAs. a multipurpose o optical system has been developed (see Fig. 9.7). The < u same basic system can be used to obtain either a: 1 1 1 O 5 tO 15 20 APPROXIMATE ELUATE VOLUME (ml) 13. N. C. Anderson and C. A. Butt is, "GeMSAEC Fast Fa*. 9.6. Separation of LDH isoenzymes at 10 jil of \ Clinical Analyzers," p. 521 in Clinical Biochemistry - Principles MMikf ehrwow ckctiofjwunau at 1200 V for 30 MM win a and Methods. Walter de Gruyter. Berlin. West Germany. 1974. S-Ml/hr buffer (0J5 *f mw« phosphate, pH SJt) now at each 14. N. G. Anderson. C. A. Bums and T.O. Tiffany. cud of the tulwn, Quale monitoring is by reagent develop "Enzymology. Clinical Chemistry, and (he Development of Fast ment. Analyzers." p. 155 ir. Er.zymdogy in Medicine, ed. by P. Blume, Academic Press, New York, 1974. 15. T. O. Tiffany. C. A. Burtis. and N.G. Anderson. "Fast 9.2 CENTRIFUGAL FAST ANALYZER Analyzers for Biochemical Analysis." in Methods in Enzymat- ogrv. vol. 31. Academic Press, New York, 1974. DEVELOPMENT 16. T. O. Tiffany, "Centrifugal Fasl Analyzers i.i Clinical Laboratory Analysts." p. i29 in CRC Critical Reviews in The basic objective of this effort is the development Clinical Laboratory Sciences, The Chemical Rubber Company, of fast analytical systems for clinical, small animal, Cleveland, Ohio, 1974. genetic monitoring, environmental, and other related uses. The first system developed under this program was OMI en T> m the GeMSAEC Centrifugal Fast Analyzer (CFA), which riac* O»TIC | -, features the use of a centrifugal field to simultaneously -'WV/W^—» I CMVfT I >K •MPII I » initiate and transfer several parallel reactions into their respective cuvets, where they are rapidly and sequen LtM MO tially monitored by a stationary photometer or fluo- rurtu rometer and an on-line digital data system.13 ~' * These ossiaatv [sjvr] GD analyzers have been commercially developed, and ap proximately 400 to 500 of them are now operating in I "r I——L—umiil Icouwrnl clinical laboratories located around the world. In general, their acceptance has been good, and although Fig, 9.7, Schematic of the tmtitipmtpom optical system the technology is new, a sizable source of reference developed for use with a Centrifugal Fast Analyzer. 43 transmission, fluorescence, chetniluminescence. or light- continuing i which reagents aie ryophih/id wiUnt the scattering measurements. This is achieved by combing cuvets of the rotor, followed by dynamic recomtiturion different light sources, fiber optics (Fig. 9.8). and rotors at the time of analysis.23 Stability studies indicate that of various designs constructed from appropriate win some reagents are lust during the lyophiluation process, dow materials (Fig. 9.9). and by using a relative after which the remaining reagents are stable for at bast geometrical location to a photomultiplier tube.17-1* ten weeks. A collaborative program with one or more of In addition to the miniature analyzer, a portable ihe commercial reagent manufacturers was initiated in version is under development-2* It is anticipated that order to couple the in-house reagent technology of the portable CFA will ultimately be a small unit that commercial firms with the CRNL Fast Analyzer tech will contain both the analyzer and data system in a nology. single cabinet. The evaluation of the second prototype of portable CFA was completed during the past year. Analytical Appicatiims Based on this evaluation, a third prototype was de Work continued on automating the various techniques signed and is being fabricated. The new prototype (Fig. utilized in blood banking. To date, dtis includes blood 9.10) features an improved mechanical drive and grouping analysis and the measurement of prothrombin braking system to facilitate the efficiency of transfer times. In addition to the hematology applications, an and mixing, and a new temperature control system that effort was initiated to develop analytical procedures in utilizes a thermoelectric heat pump. The analytical the general -irea of environmental water analysis. Work moduk alrng with a microprocessor data system will be also continued on the use of CFAs for genetic monitor incorporated into a single cabinet. ing. A dedicated microprocessor data system was designed Hood grouping analysis. In the initial feasibility and fabricated (Fig. 9.11). The heart of the system is an studies.1* the technique of Mood grouping analysis lntel-8080 microprocessor chip. This chip, with about using a CFA was demonstrated on an early prototype 30 additional integrated circuit chips, will make up the coupled to the old GeMSAEC computer system. The microcomputer that can control the analyzer unit and loading of aliquots of blood samples and antisera was the data acquisition and manipulation, and can print performed manually. This technique has now been the data and identifying information on an alpha adapted for use with the miniature analytical system numeric printer. routinely operated in the clinical laboratory of the Rotors of various designs were fabricated and Health Division. 2 J 2 tested ' " in a continuing effort to develop one that The use of an automated loading system2' to put the contains preloaded reagents and is capable of accepting, aiiquots of whole-blood samples and antisera into their processing, and analyzing a whole-blood sample. In ' :spccitvc chambers in the rotor was a major improve regard to the prepackaging of reagents, studies arc ment in the Wood grouping procedure. Since the automatic pipettes in die loading system are wd 17. T. O. Tiffany. J. M. Partita. W. F. Johnson, and C. A. primarily to measure and dispense liquids, their use Bum*. "Specific Protein Analysis by Light Scalier Measurement with aliquots of whole blood was a concern. Studies with a Miniature Centrifugal Fast Analyzer." Clin. Chtm. 20, indicated, however, thai jliquots of whole-blood sam 1055 (1974>. ples could be measured and dispensed without en 18. T. O. Tiffany. J. M. Harelb. C. A. Burtis, W. F. Johnson, countering plugging or carry-over problems. Saline was and C. D. Scott. "Blood Grouping with a Miniature Centrifugal Fast Analyzer." Clin. Chem. 20, 1043 (1974). used a? the diluent instead of distilled water, which is 19. C. A. Bums. W. D. Bostkk. and W. F. Johnson. "De ii.'Kmally used v the routine operation of the loader. velopment of a Multipurpose Optical System for Use with a No problems were encountered in the loading of the Centrifugal Fasr Analyzer," Clin. Chem. 21 (in prc*t. aliquots of antisera. In addition, improvements and 20. C. D. Swtt. W. F. Johnson. L. H. Thicker, and C. A. refinements were made of the basi- technique to Burtis, 'A Small Battery Operated Centrifugal Fast Analyzer." Clin. Chem. 20, 1003 (1974). provide better discrimination between the antigenic 21. C. A. bunts. W. F. Johnson, and J. B. Otcrlon. reactions of the veakcr hemagglutinating antibodies "Automated leading of Discrete, Microliter Volumes of Liq such as anu-C(rh'), anti-D (Rho). and anti-E (rh'). A uids into a Miniature Fast Analyzer," Anal. Chem. 46, 786 (1974). 22. C. A. Burtis. W. F. Johnson, and T. O. Tiffany. "The 23. C. A. Hurt's. W. F. Johnson. J. 1. Overton. T. O. Tiffany, Development of Rotors Having Separate Sample and Reagent and J. C. Mailen. "Optimization and Analytical Applications of Transfer Channels for Use with Centrifugal Vast Analyzers." the Technique of Dynamic Intr-tduc'ion of Liquids into Cen Anal leu. 7. 591 (1974). trifugal Analyzers," Clin. Chem. 20,932(1974). A B ORNL PHOTO 2917-74 A t Ffc. 9.S. Modification of (he optical head of the Centrifugal Fait Analyxer which illowi for either of two fiber optic configurations. (/I) 180° orientation; (B) 90* orientation. 45 PHOTO 0776-75 £v 'si •* B Fig. 9.9. Family of rofon designed and fabricated for as* with tut nwniaffi Centrifugal Fart Analyzer. (A) General-purpose transmission rotor, body fabricated of 0-5-cm bbck acryk.' plastic (chambers in serial army), windows fabricated of ultraviolc'-transmittinc (UVT) acrylic plastic; (0) feneial transmission totor having quartz windows; (O deu-body rotor, body fabricated from 0.5-cm UVT acrylic plastic, chambers in serial array, UVf windows; CD) clear-body rotor, chambers in parallel amy, UVT windows; (*") clearoody rotor, bbck aaylic top window, UVT bottom window; \F) Mack-body rotor with quartz cylindm sealed into the peripherai wall of each cuvet. UVT windows. 46 urn Mive »otc. IW IKS"! JOWKt 0*M.-fMOT0 MNII-7J •> » r F«.9.I0L Si* view of the prototype of the portable Ccafnfapi Fast AMtrset. O«N«.-*HOT0 0111*1-75 OAU,"STATUS LIGHTS DATA ENTRY SWITCHES COMPUTER CONTROL SWITCHES W* AOVANCf # / ROTOR SYMC i' CUVITTI SYNC ANALOG SIGNAL SJVEN COLUMN SEVEN SEGMENT THERMAL PRINTER Ffe.9.11. Mkropioccaoc d»tt system. 47 study was made in which the modified procedure was of the reference tedmique due to the lower operating compared with the manual protocols used by the temperature (30 vs 37*C) currently employed. medical technologists of the ORNL cluneal laboratory. Einwoaaatatal iiwjijij. Specific environmental analy Equivalent results were obtained for all but three of the ses must be adapted or developed to utilize the portable more than 100 samples analyzed in the study. Two of CFA. Consequently. a program was initiated to adapt the discrepancies were due to transcription errors, while cr develop chemical reagents and specific methods the third KS a sample problem. for water analysis using the CFA. These developments Protocol devdofHKM. After the improved Wood inchide: (I) analytical procedures for phosphate, zinc. grouping procedure was adapted for use with the ioduK. lead, and sulfate; (2) methods for other water nunbfure analytical lystem. a protocol and instruction analyses, especially for nitrite and potassium:(3) deter manual was written. The manual describes (I) reagent mination of arsenate in solution; and (4) determination (antibodies) requirements. (2) antibody titering. (3) of the catalytic effect of Tween 80 on complex forma setup procedure. (4) operating procedure, and (5) tion. computer programs. A copy of die manual was supplied Genetic •awtnrag. In a program funded by EROA to NIH and will accompany the analytical system that and conducted in collabo.ation with the Department of will be evaluated by an external laboratory. Human Genetics of the University of Michigan. Ann Pluthwibin tine dmi—iijtioti The principle of Arbor, we investigated kinetic spectrophotometric pro the CFA was applied to the field of coagulation cedures thai can be adapted to a miniature CFA for testing.14 The mult sample parailei-moniioring capabili genetic monitoring of enzymes. To demonstrate the ties of the analyzer give it several distinct advantages feasibility of this approach, we studied the kinetics of over instrumentation conventionally used for clot de several glucose-6-phosphate dehydrogenase (G-6-PD) tection. An on-board normal control plasma can b». variants. monitored simultaneously with r.p to 16 test pusmas. The results of the initial feasibility studies demon Thus :he control and all test samples can be treated strated that the A ORNL OWG 75-5215 RUN NUMBER'S-3.0 SAMPLING INTERVAL SAMPLE GROUPS*45 MINUTES*0 SAMPLES/CUVET'S SECONOS'I A8S0R8ANCE vsTIME 0.450i i i i i I I I I I I I I I I I 11 I I 11 I I I I I I I I I I I I I 11 I I t I 0.430 - am**** *****»«** 0.4IO - 0.39O • / o 0.370 z < K 0.350 o w + 5 0.33O 0.310 * 0.290 • 0.270 It*: * 111111111111 ii 1111 ii I I 111 1 •• I I llll 1 I III 0.250 45 TIME IN SECONDS F* 9.12. Foar kydx GcMtfqpl Fart Ammyn$ in He 10. Environmental Studies III AUTOMATED ANALYSIS OF POLLUTANTS 1. Over 100 refractory-organic compounds can be present in effluents front municipal sewage treat Surface waters ar.- becoming increasingly important in ment plants at ppb leveb: some of these refractory this nation as the source of water for potable and compounds are chlorinated under conditions that industrial water systems. Characterization of the or exist when effluents from sewage treatment plants ganic constituents in surface waters assumes importance are chlorinated. in direct proportion to the use of these waters for 2. Kigh-resokicion anion exchange chromatography human consumption. Relatively little is known about provides a reliable and useful tool for determining the health significance of the very low concentrations (ppb) of stable organic and chkxo-organk compounds found in water, although some chlorine-containing constituents have been found to be carcinogenic, I. T. F. X Corn** and C H. Wdfcnms, Teratogenic StwJirs mutagenic, or teratogenic.1 ~J Regardless of the source, with 2.4>T and 2,4-DwtlK Hamster,"»A£*r»^ CoiOewi- whether domestic, industriai. or agricultural effluents, Tiuaicl 6,559(1971). IC. L Litttrsf and E. P. Lkhtenstcm. "Effects and atmospheric washout, runoff, or by-products of natural iMcnciioas of EntiroKueatal Chemicals on Hainan Ctfc m biogeochernicai systems, it is imperative that identities, Time Culture." Arch. Enwwom. Hembh 22, 454 ( 1971). quantities, and loxkotogkal effects of the individual 3. R. SL Pafdmi. "PotydNotmated Bjohenvb (PC»>: Effect on organic constituents and pollutants be established. Quan Mitochondrial Enzyme Systems." Butt. Enriron. Contmn. Toxi- titative information concerning these trace compounds rrt 6.539(19711. and the effects of treatment processes such as chlorina- 4. S. Kali. W. W. mi. Jr.. C. D. Scort. and A. A. Rosen. The Dctciminatmr. t»f Stable Organic Compounds in Waste Effluents tkm is essential for assessment of aquatic ecosystem a( Microgram per Liter Leveb by Automatic Hn^-ResoMlioa effects and the ultimate effect on mankind. Ion Exchange Chromatography," tmter Res. 6,1029 (1972). High-resolution anion exchange chromatography is 5. R. U loUey.W. *- Put. Jr.. and C. X Scoil. "High-Resom- used as the bask separations method for analysis of tion Analyses of Refractory Organic Constirnenis in Aqueous Waste Effluents." pp. 247-52 in Reditu m Enrwonmemmi trace organic* in various polluted waters because of its Testing «•* Controi {Proceedings ofth • 19th Annum! Techmcml sensitivity and capability for analyzing many low- Meeting. Institute of knwwonnunul Sciences, Anaheim. Cmhfor- molecular-wcighl refractory organics in aqueous sam mM.AprM2-5.l97J). ples.4'* A routine multkomponent analytical scheme 6. R. L Jofky. Chhrwmlkm Effects on Organic Constituents utilizing additional ion exchange chromatography, uv m Effluents from Domestic Sanitary Sewage Treatment Plants, ORNL-TM-4290 (October 1973). spectrometry, gas chromatography, and mass spectrom 7. R. U JoRcy. W. W. nil. it, C. D. Scoti. and M. D. etry is used for determination of the chemical structure McBride. "Determination of Trace Organic Contaminants in of the separated unknown organic constituents.' Natural Waters by Hqrh-Rcsohirjon Liquid Chromatography." pp. 397-412 in Proceedings of the First Annum! ffSF Trace Contaminants Conference. Oak Ridge National Laboratory. Oak Ridge. August 8-10. 1973. iffhtents from Sewage Treatment Phats 1 W. W. nil, R. L- JoHey, ami S. KaU. >4«r 49 50 refractory organic compounds present at low levels quantitation. In addition to the identified compounds, in sewage effluents and other polluted waters. more than 100 mass spectra and gas chromotography 3. In addition to uv-absorbing compounds, numerous retention values were obtained of unknown compounds other compounds can be detected by sulfatoceric found in chromatographic fractions of both primary add oxidimetry. and secondary sewage treatment plant effluents. 4. The detection of sources of pollution, die testing of Natural Waten the effectiveness of sewage treatment steps including possible tertiary steps, and the determination of the The identification and quantitation of trace organic* ultimate disposition of pollutants are nbvi-jus >*nd in various natural waters are being studied by using uses of the high-resolution anion exchange chro high-resoluiion anion cuwnge chromatography. ?•'.*<£? matographic systems. samples from ti-e of ttrc six sites dec-en for this study" were examined. The concentrations of die This research program was limited to the adaptation identified constituents in the original water samples of existing analytical systems for use in the determina have been estimated and are given in Table 10.3. tion of refractory-organic compounds in polluted Nineteen additional unknowns were characterised with waters with a minimum of instrumental development. respect to gas chromatographic and mass spectral The scope oi the program did not include exploiting the properties. capabilities of the analyzers for detecting sources of pollution, testing the effectiveness of sewage treatment Efflftt from Coafcftwrc ning Hats j-tints, determining the ultimate fate of pollutants, or Because of the high probability of coal becoming the identify ing positively ail of the separated organic major energy source in the near future and the constituents. consequent utilization of coal for production of gaseous Significant expansion is recommended of the use of and liquid fuels, two coal-iiquefaction plant effluents of high-resolution liquid chromatographs with uv photom possible environmental con-jern were examined. These eters and cerate-oxidathre monitors for determining aqueous samples were from: (I) die product separator, refractory-organic compounds in industrial and other sample 12131 (dissolved organic carbon (DOCK av polluted waters. This can bt accomplished either by 10.500 fig/ml: pH. 9 0|; 12) the dryer-stage first off-gas fabricating additional UV-Analysers developed at scrubber, sample 12132 (DOC. av |40ug/ml:p?'t. 2.8). ORNL or by modifying commercially available high- Both samples were extracted with methylene chloride, pressure chromatographs. A vigorous effort should be and the extracts were exammed by gas chromatog continued to determine the identities of the residual, raphy-mass jpectrometry. The extract of the product- stable organic compounds being discharged into surface separator sample contained a complex mixture of a waters. Also, potential hazards of these compounds, large number of compounds. Mass spec tea were ob particularly those that are chlorinated, should be tained for 15 constituents, of which phenol, three evaluated. High-resolution analyzer* have been devel cresols. three dimcthylphcnols. and xylene were identi oped to the point where they could be used by fied. In the less complex extract of the off-gas scrubber appropriate agencies to determine the sources of pollu sample, two major and several minor constituents were tion, the effectiveness cf sewage treatments, and the detected by gas chromatography: one was identified as fate of organic pollutants - all on a molecular level. dioctyl phthaiate by mass spectrometry. This effort should be closely coordinated with the Analytical-scale high-resolution chromatography of anlytical development program to take advantage of both samples revealed numerous uv-absorbing constitu improvements as they are made and of "feedback" ents and cerate oxidi'aMc compounds. Over 80 uv- information relating to problem areas that would lead absorbing constituents were separated from the product to necessary modifications of the instruments. separator sample in a preparative-scale chromatographic A total of 56 organic compounds were identified in run (Fig. 10.1). Six of the separated compounds have primary sewage treatment plant effluents (Table 10.1), been identified by gas chromatographic and mass and 13 organic compounds were identified in secondary spectral properties of the trimethylsilyl derivatives of effluents (Table I ..2). Forty-six of the constituents the compounds and were quantified based on FID identified in primary effluents and five in secondary response (Tabic 10.4). Several unknown constituents effluents were quantified based on a flame ionization detector (FID) response. Many of the constituents do 10. Chem. Technnl. 0tr. Anna. Trap. Rrp. Mar Jl. 1974. not absorb uv light, which was the previous mode of ORNL-4%6. 51 Taak IOLI. Coaoeatntiaar CtMBiitacat* IdcmiTicauoa method^ Carbohydrates Gataruwe'' AC.GC ChK 2-Dco&jra4yccnc acid MS 7 2 ,5-DidciuqrptatQak adr MS 6 3.4-CMeoxrrmi<*ic add MS 13 2-Droxyictroak acid MS 6 4-DeoxytcttoaK add MS 6 Glyceric arid MS 5 4-llydwaybacytic acid CC.MS 6 ' .fydroxyisobBfyric arid GC.MS 4 Oxalic arid AC.GC. MS 2 Qaavxariar MS SO RaVoaicacid MS 4 San am arid AC. GC.MS 24 Aroantk orpak acids •eazokacid* AC. GC.MS 3 2-Hydroxyberzoac acid' AC. GC.MS 2.7 3-Hydroxybcazok arid* AC. GC.MS T.40 4-Hydroxybcazok arid* AC.GC 1 4 ItydruAypatayLiciijc nan AC. UV. GC.MS 16-S2.190 34lydroxypiieayliydracrybc acid AC. UV. GC.MS 10-22 3-HydroxypaeaylpTopkMic arid* AC. GC.MS 6.20 Pfceaybccfic arid AC.GC 10 o-Fklhanc acid* AC. UV. MS 200 ^attyacids •akniticacid GC.MS \ 12 AMiao acids nteaybiaMiae AC. GC.MS 50.90 Tyinjaw AC. GC.MS 34 Aawots Urea AC. GC.MS 16-34 Pfceaotk compounds pOesol AC. GC.MS 20.29 AC. GC.MS 6.12 Indoles 3-Hydroxyindok MS 2 AC.GC.F 1,2 Pyridine derivatives >V( -Methyl-2-pyridMe-5 Title 1*1- < C*KeBt»uuar Coastiracat Ucmvitatinm attibod' AC. CC. UV. CC. MS 4 2*. 50 Hyaonaduac' AC. CC. MS 12 -41 JS lnosiat' AC.CC.UV.GC.MS 11-23.50 1-MctayisjaifcaK* AC.CC.UV 70 3-MttfcjrtaMlnK'' AC.CC 7-MciiiytuadNaf'' AC.CC.CC 2.#0 AC.CC Unocal* AC.GC.VS » Xaadnae' AC. CC. UV. CC. MS 2-7.70 ^rtwMdnc duifcjinvi 5-Acctyfimino-^nnHo- 3-*e*»lwadr* AC.CC.UV.GC M© anoctcM*' AC.UV.GC.MS 2.5 TayaMae' AC.CC.CC.MS 7. «-2» Uracil' AC. CC. UV. GC. MS U-5S. •#• *A1 coMterats were MeanAc* ia caloriaMai efflacats decaf I *AC-aaiciCTiiiiBi danawmiajaj ;CC - caDoa iiihjaai i aiuaniu»i a*j: UV 9^uoiuiar;GC-pstlaToauiotMBfcii oa nw> nihanu.MS - IIIII •jrrtiuni:ri;F - c Myofc Qrceriac AC.GCUV CMRW MS I rOnoi AC.CC. MS 20. 3-HyAoiymcoic MS 2 faaMe-^aoetic seal MS 13 1.7-DMedrjrtuMlM** AC.CC.UV « AC.CC.UV 20 I Mcrayaaoaw. AC.OC.UV ,* 1-MnfcrtaMlMK AC.CC « 7-MrdqrtJuMhMc ACOC.UV 5 S-AifBH—ima I awaiu 3 amhjlaijii AC.OC.UV 30 Undl ACCC.UV.MS H.JO GC — fiv cfcnMtofognpfcy; UV - arfbiviolft ^vctrwoopy; MB — JMM ^tvcraMdrT- S3 iaj. Comwint* -«*.„-• > Caoceatnaoa (PI*) rwyol vcnvstivcs DK*yfcar (fared Mctbyt«4>ffcro?ynangaV<4> AC.GC.MS 30 MctlqrWHiacopyaMffi le«> AC.OC.MS 3 0-Mcd*lim«oltl.2.3.4.5> GC.MS 0 3 10 Xyfcfot (S) AC.OC.MS 1 GarbafcjraVttR SaCMOtfl.S) AC.GC.MS 2 Fatty acafc LaMfckacalfI.5) GC.MS 0.7-1 J Okie acrid.S) GC.MS 0.7-14 hkMQcacatU.5) GCMS 0.3-O4 Stearic arhli I) GC.MS 0-5 Oydacd) AC. GCMS 2 MSwoH3> AC.GC.MS 7 <.V-Di»jrri*1<4> MS 4 Vwa (1.2> ACGCMS >• ^CoasMacats KK nkanficd • SMMB takes fiwa «M$ dcapntea by the paMHkars: (I) Lake Maris*. 12) r « Unta Lake. 13) Hobtoa RWCT. 14) Maanrpi Rim. (S) Wattt Oar Lake. *AC - a— esrfciaar thfWBlufijph; ;CT - catMM opfcy.lJV - afcHwiuiM ajectfparooy.GC - fatdtroatttofjaphy.MS 1*4. Coacraoatwc fate/atrr) Cowttitaca i nW Emywe* '"M*"" A*AC*~I Catechol M0 5*0 3*00 2000 3-Meibykatcchol 170 44fethyfcaicclMl 110 Gticiw4 120 3M 500 Roornnoi 220 790 1000 2'MethylK>offneo| 14 100 10-IS on flaaie noeafiMi etetertor rapoMfc •Briaf ea* rk *A*a)yiea> by »\ Z. FJM asa*; a catechol •atcalc eaxyaK < •eatd os Ike av aktoihaace of ihe picpjucav-scalt tktom-Muej ashic peak. *•««• oodKTihjerhjocT of ihc awlj m d m. jh efceowa1 54 CWH. oas T»-U«S»«« • wo c» wins STEEL rooccss A-ZTMESW. TO 10K «T On »r; fUKHT WUUWT- AOA • TO S-Og MMH BiAt FujOO MOTE- • M/*» F«. Mil. of on 12131* of a . were abo characterized with respect 10 mokcular ess effluents for identification of chlorinated organic weigh!, mass spectra, and fas and liquid cnromatog- compounds and for detcrrmnaliun of bfotoxidry is raphK ehition characteristics. bemg applied oi ;his mvesiuption.' *"' * 10.2 ENVIRONMENTAL EFFECTS II. I. ' nraky. The Tmimtni of Otahmf Wmim wait OF ANT1F0ULANTS CMomr. ANL F5-l2«Frbnjr> l*72l. I J. R- U Mky. "CMrmfCooiji—if. Orpwc (owuuroii* In contemporary technology. chlorine is the principal •I Scwjft tmmaa%J~ J. tftttr lUfer. Cnttnt f-rd. 47. Ml biocidc for removal of biological surface films in the • I»75IL cooling sysrems of electrical power-producing plants.'' I J. C. D. icon et d.. Exprnm-lm Fmtmrrrmf Srri. Removal of films is required t> maintain a high Snmvmm. hnw. Hep. Mm. I to Amg. SI. 19?I. ORM.-TM- 4777|J»I» W5». production effiurncy. Clworauiioi. of waleis con lam 14. C. W. Gehn. L D FrmjM. R. L Joky, jnd J. F. ing low concentrations of organic* with ppm cMohne Tkmnpmi. "F freer* of SteMe fMonae-rnaijMM* Orfamct on concentrations may result in the formation of chlorine- AqmiK Fovwowftv" Mmlwr 249. *75 < 1*74). containing organic compounds.*''1 Consequently, the 15. C. W. Gcfcrt j«i R. L. JoHry. "Ckinnw (OWUM* practice of chlorinating cooling waters is being evalu StaMt Oijnokt' New Coiowo«orf> of Fnw>nmcwiiro*cicni." hocet+mp of the 19th Contra of the Intrrmlwmm Assort* ated with respect to ihe possible formation of chlori rwm of Ijmmoiogt, Wmimpn, Mmmtoht. AupiU 22 29. 1974 nated organics. The methodology developed with proc fmprro). UK*** >••».«. lt"W Mti*K. w lm>>*a >•««.». • itft'M «*t»«l. • ! IM.I *» Mlft »4* till Ml|* MMM«Utl» imi. . _ *•«•» It*.I •> «»| (M iHI Hl|l «H**W*I<> '« k»»•«'••» HHMI I 4 «»""«« IMtHtlt «lH»«ml MtlMMl ,MIN*1*tKIM I (•MINI**"!* itMl, (rrrrr. tV^M?"*"* Pit. 10.]. Chromtiugfu* anowdti fcoUi "CMi^td vMofintt-unUMni Mttf uv-abMiblnf ton lltutnli In • Mmplt of KlngMun Slwm Mini cooling wiltr llw teborttoiy. A chrom»l Over SO chlorine-containing organic constituents were secondary scwap. treaiment plant which had been separated from a sample of Watts Bar Lake water that chlorinated in a like manner (Fig. 10.2). had been chlorinated to a 0.5-ppm chlorine residual. After a detailed examination of the experimental The constituents were separated and detected using the results, the major conclusion was that the yield of coupled **C1 tracer-high-resoiution chromatographic chlorinaiion associated with chloro-organics is about procedure.4'14 The radioactivity chronutogram was OLS^X of the chlorine dosage for reaction conditions quite ^.lular to that obtained for effluents from a similar to those at the Kingston Steam Plant. With an estimated 50.000 to 100.000 ions of chlorine being used annually in cooling waters, several hundred tons of chlorinated organks are produced annually by chkxina- tion annfoulant treatment of cooling systems, even at I*. It. I_ JaMcr. "IXefrrauBatiua of CMoriarCoMamt the low-reaction yield determined in this study. As the Orgaatrc • CMorinutf Sewage EiYhteau by Gwpfad MCI rnce H^j-ltnolntua CkntmutcfOfkf." Enrwoa. Lett. 7, national production of electric nnwer increases, this 321(1974). quantity can be expected to increase proportionately. il. Biochemical Engineering I I.I ENZYME-CATALYZED PRODUCTION correlated in a plot of hydrogen production rate vs 1/7 OF HYDROGEN (Fig. 11.2). The apparent activation energy (11.5 to 12 J kcai'moie) obtained from such a plot is similar for 1 A previous report discussed a cyclic process for both dithionite and pyruvate substrates. producing hydrogen (sad oxynm) from water, using Under optimum conditions with a fixed amount of sodium dithionite as a reducing agent and ferrcdoxin emyme. the initial rate of hydrogen production with and hydrogenase as catalysts. This process involves two dithionite was greater than that with pyruvate. How reactions: ever, the maximum amount of hydrogen obtainable from ditluonite was reached after about 2 hr: the yield fcr,rto was 0.21 mole of Hi per mole of dithionite. The Na2S,04 • H,0 '" > H, * Na^O, fcyt'roecnssc pyruvate, on rhe other hand, continued to produce Na.SjQj-^^O, •Na,Sj04 However, a problem has been encountered in the OVML m 7w-Mosm thermal regeneration of the dithionite. namely, that Q.40O, heating the higher oxides, such as NajS205 and r Nij S: 0». produces S02 - 0 several possible alternative reduciants tried, sodium pyruvate appeared to be the most promising. Therefore, the rale of hydrogen pro- auction was measured is a function of pyruvate concentration, solution pH. and temperature, and the results were compared with those obtained with sodium \ 03001- dilhinnile substrate. As with sodium dilhionile substrate, hydrogen pro duction is inhibited at higher pyruvate concentrations.2 The optimum pH for hydrogen production rsie is ft.5 to 6.7. %-bich is similar to thai observed with sodium dilhionite substnte (Fig. 11.1). The initial hydrogen production rale increased with So wo increasing temperature over the range 25 lo 50°C: however, after about I hr at 50"C. the rale decreased considerably. Similar behavior was observed for dilhio nite. indicating possible enzyme degradation al 5(VC. However, ihe data obtained from initial rales can be 0100 1. CKm. Teehnol. On. Anmi. ftnff. Rep. Mtr. 31. 1974. •o • t • « • • T.O 7.1 ORNL-4966. pp. 47 4*. 2. C. D. Scott et al.. Experiment* Kntmrerntt Seel. Semi- tmu. hngr. Rep. Mm. I. 1974. to Aug. J I. 1974. OKNI.- Fig. I I.I Optimum fH for hydrogen ftofccliDW compwvd TM-4777 tJuly »«»75). far 57 ss f V « osoo- O SOOIUM OITWOWTC o soonm PTHUMTS J WO IOOO/T Fig. 11.2. Effect of toMpentBieoak}*ro|mpio4«ctk>«»te. hydrogen even after 5 hr. reaching a final yield near >wai tmt H-MO«* 0.91 mole of Hj per mole of pyruvate (Fig. 11.3). In either case, the initial rate of hydrogen production can be increased considerably by increasing the enzyme concentration. During this report period we investigated the possi bility of immobilizing the ferredoxin-hydrugenase enzyme system,3 using a ceil extract containing both ferredoxin ind hydrogenase without further separation or purification. In various experiments we succeeded in trapping the enzymes in polyacrylamide gels by in ducing polymerization of the monomer in the presence of the enzyme extract. Quantitative comparison of the activity of the gel-entrapped enzymes with that of the free enzymes is complicated by the difficulty of measuring the enzyme concentration in the gel. Never theless, none of the gels we prepared appeared to give more than 1% of the hydrogen production rate ob o 9.9 • SODIUM DITHIONITE M' liter served for the free enzyme. However, the immobilized • 1.0 f SODIUM PYRUVATE enzymes remained active for several days: the hydrogen ft liter production rates obtained by addition of fresh dithi- onite aftc several days compared favorably with those obtained initially with the freshly , epared gels. °i A «lft Jo 4o &4o&i>6i»»toottoa40»o»oaoo Tint (atiMinl 3. ('. D. Sc»>tt el al„ hxperimenlal Hnxmeering Seel. Semi- Fig. 11.3. CompariKM of hydrogen production by wdnim amu. Prop. Rep. Sept. I. IV74. to Mar. 31 I97!<. ORNL- dMrioMt* and fodam pyruvate. Solution. 0.05 M phosphate: TM-4%1 (in orc»). pH. 6.6; temperature. 40°C. \ 59 112 BIOREACTOR DEVELOPMENT yeast, making pH control difficult To alleviate this situation, a pH controller was added to the activated Three types of reactors are being studied as potential sludge unit. This unit worked satisfactorily, efaunabng bioreactors: (I) continuous stirrcd-tank reactor the need for manual pH adjustment. Because the (CSTR). (2) packed-bed reactor (PBR). and (3) tapered mixture became acid during growth, ammonium hy tluidaed-bed realtor (TFBR). droxide was used to adjust the pH via the controller. The CSTR operates on a continuous feed basis. For Coatiuon* Stined-Taak Reactor our preiimmary work, growth medium (minus thia mine) phis phenol at : concentration of 0.05 M was Since an activated sludge unit, a CSTR, is the system used as the feed solutiou. Hk votencuk flow rate of most commonly used today to process poli'ited waters, the feed was adjusted so that the phenol concentration it was chosen as our baseline processing scheme for the in the reactor did not exceed 0.005 M. With a reactor investigation of f'lenol removal from waste streams. A volume of 2.25 Mters, we were able to maintain flow small, activated sludge unit with a capacity of approxi rates of 75 ml/hr. Unfortunately, the yeast did not mately 3 litcs was assembled with a Ludte reactor and form a good settleabie sludge, and even with the settling a standard Imhoff cone as the settling tank (I-liter cone, much was lost in the effluent. With a flow rate of volume). In this system, an air lift recycles settled 50 ml/hx. all phenol was removed from the feed, and sludge from the bottom of the settling cone to the the yeast growth was sufficieiitfy rapid to maintain an reactor, and excess sludge is removed manually. The air essentially constant biomass in the reactor. diffuser is a stainless steel pipe, with several small holes in line longitudinally, which is inserted through the wall of the reactor so that i! extends across the entire width Packed-Bed Reactor Stadia of (he reactor. The air bubbling from this pipe aerates and mixes the fluid in the reactor. As an adjunct to the CSTR studies, a PPR was set up A typical growth and pH-vs-time curve for Tricho- as a test reactor for phenol removal. The l-in.-ID by sporon cutaneum is shown in Fig. 11.4. The pH was 3-ft tubular reactor was packed with Vin. Berl saddles recorded continuously and adjusted nanually. Note and seeded by filling it with a suspension of yeast in that the slope of the pH-vs-time curves increases as the nutrient solution. Air and feed sohition containing 500 cell concentration increases. To date, the maximum ppm of phenol passed upward through the column. The phenol utilization has been 0.1 millimole of phenol per feed pump was initially adjusted to deliver approxi liter of reactor volume per minute. mately 45 ml/hr, while the phenol concentration in the As indicated by the curves in Fig. 11.4, a significant effluent was monitored intermittently to check for variation in pH ocurs during active growth of the phenol breakthrough. The feed rate was incr* j$e OML OWS 74-10)23*1 feed rate of 240 ml/hr could be maintained without breakthrough. The air flow rate was maintained at 440 ml/min. Start-up and routine operation of this reactor have been trouble-free. Start-up proceeded smoothly, with growth plus attachment "xcecuing washout. Thus, z visible, stable biomass quickly formed at the lower end of the reactor and slowly increased in height until it filled the reactor. Yet, significant occlusion of packing voids or general biomass fouling did not occur. The shear developed by the h'gh flow rate of air through 'Jte reactor should help to minimize the occlusion by excessive biomass. Air distribution throughout the reactor is fairly good. A cylindrical glass frit is used to sparge air into the CIOCX TIMC bottom o' the column: however, the packing appears to Fig, IM. Typical growth cuve and pH cydma of CSTR augment the rapid coalescence of the small bubb?,j. without an automatic pH comroBrr. The problems involving air-liquid contact and dissolved- 60 oxygen availability obviously demand considerable the bottom end, and 3 in. in diameter at the top end: attention. An oxygen probe will be used to aid in this (2) a feed tank and feed pump: and (3) a top gas-liquid investigation. separator followed by a solid-liquid separator. A tapered fhridized-bed section was fabricated from a ispcvcw emmnEw-wcu HCBCMV 3-m. section of glass pipe by forming on a tapered carbon mandrel. The total length of the reactor is 42 A TFBR b a special adaptation of fluidtzcd-bed in.: its capacity is 2349 ml. The angle of the taper is technology winch appears to be especially wiled for 0.68° from the pipe center (Le., an included angle of bioreactor operation. A TFBR can be used as a I J6°). The gas at the top of the fluid bed is water btoreactor for liable bacteria or yeast systems where sealed and is vented through a wet-test meter for the host is cither self-attached, chemically bonded, or volumetric measurement. Sofids that overflow from the entrapped, and also for any type of immobilized fluid bed are recovered in setting chambers which can enzymatic system. The use of a TFBR as a bioreactor be drained when necessary. for denitrifkation of nitrate in waste streams was investigated. Using anthracite coal as the bed material, for we obtained a maximum removal rate of 5 moles of NO)' per hout per liter (volume as settled packing For an ideal plug flow reactor, the design equation is volume), based on a feed stream concentration of X approximately 9 moles of N03~ per hour and a / = S./ rfAT/(-r), <» residence time of 1.2 hr. The use of contained microorganisms for chemical where X is the percent conversion. 5S is the substrate conversion of a feed stream to produce useful products eventration in the feed, and t a the residence time. or to eliminate pollutants can be accomplished by the For Midiaeiis-Menten (M-M) kinetics, the reaction rate use of a TFBR as a bioreactor. A TFBR has an included angle of I to 4°: this degree of taper provides a decreasing .'meat velocity with increasing column KWS.(1-X) ( 0 = (2) height. Such an arrangement gives a stabilizing effect Km*S,il-X) because the top of the bed is more dense, thereby eliminating any tendency for the bed to spout, even at high flow rates, where the bed is very dilute (90% void OMH. MS 74-IOI20RI volume). Thus, the TFBR has desirable hydraulic characteristics that allow it to operate over a wide range of flow rates in a stable fluid-bed mode. The TFBR also has a number of attractive biological characteristics. The mkromovement of the stable fluid will grind off layers of bound bacteria which, under normal fixed-bed operation, would bridge from particle to particle, thereby filling the void, decreasing the suitable flow area (SO to 80% void volume at typical fluidization flow rates), and restricting the availability of all of the bound bacteria to the feed stream MMIM chemicals. Many fluidizable materials can be found that are compatible with microorganisms. Bacterial compati MPCWC0 FLUID K0 bility is linked to a number of physical and chemical properties, such as size, porosity, surface texture, yt»r4*m !•» chemical positioning, and solubility. The TFBR is a IS*' i* completely closed system; thus, air can be easily excluded for strictly anaerobic operation. Seeding the bed with a bacterial suspension by recycle is easily accomplished. The TFBR equipment (Fig. 11.5) consists of (I) a tapered glass column 42 in. long, I in. in diameter at Ffc. I IS. Taaeml Matei-M Momctor. 61 Thus when M-M kinetics are applicable, the IIJ MOTItOCESSDEVELOPMENT equation becomes t S. Km In (I JT) The CSTR was used to determine the (3) coaversmi rale of phenol for a given feed concentration and to investigate the stability of reactor operation ai For a product-inhibited reaction, the rate equation is maximum conversion. With the reagentconcentration s in use. the limit of detectabiity of the phenol assay is K^.O X) about 10 ppm of phenol: thus the maximam rate of |r)> =-^ - (4) nr.noval s determined for a phenol concentration of approximately 10 ppm in the reactor. Microbial concen tration and phenol removal rates from a feed stream and the design equation becomes containing 2500 ppm of phenol ire shown m Figs. 11.6 and 11.7. Significant drops in microbial concentration L-h. Ii _l:", K' i^r-^-^.is) at the middle and end of October 1974 were due to cei X VmV Kt\ Vm I • K, \ X washout resulting from excessively high flow rates. We found that residence times of less than 20 hr would lead In either case, plotting t/Xvz\n(l - XVX should give a to a net ceil loss from the reactor: that is. cells were straight line. being washed out of the reactor at a greater rate than For a substrate-inhibited reaction, the rale expression they were being generated. Since the bmnass never is formed a good setdeaMe sludge, sludge recycle was not effective in maintaining a constant concentration of KmS, 0WR. M6 79-4SM i/^V. OCT I «K>V 0CC IS 20 29 SO « IS 20 30 ft 10 IS 20 TIME (days) Fig. 11.6. Operating history for tkt contiwoi sarnd-tank reactor rotative toMCIOD M oonotntration. 62 DVfc 7S-4990RI OCT NOV oec. 15 20 25 K) IS aj 25 30 10 15 20 TIME (days) RB.11.7. The maximum flow rate the reactor could accommo C4ML 0** 7S-4MSHI date was I27rnl/hr. TO- Toward the end of November a malfunction occurred that caused the reactor to be without feed for one to /" two days. The performance of the reactor decreased noticeably after this period. Microscopic examination < / of the reactor biomass showed that the yeast popula X 1 tion diminished to undetectable levels within a week 40 after the malfunction. The bacterial population that had established itself in the reactor continued to S iO- degrade phenol; however, neither the biomass concen tration nor the rate of removal of phenol could be increased to their former levels. Thus, during December, the reactor was shut down, cleaned, and reseeded with 10 fresh Thchosporon culaneum. This work illustrates that, for biological oxidation of s • • a is • ai M tri 2 s e 11 M irioa phenolic wastes in a strrred-iank reactor, the reactor can — mute* be operated quite well near the residence time at which Ftp, 11.8. tafomuMcc of ike packed-bed reactor wit* cell washout begins. Table 11.1 compares the perform rapect to pkeaol removal for the firtf 1.5 moadks of operation ance of our reactor with that of Bethlehem Steel's pilot-plant system for phenolic waste ire?'..nent. reactor was being operated with a residence time of As described in the previous section, a packed-bed 1.12 hr. Phenol was not detectable in the effluent; reactor was investigated for use as a bioreactor for however, since phenol breakthrough had occurred a few removing phenol. Its performance with respect to days previousiy at this same residence time, we assumed phenol removal for the first I.S months of operation is that the maximum throughput of the rezctcr was being shown in Fig. 11.8. At the end of this report period, the approached. 63 Rcantts of studies! Paraaetef ORWL I cmccMranoa 3500 ppai 2500 ppm Reactor votaaar 10*2 cat 2.25 htcn Flow rate of phcaoi vibatioo »l.2pl/hf USad/hr HowiateofdlMi) 330pl/kr 0 rfataBoi mnoval rate 4.Sf bier'1 day'1 4.2 j liter"1 day" Rendeacc tint Total flow = 2.7 hr: 20 k pfecaoinow»l7fcr Efnaeat concentration 0.4-0.7 i —lOms/litcr Oxygen iiqeauranrnii for the biological oxidation of cation in a bioreactor to eliminate nitrate from tes' phenolic wastes. In developing a fluidized-bed bio- solutions. reactor for aerobic microorganisms, allowances must be Two series of tests were performed in the TFBR made for the oxygen requirements of the biological described, using about 530 mJ (~400 g) of settled coal reactions occurring in the reactor during routine opera per test. The size of the coal used in the first series was tion. Complete biological oxidation of phenol to carbon -65 +80 mesh, whne that used in the second series was dioxide and water is characterized by the following -200 +375 mesh. The surface areas of the two sizes of equation: coal are 3.2 m2/g and 58.6 m2/g respectively. After fines had been removed from the TFBR by flushing C«H,OH + 702 -6C02 • 3H20. with water at maximum anticipated operating flow rates, the feed solution containing nitrate (Table 11.2) Thus the theoretical oxygen requirement is 238 mg of and seed bacteria was introduced into the system. oxygen per milligram of phenol. For a feed solution Methanol was added to supply the necessary carbon for containing 500 pom of phenol, the oxygen requirement bacterial growth; however, cheaper sources of carbon would be 1190 mg of oxygen per liter, which is could be substituted. Nitrate served as the terminal equivalent to 4.45 liters of air per liter of solution. In electron acceptor for the bacteria in the anaerobic practice, the actual delivery rate would be significantly reactor environment; its presence in the feed stream in excess of the stoichiometric requirements. This high resulted in the evolution of nitrogen gas and a wry air-flow rate is expected to disrupt plug flow charac small amount of COj gas by the bacteria. The effluent teristics in the reactor, contributing to a significant loss was recycled for two to four days, at which time the in stagewise efficiency. This loss will be studied bed started to discharge nitrogen gas. experimentally. The nitrate ion was assayed successfully with the use of a nitrate ion specific electrode. One variable not Denrrrifkation Tests measured was the amount of bacteria attached to the coal (reactor biomass); no satisfactory method has been Low-level aqueous nitrate waste streams (500 to 5000 ppm of NO3" after acid recovery) that may contain small concentrations of alpha emitters are generated at Table 11.2. Compontmi of feed sokrtioa for ike ERDA installations where large volumes of nitric acid anon bjorartor are used during the processing of uranium. Various regulations prevent this waste from being discharged Component Concentration Competition directly into the environment because nitrate con NH,NO, 2.8S g/litei tributes significantly to high rates of eutrophication, KH3PO4 0.002 g/liter and alpha emitters are undesirable contaminants. We are M«S04-7H,0 0.01 it/liter interested in the removal of nitrate from such streams Methanol 0.6S ml/liter via biological processes. Since there are microorganisms Iron solution 0.65 ml/liter 6 $ FeClj/lrter Molybdenum 0.001 ml/liter lgNa Mo0 -2HiO/lit«r that can remove nitrate under anaerobic conditions, we 2 4 solution are attempting to utilize controlled bacterial denitrifi- 64 found that * . measure the total weight or ml—it of g-mdes of NO/ per hour, during the trap** portion of btomass in the reactor. However, we expected that the the lest, the removal rate was approximately 2 e-motes amount of biomass would remain fairly constant once of NO/ per hour. The off-jas composHion was found steady-state operation was achieved. If the layer of to be greater than 99% N, by gas diromaiography: the microorganism on the coal becomes loo thick, the rcmamder was probably COj. abrasive action of the fhudiaed bed wul femove it. The Test with 2tSHuesh cwaL The fhridned-bed test with loose biomass will wash out of the coiiwM under the 200mesh coal extended over a period of about 38 days. appropriate hydraulic conditions. The rmidizaiiou flow rate before bacteria were added lo Test with tS-moh coaL The ftmhzed-bed test wr* the oohunn was about 23 ml/mi* or 9.00028 fps: the 65-mesh coal was operated continuously for 40 days. calculated flutdszation velocity- was 0.00034 fps. The The outlet flow rate to the drain was 12 to 90 mi/mm height of the fhwdoxd bed decreased with time, (90 ml/mm - residence time of 24 mm). An internal mdiciiiiig dnt the bacteria caused the effective size of (recycle) flow rate up to 180 ml/min was used to attain particles lo increase. The agglomeration of particles was fhndization velocity. The maximum velocity at the 3-m. confirmed by microscopic examination. section was 0.0022 fps. The avenge use ratewasaboui3g-mofcsof NO," per During the test, a few particles that appeared to be hour (I to 5 g-moles/hr). The volumetric gas rates, dumps of bacteria were flushed from the column. No when converted to oaks of NO/, agreed weB with the signs of bed material agglomeration were evident during denitriS'katM.-n rates. On the basis of das run. wr the testing period. conclude that small amounts of the bed should be The nitrate input varied from 4 to 36 g-moles of NO/ withdrawn and cleaned periodkaly to minimize par per hour. The nitrate removal varied from I to 4 ticle agglomeration and numtain steady-state operation. 12. Coal Technology Program 121 HYDROCAftBOMZATlON RESEARCH been competed, and a summary report' has been prepared and submitted fcr approval by ERDA - Fossi tydrccarbonization is an important type of coal Energy. liquefaction process that combines low-temperature, high-pressure, and fluidized-bed operation using hydro The experimental dtnlapitK effort progressed gen-rich gas for fluidization. The hydrocarbuuizatwn significantly in two areas. Lucite models of a recirculat process can produce liquid fuels, desJfurized char, ant* ing fluidized-bed concept were tested over a range of substitute natural gas. The relative yields of these conditions. These results contributed to the design of i pr-iucts can be controlled. The char is suitable for use bench-scale hydnxarbonization reactor. A bjgh- without stack-gas treatment in fluidized-bed or travel teroperature experimental system was designed and ing-grate boilers. The liquid fuels include naphtha, light built, and operations were started. This system permits gas oils, and heavy gas oils. Conditions for hydrocarbon- relatively rapid and inexpensive testing of various ization include temperatures up to I500°F and components of the bench-scale hydrocarbonizer at pressures up to ISO aim, but optimum conditions may atmospheric pressure. be significantly milder. The bench-scale hydrocarbontzer is in the design phase. The conceptual design includes the following A thorough review and evaluation of existing informa objectives: (1) coal feed rate of about 10 fc/hr, (2) tion in the literature on hydrocarbonization and pressure vessel design for 350 psigand 1250"F,and(3) carbonization (low hydrogen pressure) processes have gas superficial velocities of up to 2 fps in the reactor. The 4-in. nominal pipe size reactor shown in Fig. 12.1 I. J. M. Holmes. H. D. Cochran, Jr., M.S. Edward, D.S. was designed to permit demonstration of the recirculat Joy, and P. M. Luttz, HrmvemtoMZttkm Restart* fhmt 1 Report: Renew mid giunnririit of HjnMouMbumxstiom Do*. ing fluidized-bed concept on the smallest practical ORNLTtMS3S (Aueart 1975). engineering scale. /WW/WW^»^ 65 66 112 SffAKAHOIS1H»IOUKY 12 J shows somts from UFO. and Fw, 12 J shows the latter stages of an ajlliimi i itww produced by totwme. of the oven! Un&e the UFO. nearly al particles are associated, and tmtinVririnn of foar bask steps: the area between •xlnmiiiiri is relatively char. In the pretreafmeat. solids aincenuatioas. solids separation, of agehmieracmn. smal "bridges" of and posttreatmeat The number of steps reqwhed for a particles covered with an oil solution are given separation depends on the characteristics of the up to fadhxate the transfer of hqnid and partkies stream to be processed and the specifications nx the from one ag^omerate to another. effluent from the separations section- Large variations In the two-phase system of unfitered raw oil- exist, both in the coat bnnetactioa process streams and tetrahydrofuran (UFO-THF). three categories of parti in the degree of separation required. Thus the sohds cles tended to colect at the interface; those that bqmd separation scheme most be tailored to spedfic remained in the oi-rxh phase, those that «inward m processes. However, a number of conditions are com the TMF-rich phase, and Jhost that collected at die mon to al conversion processes: high pressure, high interface. During dissolution by qmnohhv. many smaH temperature, high viscosity, small (colonial) particles, particles tended to agglomerate and float to the top of and bqvd phase JS the more valuable product. These the turn. The larger particles remained near the bottom properties were used in choosing separation schemes for and were well dispersed- Both pyriinv and mineral oi more-detaled study from the many properties available produced less-pronounced agglomeration; however, it m the broad field of sobds-Uquid separations. was significant enough to warrant further studies at The initial experiments, which began January IS. i^ther concentrations. I97S, were limited to pretreatment techniques Farther tests of the agglomerating tendencies of principally mj,f imn it inn and solvent extraction. solvents in wtO-mixed dtptnkm with UFO showed no Studies of methods for concentration (hydrodones) flotation or interface effect However, the aggtomcat- and solids separation (pretoat filtration, centrifugation) ing effect in the presence of toluene was still evident. are planned for th? coming year. Benzene and xylene insotubles were agglomerated simi larly to the toluene insolubles- The large agglomerates Solent Extraction of COED in the latter cases suggested that solvent extraction UnfihoedRawOi followed by settling or centrifugation might be a viable separation scheme. Initial settling rate measurements The Char Oil Energy Development (COED) process were promising, but the economics would depend on has been developed through the pilot-plant stage by the the solvent recovery step and on the degree to which FMC Corporation. There B a need for an improved the inorganic sulfur accumulated in the heavy phase. solids-liquid separation scheme for the COED unaltered Prdiminary studies using the electron microscope indi raw oil (UFO). The relative abilities of several solvents cated that most of the pyritic sulfur was in the heavy to extract solid material from COED UFO are presented phase. in Table 12.1. Results are listed in decreasing order of ability to dissolve the oil phase and to reduce the solids content. Particle Size Dbtribution of The agglomerating tendencies of the iolids in the HCoalSoKds presence of solvents were particularly noted. Figure Panicle size distributions were determined on a sample of filtered solids from the H-Coal process of TaMe 12.1. Sowcnt extraction of am uMamd ofl f ram the COED proem Hydrocarbon Research. Inc. One of the objectives in the initial particle size determination was to evaluate Heavy phuc/UFO available techniques for sizing colloidal particles from Solvent Rank (weight ratio x luo> coal liquefaction streams. H-Coal streams have proved to be among the most difficult to filter; thus they 1 QwnoKne 3 provided a severe lest. The sizes of the particles, which Tetrahydrofuran 2 4 Pyridine i 6 were too small to be measured by either an optical Acetone 4 6 microscope or a Coulter counter, could be determined Toluene 5 14 only by using the electron microscope. One-half of the Xylene 6 19 total number of -«aitides had sizes of less than 0.11 u, n Benzene 19 while one-half of the total sample solids volume was 67 0.001 INCHES 0.0O3 0.004 F*>1U. UFO how Ike COED | IfagMfkatM, lOOOx. composed of partides smaller than 0.98 p. Unfiltered indicated, depending on whether the sulfur was present material from the COED process or from the Solvent principally hi the larger particles or hi the smaller Refined Coal process, developed by Spencer Chemicals, particles. It is also important to determine whether the is not expected to contain as many small particles. mineral matter goes to the heavy phase of a solvent Optical microscope results show a much broader par fractionation. A qualitative evaluation using an optical ticle size distribution for the COED material; the sizes microscope with polarized light indicated that most of of a significant portion of the particles are above 10 ji- the pyritk sulfur was associated with the smaller particles. IdeatiTicatkM of Pyritk Sotfor in Chainteiizatkwi of COED Proem MteiwJi COEDUafltocdOl Chemical an»'y*es vatt made of UFO and filtered oil The size range of particles containing sulfur is from the COED process. Significant observations were important. Different methods of separation would be as follows: fO 20 MICRONS 60 70 -»—1000 X—H- I i H 0.001 INCHES 0.003 F*. I2J. UFOrmMdwCOD MagnKkation, lOOPx. 1. The carbon/hydrogen ratio decreased slightly with 12 J EXPERIMENTAL ENGINEERING SUPPORT filtration, indicating that highly unsaturated hydro Of AMN SITU GASIFKATION PROCESS carbons were removed with the solids. Experimental engineering support of the Lawrence 2. Much of the ash (inorganics) was removed by Uvermore Laboratory (LLL) in-situ gasification project filtration. was initiated by Jie USAEC Division of Applied 3. The amounts of the following elements were Technology (USAEC-DAT). Early efforts were directed significantly reduced by filtration: aluminum, toward high-temperature desulfurization of the boron, calcium, chlorine, potassium, manganese, gasification product stream using molten-salt sodium, and nickel. techniques. Subsequent meetings with LLL and 4. The amounts of the following elements were signifi USAEC-DAT representatives, however, revealed cantly increased by filtration: iron, magnesium, significant information gaps associated with the silicon, strontium, and vanadium. chemical reactions and fluid-flow patterns which will be *9 Therefore, the work, of the of the funded by ERDA - Fatal Energy, has 1 to include more urges* sodas of pyroryas of large coal a deep-bed pyroryzer with a aaMung blocks and pyrolysB in tamt-damicr beds. t ctoany sanabte in situ pyrotysB. A The LLL at situ g&featk* coacept reactorS in. i by 8 ft long deep, thick rosf staaabc fractarcd by u coal; a lajk exphtsnes. After fractunag, oxygen 3 be used to a rhc leaaander of ore be piped to da; top of the seam to feed a flame fn reactor. As the raraace moaes dowa da; length of owe that wal anae dowry down throagh the bed. Within a : arrow band, which aqjudti the tame front, cod wal into da? treatment, and atafrrii aait bait for the baxfc we coadHBted aad gasified. Ahead of das rexctioa i pyroryaer- Boa axial a coal wal be dowry pyrolyxed. Product gases wal penetrate the fractured coal seam aad be recovered stream of the furnace, aad revaporisd; drersforc. gas from the *.4tom- yields any be lagher a a result of tar cracking. Host pyiulysa itaaki have been confined to rhe Construction of the reactor was conadrted in catty beating of aaal. fiady groand samples of bitaaanoas January 1975. bat amalition in me laboraUiry has coals. Expiosne fracturing, however, is Hccry to pro- been delayed. dace hrgc blocks of coai that wal not necessarily Health haards posed by caamugua. ccannaaartsof behave as powders daring pyrotysis. A block pyroryzer coaldcimd haaab were evaluated, aad a foraauKed was constructed for iaitial experiments that utilize 6- description of both dut maw dying safety phaosophy by 6-«. right circular cylinders Kiduned than targe and the operational procedr'es gov*ruing the conduct blocks of subbituaannus coal and instrumented with of work in the Experimental Q^ajawriag Section was thermocouples. Figare 12.4 is a schematic rprescnta- tion of the block pyroryzer. internal memorandum, pendau; fornrafatton of Labora One objective of early experiments on instramented tory-wide safety procedures. ComrKebensive area aad coal Mocks was to determine bulk-heat transfer proper personnel monitoring programs are I ties during pyroiysis. The effects of an adherent ash and HI cooperation with the Health Division. •LOCK TMC«*OCOV*IC CMlt IHl.IT MAC' LCCTMC \.7> rwuwct •I^1 M.ewn ffig. 1X4. Mock pyraiyxw. 13. ActmkJe Oxides, Nitrides, and Carbides 13.1 ECTMAIIONOF ctiromium with iron or nickel (B eJtnponent). Chrom THEKIIOCVNAMK DATA ium alone does not form mtermetaSk compounds with uranium.1 but chromnra with iron or nickel could A method was developed to estimate Gmhs free combine with uranium to form Lavcs-phase com energy factions (fef> from 2S9 to 20D0*K for many pounds. •yy»e« of crystalline compounds. This method was We used Pauling's valence bond theory of metals2'3 as developed wt.mt mobr heat capacities tot many a basis for calculating bond numbers in uranium-transi actimde and Unthaniac carbides a..d nitrides ot interest tion metal and transition metal-transition metal I-**cs- to nuclear technology have not been measured; thus it phase compounds. Relationships given by Pauling is not poonble to calculate the fef values from experi enabled us to determine the d orbital participation in mental data. A paper describing the method was bond formation of the transition metals. We found thai prepared for submission to the Journal of the American the inability of chromium akme to form Laver-phase Cenmmc Society. The abstract follows; compounds with uranium is due to the inability of the "Esfcaanoa of Gate Free Energy Functions." by T. ». chromium d orbitab to take part in bonding to the Lmdrmn Abstmct: A computational Method Insbeen derived extent necessary for compound formation. These calcu for the est.moMi of the Mofar heal capacity contribution lo lations also indicated, however, that chromium would the GM» free energy function (fef) from 29S to 20Q0*K.The method is based on the observed temperature invariancc of combine with iron and. possib!y. with nickel to form certain niios ot" the integrals of these mobr heat capacity Lzves-phase compounds of Ihe type lKH,Cr|_.,)j, contributions. This method has been applied lo the analyse of where M = Fe or Ni. fef data for metal carbides, nitrides, fluorides, bolides, ami Based on these calculations, alloys of uranium, iron, abodes in (hr aystabme state. The estimated fef foi a given compound is more accurate than thai obtainable by other and chromium were prepared by arc-mehing mixtures known estimation techniques and permits a more accurate calctbtittt of ACJ- than is possible from the commonly used approximation A<7* - Art],* - 7" Alffa- 1. C. B Brook, G. I. Williams, and t. M. Smith. / Inst. Meub 83.271(1954). 2. L. Pauline. P- 220 in Theory of Alloy Phases. American 13.2 NITRIDE PHASE EQUILIBRIA Society for Metals, Cleveland. Ohio. 1956- 3. L. Pauline., TheNttw of the Chemical Bond. 3d ed.. Compatibility studies of uranium nitride with chrom CorneU University Press, Ithaca. N.Y.. I960. ium, iron, and nickel indicate that compounds of the ABj type, such as UFelr may form according lo the reaction Table 13.1. UnahMi 70 71 of die respective elements and annealing in flowing the greatest chromium content (S5.4 at. %) had argon for 66 hr at 800'C. The compounds thus formed chromium or iron peaks present in the x-ray spectrum were Snttle in nature and were ground into powder for m addition to peaks caused by the Laves-phase coat- exasiKatioa by x-ray diffraction. The results of the pound. The values of the lattice constants are conustest x-ray analysis are presented in Table 13.1. These results with our analysis of Laves phases in terms of Pauling's confirm that compounds of tbc type U(Fe,Cr, _,)j do metal bonding theory. exist and that the)' haw theClS Lam-phase structure. A report entitled Lmms Ames of Urmman mid The lattice constant increased with additiocal chrom TmnsitkM Aretes was prepared and is being published ium up to a value of 7.1660 ± 0.006S A. The aHoy with asORNL-TM-4915. 14. Studies in Chemical Engineering Science 14.1 MASS TRANSFER RATES IN The mass transfer coefficient was also correlated using OPEN BUBBLE COLUMNS dimensionless groups as follows: Measurements of mass transfer rates in 1.5- and NSh = 1 11 X 10 -'' - /!••*** • A/Jc«° • N& *, (2) 3-in.-diam open bubble columns were continued during 1-3 this report period. Results were extended to where include the effects of liquid viscosity as well as the iV - modified Sherwood number = (K a)D 't/D,2, effects of liquid and gas flow rates on mass t.ansfer Sh L c rates of COj into aqueous solutions. These data, along ^R, = Reynolds number =/)cl/cPt/Mi . 4,5 with selected previous data, were combined to tfSc = Schmidt number = VLIPLP\a ? produce correlations for estimating the effects of gas A'Su = Suratman number =De pL aLliij}, velocity, liquid viscosity, and column diameter on Dc = colunn diameter, liquid-film mass transfer coefficients. D = diff'jsivrty, The overall volumetric mass transfer coefficient was l3 p = liquid density, correlated with gas velocity and liquid viscosity over t both the "bubbly" and "slugging" flow regimes* as aL = interfacial tension. follows: However, there groups include other properties, such 43 5,9 #:Jrfl = 0.C049^• *l^* . (I) as liquid density and interfacizl tension, that were not significantly varied in this study. The dimensionless where correlation is recommended for estimating mass transfer rates for liquid-fiim-cor rolled systems other than the K a = volumetric overall mass transfer coefficient, L carbon dioxide-aqueous glycerol system, hut caution corrected for axial dispersion and end effects, should be used when extrapolating to physical sec". properties widely different from those used in this VQ = superficial gas ve'ocity, cm/sec, study. HL - liquid viscosity. cP. 14.2 PERMEATION-OXIDATION STUDIES 1. A. Gnueret *l. Axial Mixing in en Open Bubble Column, tort VIII: Mast Transfer Effects. ORNL-MrT-193 (1974). The escape of tritium from fusion power reactors by 2. S. C. r^wion et al.. The Effects of Viscosity on Mast permeation through externa' piping or heat exchange Transfer in an Open BubbU Column. ORNMtflT-199 (1974). surfaces can result in unacceptable tritium release rates 3. S. A. Rrber et al. the Effects of UauU Flow Kate and to the environment or severely effect process Viscosity on Mast Transfrr in Open Bubble Columns. ORNL- requirements for tritium blanket recovery systems. A MIT-201 (1974). 4. J. 1. Toman et al.. Axial Mixbg in an Open BubbU secondary containment system wil be more effective if Column. Part VI. Matt transfer Effictt. ORrLWT-175 •he tritium is oxidized to a nonpermeating and (1973) recoverable form, TjO. Oxidation has also been 5. A. S. Y. Ho et J.. Axial Mixing in an Open Buibte proposed as the principal process for recovering the Column, run VII Mas* transfer Effects. ORNL-MT-U3 bulk of the tritium produced in a controlled (1974). 6. Chem. Ttthnoi. Dn>. Annu. Prop. Rep. Mar. 31. 1974, therrxmudear reactor blanket. T.itium would be 0RNI.4966. pp. 55 57. allowed to permeate from the blanket into a helium 72 73 coolant ar*H would then be continuously oxidized to catalyzing the oxidation nonpenneable T20 ana letovticd on moPerw*ar sieves. Hence an efficient oxid ition techniojue could be used i of the J both for containment jf tritium ;*ermearmg external hydrogen isotope penneat ion-oxidation piping and for recovery of tnrjun from a blanket B shown in fig. M.l.BakaBy, the system system. The effectiveness of the oxidation step is of a type 30C i imlf steel permeation tube crucial to either ippbcation. by a 1 ^-m.-dnm tubular vacuus clamber The phenomenon to be investigated in mis study is and furnace, a VacSom roughing pump, a 204iter/sec the oxidation of tritium as it permeates through the Vacton pump, and a variable leak valve. A UTI model first containment or heat exchange surface. An 100 C Pieusion mass analyzer and two nude ion gages anoortant coraderation is chemical foam of the (miStorr and uttramgfc vacuum) are attached to the tritium as it leaves the .meated surface. Low iW-aaa vacuum chnber. The W-dmm concentrations of oxygen are tikcty to be present in permeation twhe has a 32-mi wal thickness and a either die hehwn coolant or reactor containment bated length of approximately 12 m. The tune can be atmosphere (and hsjher concentration of oxygen could easily replaced to pnant testing of other materials. be added). Atomic tritium, permeating a metal barrier, Prior to assembly, the surface of the permeation tube should react rapidly with oxygen in the gas phase. was limtil bv etectroMxmlunc However, the effectiveness of certain metals (i.e., those Six runs were made in the permeationnnidatioc being considered for farion reactor piping and heat system; in each run, 99.7S vol % deuterium was fed to FUMMCC • M.V ELEVATION Fig. 14.1. I SMMUMI far 74 the inside of the stainless steel permeation tube at a Therefore, an experimental study was made of flooding pressure of 20 psg. The temperature of the permeation rates with Goodke packing in an air-water system to tube was maintained at 300. 350, or 400*C. Partial assist in evaluating tins material for use in KALC or pressure data were measured for residual gases until the other gas-bquid sorption processes. system approached steady-state conditions (up to two Figure 14.2 presents flooding curves in the form weeks for each system perturbation). The objectives of suggested by the manufacturer. The air flow at which the first four runs were to test the system for leaks and flooding occurs. Gm%t. is plotted against the ratio of to determine the cot^entrarion of residual gases in the water flow rate to maximum air flow rate, LIGmtx. original vacuum rh—brr as a function of temperature The upper curve represents data collected for a smubu before oxygen was added to the system. In run 5, which system at the ORGDF.1* The three lower curves was nude at 300°C. the variable leak van* was opened represent experimental data obta-wd in our study. The two and one-half turns to permit the huVahagr of 993 &st results we obtained, which are shown on the vol % oxygen, within 24 hr the electron multiplier bottom curve, were considerably lower than those current from the analyzer was fluctuating for all nans predicted by the Goodkie correlation. This implied that numbers. Therefore, with oxygen partial pressure ttus there was a constriction in the column; therefore, the Ugh (or higher), the existing tungsten Wamenti in the entire rohnmi was inverted 180s and retested. The analyzer probe must be replaced with thoriated-nidium experimental data from the inverted column were rnaments. IP run 6 the temperature was maintained at higher and, for HGma% ratios greater than 10. agreed 300°C. and the variable leak vahe was closed to shut well with the correlation; however, at lower l/Gmn% off the supply of oxygen. Within 24 hr the electron ratios, the experimentai curve dropped below the multiplier current was restabiized. After oxygen had correlation. been admitted to the vacuum chamber, the partial The column was then completely repacked with new pressure of deuterium decreased by a factor of 30. Goodloe packing. In replacing the column, extra care Apparently, the permeation rate through the tube was was exercised to ensure that axial compression of the reduced because of the oxide film produced on the type packing was minimized, in accordance with the manu 304 stainless steel surface during run 5. facturer's instructions. The results from this new Deuterium permeation data will be obtained at packing were essentially the same as those obtained for 400*C. and posabry 500*C. using the existing oxidized the inverted column. stainless steel surface with little or no further addition These results indicate that the flooding behavior of of oxygen. Then an orifice will be mstaSed between the Goodloe packing can be difficult to predict, and that vacuum chamber and the ion pump-mass spectrometer considerable care should be taken in preparing the probe o permit a relatively high oxygen concentration column. In designing systems with this type of packing, in the test chamber while stitt limiting the flow of we recommend that the "new packing" flooding curve oxygen to the ion pump and mass spectrometer probe. of Fig. 14.2 be used. At low values of LIGm„. 'his Oxygen partial pressures as high as 0.001 torr in the curve is lower and mor»- conservative i/ian the manufac volume surrounding the permeation tube are desired. In turer's curve. Since it is unlikely that exact packing the immediate future, permeation-oxidation studies will properties can be reproduced, a further allowance for be made with an existing palladium tube and perhaps 30% scatter from the most probable curve is rec with nickel or a nickel alloy. ommended. 14 J FLOODING STUDIES IN COLUMN'S 7. "Goodhue Cotoma ftctaf." galrtin Ho. G-702, Fwtcrf FILLT J WITH GOODLOC PACKING CossawCo..EawM,NJ. I. C. 0- Scott ei *.. CjcnffWMMMf fiutiwan Stmkumu. The Krypton Absorption in Liquid COj (KALC) Prop. Rep. Mm. I. 1974. to An- 31 1974. ORNL-TM-4777 development facility uses Goodloe packing7 •* in a (My 1975). 9. "tacked Cotonn InforfMtion ••fctin." Packed Cotamn 3-in.-diam column, but earlier tests indicated that the Co.E4aon.NI. capacity (flooding rate) of this column was significantly 10. M. J. Sfepftcmon, OftCDP. perxxul conumiiacatiua. less than that predicted by the packing manufacturer.* 1974. < J OML-MTC rs-asa K> I I -rr r—r i i i i 8 6 V OBGOP EXPERIMENTAL OAT* A ORIGINAL COLUMN EXPERIMENTAL ' OAT*. 4 O INVERTED COLUMN EXPERIMENTAL OAT* O INVERTED COLUMN-NEW PACKING EXPERIMENTAL DATA GOOOLOE 02 01 L _i_l_ -I-X e 8 io 2 e io f*l4.2. 14.4 SALT-METAL CONTACTOR DEVELOPMENT assumption mat th* interfaciaJ reaction is instanta EXPERIMENTS WITH A Rf ECHANICALLY neous. Results from trust tests were inconclusive. AGITATED NONDtSTERSINO CONTACTOR An investigation was initiated to determine whether USING WATER AND MERCURY poiarognphy is a viable ^'tentative method for measur ing mass transfer rales in a stirred-interface contactor Mass tntiisfer rates between water and meicury were using mercury and an tqueuus electrolyte *->hition. measured in a mechanically agitated contactor using the Although several electrolyte solutions were investigated, reaction none was found to be entirely wert to mercury. Information in the literature" suggested that an Pb*fH,Ol *7ji\Ht\ -Zn*-[H,01 *Pb[Hg|. Fe3*-Fe** redox couplr (using iron complexed with oxalate ions) may bt suitable as an electrolyte for our which wa* assumed to be instantaneous, irreversible, and application. Further tests wflt be performed to de occurring entirely at the water-mercury interface. termine whether the iron oxalate electrolyte will Data from a series of five experiments performed in produce suitable poiarcframs the watei-mercury contactor were reanalyzed in an attempt to determine whether an apparent change ;n 14.5 PREPARATION OF mass transfer coefficient during the operation of a run SMAIX#ARTICl£ SORKNTS was due to a change in the controlling resistance f«»mass transfer from one phase to the other. Several inconsist Numerous industrial processes i../olve interaction and encies were found between the model and the experi mass transfer between solid parides in f:xed beds and mental data. Runs were made in the water-mercury contactor at an il I. M. KohRoiYaMi S. I Liumne. noimognphy. 1st •*., elevated temperature ("*4C*C) to test the validity of the ImmcWwc*. Ntw York. 194C. 76 gas or liquid streams. Generally, the limiting factor on stainless steel nozzles about 25 u in diameter were the efficiency or effectiveness of the process is the fabricated and tested. The results indicate that nozzles resistance to mass transfer, both between the stationary of 'his size present insurmountable difficulties (i.e.. and mobile phases and within thr stationary or soM plugging}. The snhere-forming process :hat produces the phases. These resistances can be reduced by decreasing most unifo-.mly sized drops involves the use of a the size of the particles in the fixed beds. However, two-fluid nozzle with laminar flow and an imposed smaller particles require a higher pressure to force the vibration in the drive fluid.14 For 10^i-diam drops, the fluid through the bed. The pressure fosse; for particles maximum production rate using this technique is about of a given size can be minimized by using uniformly SjOOOjOOO drops per minute, or about 0.003 cm3/mm. sized sphsres as the bed material. Thus, for a satisfactory total production rate, some Sol-gel processes for preparing uniformly sized metal multiple-cozzle arrangement is necessary. Two designs oxide spheres in the range of several hundred microns in were fabricated and tested, but equal flow through each diameter have been developed and successfully demon nozzle could not be attained. The difficulties en strated at ORNL.1213 The goal of this research is to countered indicated that sufficient throughput and extend the cap Jity of these processes to particle sizes small, uniform product cannot be obtained by using the has than 10 u. two-fluid nozzle and laminar flow. Nozzle design. Although there is apparently no inherent lower limit to the diameter of spheres that cap be formed by the sol-gel processes, several considera 12. S. D. Cfcwton. P. A. HMS. aad L. J. Hath. "Process for tions impose practical lower limits on such diameters. Frepwun Oxide Cd Microspheres (torn Sob," VS. PatMt The most constraining ones are: (1) nozzle fabrication. 3.290.122 (Mr 2*. 1964). (2) sphere production rate, and (3) nozzle plugging. 13. *. A. Haas sad S. D. Ctintoa, Trepanim of TfcorwM Discussions with both glass! towers and metallurgists and Mn«d Oxide Mkrosphcrcs." Ind. fiqt Chem.. frodmct Res. Dertlop 5<3). 236-44 < 19*6). indicated that the practical lower limit for the inside 14. P. A. Haas aad W. J. lackey. Imputed Sat Uniformity diameter of the nozzle is approximately 10 to IS u. of Sol-Gel Spheres by Impotmg e Vtbntkm on the Sal i* Glass nozzles approximately 20 u in diameter and Dispersion Nozzles. ORNL TM-4094 (May 1973). ORNL 0W6 75-874RI 60 j r 1 1—i—i i i i i T 1 »—l—r i ri r- -i 1 1—i—i i i ** I" 1.0. "1.5mm *«'10.000 > I 1 > I '-A -I ' f • I • 1 L _l • • • • ' • 10r0 1000 10000 FLOW RATIO Fif. M-3. Eiffel of *wtflwWsri«rt«aKtrfc few-rate nto 77 Earlier research showed that sol drops with mean uniform drops were formed when a vibration of about I diameters as small as 20 ft can be formed by using kHz was imposed' n the drive fluid above the nozzle. two-fluid nozzles in conjunction with turbulent flow.1 * The effectiveness of sol-gel-prepared metal oxides as The data were correlated by the foflowing equation: column packing material for use in adsorption chroma tography was investigated. The erbium oxide spheres $ (/yiD)= l©30(G/flP * Re' . were used as column packing for sorption chromatogra phy m the characterization of coal-derived liquids. Approximately 30 chromatographic peaks were ob Ds = sol droplet diameter. tained using a •emperature gradient during dution. ID = inside diameter of drr*e-fluid nozzle. Funic paw. Two approaches wil be followed to G = flow rate of drive fluid. achieve the objectives of this research: (1) the effects of F= flow rate of sol. vibrations on the uniformity of spheres formed by using turbulent two-fluid nozzles wil be established; and (2) Re = Reynolds number of the drive fluid. 1 the method described by Flack and McClanahan, * Figure 143 shows a plot of this corrdatioa with whereby the sol feed stream is subjected to ultrasonic Reynolds number as a parameter. The correlation (20-kHz) notations, wil be mvestigated. predicts that drops smaller Aar 10 fi can be obtained with Reynolds numbers greater than 7500 in a 14* ANABATIC COMBUSTION 1.5-mm-ID flow channel. Consequently, we fabricated OFGRAfnTfE and tested two two-fluid nozzles, one with concentric Equipment is being fabricated to determii.» the entry of the fluids and the other with sol entering feasibility of using recycled, cooled flue gas for -on- perpendicular to the drive fluid. The nozzle with the trotting the temperature of a graphite burner. TL^s right-angle entry performed best, and the results from facility, shown schematically in Fig. 14.4, will burn this device are described below. Resuta. Spheres of erbium wide fd 2 to 20 JI in diameter were formed using isoamyi alcohol as the drive IS. P. Alton. Tnpmtkm of SoMM SpWm I 200 leaoMWUKMri Ftunastxm," Mri TtttmoL M. 213-92 fluid in theright-angle two-fluid nozzle. Althcugh the (1971). uniformity of size of the collected drops was not as It. H. P. Fbdc mi K. H. MrChmum. good as desired, microscopic observation indicated that Procat." VS. HUM iMIMI (Anj. 2*. 19*9). IMMHV VtUT Ffc.M.4. 78 solid graphite rods 1 to I ^ in. in diameter and 24 in. cooled, pressurized, and recycled to the burner en long. The burner wB be adtabatk; aB beat wiD be trance. The graphite temperature wii be measured at removed by the flowing gases. The oxygen inlet rate several locations, and the ofT-gas wnl be continuously will be fixed, whereas the recycle rate w9 be varied by analyzed for Oa. CO. and COj. A compute: program, an automatic control system to maintain a preset exit which was written to simulate the system, will analyze temperature for the floe gas. The flue gas wiD be results as they become available. 15. Controlled fbermonuclear Program The controlled thermonuclear reactor (CTR) studies ably by interaction with related programs within the in the Chemical Technology Division are concerned Tlieraionuclear, the Chemistry, and the Metals and with tritium and deuterium handling, processing, and Ceramics Divisions: significant cooperative efforts have containment. Fusion reactors will he required to recycle been made with each of these divisions during the past and purify large quantities of tritium and deuterium year. Funding for the studies comes from the Division unbumed in the plasma and to recover, for future use. of Coatroled Thermonudear Research (DCTR) and die tritium bred m the blanket system. These operations DivisRm of '•hyiical Research (DPR). Conceptual evalu must be performed with minimal release of tritium into ations and more strictly applied studies are funded by the environment under either normal or emergency DCTR, while the more fundamental work is supported operatraj conditions. This relatively new program for by DPR. A related study is abo discussed in Sect, 14.2. support of CTR development is concerned with process problems of future fusion power reactors as well as 15.1 SCOMNGSTUMES OF A TRITIUM problems of near-term experimental and demonstration devices that will be required during the next few HANDLING SYSTEM FOR AN EXPERIMENTAL FUSION POWER REACTOR decades. In many casts, the handling and processing techniques needed for fusion experiment* are the same ORNL has initiated scoping studies for an experi as those to be used in reactor *y«eniv sometimes, mental fusion power reactor (EPR) which is expected however, simpler techniques can be used in experi to begin operation in 1985. These studies are being mental systems. Often the differences associated with mate to better define the purpose and size of the EPR, the scale of needed systems are r.uch 'hat practical the experiments needed, arid the relationships between experimental equipment can be designed with iiMwe the EPR. the test reactor to be built at Princeton by confidence than can equipment for fiB-scare pow;t 1980, and the demonstration reactor tentatively sched systems. uled for operation by 1995. At present, recovery of tritium from the Hsnfcei system appears to be the most dtfftcvlt processing operation. The maximum permeated concentMtioB <;f tritium in the blanket is very low and b set either by The first step in scoping the tritium systems for an limits on environments! release rates or by economic EPR is to estimate the rates of consumption and limits imposed by tritium inventory cost*. The un- throughput. Assuming 20 MeV/fusion. the consumption bemed plasma recycle system wfF be required wttfca rate n 0.135 g of tritium (or 1300 Ci of tritium per the next decade. Although it is less difficult than the MWd). If the EPR operates at an average thermal power blanket recovery system, many of the fAvmt recycle of 150 MW and 1% bum rate, the tritium consumption processing steps must be kwestisaied inntBdiaTdv. tate vrill be about 20 g/day (2dOjOOO Ci/day), and the The scope of the Chemkal Tectuotegy Drririoe Ctrl throuahput wfll be roughly 2 kg/day (20 mCi/day). effort includes conceptual evaluation of u.w&t tystcmt An obvious question it whether the projected con for foskm power reactorsan d nevr-tsam test nuttnm, m sumption of tritium in the EPR van be nippbed from well as experimental studies of tritium hen-iferj fetch- the then-existing ERDA production channels or ninues. The conceptual studies are etjwciafiy awful for whether the EPR wffl be required to breed its own identifying the most urgent weds of she CTK program tritium supply. Unclassified information now indicates and directing the experimental efforts into the most that tritium for two years of operation could be profitable studies. The program sJto benefits consider provided to the DCTR program from normal ERDA 79 80 production channels, assuming that ample notification systems (e.g. regeneraMe getters) and process systems is given and barring unforeseen higher-priority (eg., mercury d.fusion pumps) will be examined. demands.1 Therefore, tritium breeding in the EPR is Pumping speed and hydrogen isotope storage require not expected to be an essential part of the plant ments will affect these considerations. A 1% burn rate operation, and preliminary conceptual designs should and the daily regeneration of vacuum pumps imply a not be constrained to provide breeding capability. storage capacity on the vacuum pumps of 10.000 liters It wiB, however, be desirable to cany out breeding and of hydrogen isotopes. Typical cryosorption pumps recovery experiments in one or more of 'he several associated with this storage capacity would have a total replaceable blanket modules. pumping speed of 10.000,000 liters/sec. If this speed is One purpose of tritium production experiments in the much greater than the EPR Tokamak operation re EPR would be to provide verification in integral quires, then either special cryosorption pump designs experiments of caicuhtional procedures and funda (containing more sieve per unit volume) or lower-speed mental neutronic data used to predict breeding in mercuiy diffuskM pumps will be considered. If cryo fusion reactors. Another purpose would be to demon sorption pumps are used, rapid low-temperature regen strate tritium confinement and recovery techniques by eration will be necessary; experiments are under way at ths small-scale operation of a system with future ORNL to confirm this point and to evaluate proposed applicability. Choices for the experimental modules regeneration procedures. Removal of helium from need not be made until several years after the design is uranium beds will have to be accomplished efflcientiy selected for the basic EPR machine, and the EPR in the EPR to avoid loss of tritium to the helium vent. conceptual design should include a strong emphasis on The required percent recovery v/iB be considerably the primary tritium system. higher in the EPR than in the ORMAK F/BX. Larger quantities cf gas could, on the other hand, make a few operations simpler in the EPR. Removal of tritium and Process Requeanrnts for Primacy Tritium System deuterium from uranium beds may be possible at higher pressures, perhaps at pressures sufficiently high to The high throughput rate of tritium in the EPR makes permit recycling directly to the feed system. recycling within the plant a practical necessity. Assum Isotope separation capability will definitely be re ing that the bum rate is 1% of the throughput rate and quired at the EPR she. However, the throughput and 2 that process losses should be less than 10% of the burn separation needed cannot be specified at present be rate, the recovery fraction must be at least 99.9%. cause they depend largely upon the still-undefined Logistics, economics, and safety considerations dictate characteristics of the systems for injection heating and *' ; Jie inventory in the process system be as low as is fueling of the plasma. The technology of hydrogen l.~ctical. If cryosorption pumps are used, they would isotope separation is well established, and only a limited have to be regenerated frequently, perhaps daily, and amount of development appears to be required for the would contain about one day's throughput of tritium (2 EPR. : kg). Ass* ng that the inventory in the other process Considerations of other details in tritium handling equipment was approximately 2 kg, the total process equipment Jesign will be studied as decisions ate made inventory would be about 4 kg. and as information is generated in other parts of the The principal tritium handling equipment for the EPR EPR design effort. Item of particular interest to the will be vacuum system components. The systems for tritium system design are as follows: the EPR could be similar to the cryoscrption systems in the ORMAK F/BX conceptual design. Before firm 1. primary and secondary vacuum pumping speed decisions are made on the EPR, however, other storage requirements, 2. pube schedule, 1. IMa USAEC policy, chant* to «** DCTR program 3. feed methods (gas fill, injector, and solid fuel), EMM Dofcy k amiuaHi the am. Since EPR operation is 4. number of feed points, aw* UVM am ram in the fatwe. nut poHcy cooM chinas, ••pecialr if ntsarck ani protection functions in dKrcrinc 5. injector capacities and efficiencies. ajencin am Rtocat*4. 6. injection ion composition (D-T matures or separate 2. Itoeeai lone* wmu occur prefcnumittty via anew 4 or injections), nut arterial istker nam by katua* to the mxmdmy cenaaaunmt. 7. purity requirements for feed and injected material. 81 15 2 PREPARATION FOR TESTS metal sorbents appears to be a promising method for OF CRYOSORPTION PUMPING recovering tritium bred in fusion reactor blankets. A FOR FUSION REACTORS study of tritium sorption is continuing with experi ments that involve batch contacting of tritiated liquid Cryosorption pumping appears to be the most promis potassium and potential metal sorbents. The metals ing method for achieving the low operating pressures tested to date have been yttrium, zirconium, uranium, required by fusion reactors and for efficiently recover and titanium. As reported previously, none of the ing tritium and deuterium. After each heating cycle. metals sorbed any detectable quantities of tritium from Tokamaks require large pumps for evacuation of the molten potassium during contact times of up to four plasma liner so that unbumed hydrogen isotopes may days. An unpenctrV-ile oxide barrier apparently forms be recovered and recycled. on the surface of the metal and closes the interior to The cryosorption pumping technique utilizes the hydrogen permeation. Coating different zirconium sor condensation of gases on molecular sieves that have bents with nickel, vanadium, and iron did not improve been cooled to liquid-helium temperatures (4-5°K). the transport of tritium. Because such pumps need no lubricants or operating The batch contact of possible sorbent materials with fluids within the vacuum chamber, they are dean, tritiated potassium will continue; however, preparations vibration free, and unaffected by magnetic fields. The are also being made to test the effectiveness of potential objectives of this program will be to investigate the sorbent materials in tritiated lithium. The relative operating characteristics of such devices. Investigations ineffectiveness of some materials as sorbents or sorbent will determine pumping speeds and capacities of se coatings may improve in lithium, where surface oxides lected gases at specified pressures and desorpttve regen can be more effectively reduced. eration requirements. Pumped gases are expected to include the isotopes of hydrogen and hydrogen-helium 1S.4 TRITIUM SORPTION IN UTHIUM-ALUMINUM mixtures. AND LITHIUM BISMUTH ALLOYS Basically, the pumping system includes a cryosorption pump, a 6-in.-diam vacuum chamber, millitorr and Utriiurn-ahnninum alloys were proposed for low- ultrahigh-vacuum gages, a roughing pump, and a 20- tritium-inventory CTR blankets, and uthrum-bismuth liter/sec noble-ion pump. A mass analyzer probe and alloys have been suggested as solvents for extracting tri constant-leak valve are also attached io the vacuum tium from molten-salt blankets. However, insufficient chamber. information was available to evaluate the usefulness of Pumping tests will be preceded by a bakeuut period either system. An experimental effort was made to ob during which the outgassed materials are removed by tain some of the necessary data relative to tritium uptake the roughing system. The cryosorption pump will then throughout the temperature and pressure range of be cooled to liquid-helium temperatures, and sub 16.1 IODINE SORPTION ON CHARCOAL organic constituents) vs heat output (air flow and IGNITION AND DESORPTION conduction losses). In our apparatus, ignition occurs when the heat input is approximately 15 cal min"' (g Nuclear resctoi installations use large quantities of charcoal)'1. Since the decay heat in recent experiments especially impregnated charcoal for cleanup of radio is only 1 cal min'1 (g charcoal)'1, the importance of active iodine duiing normal operation. A remote pos oxidation heat is apparent. The presence of moisture sibility exists that charcoal adsorbers would be required reprices slightly the oxidation ute. partly by diluting to retain larger quantities of radioactive iodine than the oxygen in the air. The experiment* with MSA- normally adsorbed if certain postulated accidents oc 85851 charcoal show a large reduction in oxidation curred for some reactors. Our experimental prog-am is heat release with moist air. but much of the reduction being conducted to determine the effects that such should probably be attributed to the bumoff of active loading (as simulated in the laboratory) would have on sites in the charcoal during the longer time required to the retention of iodine and whether the resulting decay raise the cnarcoal bed to the ignition temperature with heat would ultimately Ie*d to ignition of the charcoal. the lower radioactivity level used in run 8. In contrast Our experimental method is to load highly radioactive to the experiments conducted at 3.8-fpm air velocity, 130 12 on a well-insulated charcoal bed 1 in. in diameter the maximum temperature during each of the experi and 2 in. deep. Air is flowed at 33 fpm and 70°C to ments that ignited at 0.7-fpm velocity reached a provide adequate cooling for 2 to 6 hr. while sequen maximum followed by a slow decrease. The calculated tially operated collection traps measure radioactive oxidation heat release rate decreased during this period, iodine desorbed from the end of the bed. The air indicating a bumoff of active sites or a combustion coolant velocity is then reduced to 3.8 fpm (25°C poisoning effect. The CHART computer program as reference) for 3 hr and further reduced 'o 0.7 fpm modified to include oxidation heat was shown to (25°C) unless ignition has already occurred. correctly calculate charcoal bed temperatures.1 Previous experiments with nearly dry air showed that The rate of oxidation heat release varied widely the heat from decaying iodine can result in ignition of among the charcoals, with the impregnants causing charcoal and that the amount of iodine desorbed before much of the difference. The relatively high potassium ignition is usually insignificant. Details of these experi content of MSA-85851 and of GX-176 tends to ments have been reported.' promote oxidation: triethylenediamine (TEDA) in GX- Our test parameters were extended to include higher- 176 oxidizes at temperatures above I50°C. Run 10 mcisture-content air as well as charcoal that has been in used Witco grade 42 charcoal which was removed from service and accumulated quantities of adsorbed atmos the HFIR air cleaning system after four years of service pheric contaminants. The principal results of the recent and which contained approximately 130 mg of ad experiments are summarized in Table 16.1. sorbed atmospheric contaminants per gram of charcoal. The attainment of ignition in our experiments Apparently this material oxidized readily, raising the depends upon the simple heat balance of heat input charcoal bed temperature sufficiently to cause ignition (radioactive decay plus oxidation of charcoal and of the base charcoal. Unused charcoal from the same purchase lot did not release measurable oxidation heat in run 9, and the temperature reached a plateau of I. R. A. Lorenzo. W. J. Martin.and H. Naaao. "The Behavior IStfC. of tfigMy Radioactne lodme on Charcoal,'' Proceedings of the 13th AEC Air Cleaning Conference Held in San Francisco. The movement of radioactive iodine within the test August 1J J5. J 974. beds was monitored by an ion chamb.-r with a 82 S3 Table 14.1- Wttco Grade 42* HSA-t>«5l" CX-176* RaailO Ran 7 (from HFIR) ,3Vcs* 1130-970 445-240 650-4S0 535-270 415-260 •10-590 Lowest m waocirjr, fpaa at 25*C 3-» a7 0.7 0.7 0.7 3J tgnjtioa ceaapentauc. *C 300 Not BwOSHCd 36* Not reached 2S3 292 Mni—• iii«iinic u kiaaji 575 3(7 431 IK 473 530 wJocit*.*C Water vapor partial pressor, totr 4 100 3 95 110 4 Oxataboa hat ictcaac ntc.r cat MM'1 (gdMRsai)-' A:200*C 0.36 0.1 -0.02 Notmeasared ft 1-2 At 300* C IS 5 1.3 Nottseasared 40 It Adsorption codTicicat,r f l(g charcoal)-'atal,1 Atiotrc 4.0 x 105 1.1 x 10s 1.0 x 10* 1.0 x 10s 0.33 x I05 lJU x 10s At200*C 2.3 x 10* 2S x 10* 1.5 x 103 1J x 10* 0.4 x :o* lix 10* Fraction ovsorbed, ppm fa annul pawn -2 1.6 -10,000 0.5 1600 3.4 Particwai: iodaat 17 1.2 IS 0.5 21 10.2 Peaetratiat initial >3.4 6S >6.4 63 94*I280* >5.6 Total >22 71 ~\0M0 64 2950 >19 "MSA-tSt5l B a cocoaat-baae charcoal impregnated with approximately 4% (KI • I]). Witco Grade 42 is a petroteaaa-basc charcoal anaRcnatcd with ippiuJumaMly 4% KI. GX-176 is a ruiuwt baar charcoal iaapmiuud with 1% KI, 1% tiw thjh wihaiaw (TEDA), and a proprietary flameittaraant . •One carie of IMI prodnces a — »im—i beta radiation intensity of -5 x 10s rads/hr in the first V«»- bed segment i aajformimattniadietwnmfenBtyof 1.3x 10* ndt/br.The half-life of,3,1 is 12.3 hr. The heat rekase rate and adsorption coefficient show a log rate (ooeflkieat) n I IT <*K) correlation. Some of the I extnpotated beyond the range of experimental data for comparison. *Tbe 9 collimator that scanned the depth of the bed in %-in. concealment by '3' mXe, an '3'I daughter that accum increments. From the observed movement within the ulates in the recirculating system. Reexamination of bed, we calculated the iodine partial pressure and the available data from these runs indicates that highly corresponding linear adsorption coefficient as shown in penetrating iodine was present but to a lesser extent. Table 16.1. The observed differences among charcoals During run 10, which was made with the charcoal from were small; the fjreatest difference was between runs 9 the HFIR, the release rate of highly penetrating iodine and 10, which illustrated the dele'erious effect of was practically the same; however, a much larger extended service life. amount of CH3l-like materia] was released at a continu Of great interest in this program is the release of ous fractional rate of 90 X 10 "* hr"'. radioactive iodine from the end of the test bed (Table 16.1). The large releases of elemental iodine occurred Attempts to identify the chemical forms of the highly wh-.n heds were operated at high temperature for long penetrating iodine have not yet been successful, but periods of time. The amount of particulate iodine various significant characteristics have been observed. released was small, even during ignition. The amount of The partition coefficient in water (condensate) at 0°C is 3 3 penetrating iodine (chemical forms *uch as CH3I that <10 g I cm' of water/g I cm" of air. and the material are not as easily adsorbed as li) was small in the did not cold-trap from air at dry-ice temperature or low-moisture runs. With a higher moisture content in from helium ai liquid-nitrogen temperature. A silver- runs 8 and 9, we discovered that the iodine released exchanged type I3X molecular sieve collects the mate during these runs was very poorly adsorbed and was rial much more efficiently than any of the common rcw«»ev continuously at a fractional rate of approxi types of KI, Kl3, and TEDA-impregnated charcoals. mately 7 X 10"* hr~'. This highly penetrating iodine The high-temperature collection on a silver-exchanged was not detected during the low-moisture runs because molecular sieve shows promise for efficient collection, of shorter operating times, smaller collection traps, and especially when preceded by an oxidizing catalyst. 84 16.2 REACTION OF ORGANIC IODIDES n-butyl nitrate was converted into COj (40 to 45%). WITH HYPERAZEOTROPIC NITRIC ACID into butyric acid (40%), and the remainder into unidentified species. When the buty! nitrate was added The purpose of this study is to determine the ultimate in ahquots to the boiling pot. about 9% was oxidized to fate of organic materials in nitric acid systems. Com butyric acid. 11% to acetic aciJ, and 30% to propionic plete recycling of all processing streams involves the acid (Table 162). Most oxidation occurred within the possibility of recycling traces of organks that can cause first few minutes. Aliphatic acids were rather stable; subsequent difficulties in separating fission products, acetic acid was unattacked by boiling in 20 M HN03 particularly radioiodine. The study is oriented toward for 4 hr, and only 20% -A the n-butyric acid was the planned LMFBR processing scheme, which includes attacked. (The carbon from that 20% remained in the the removal of iodine by 20 M HNO (lodox proc } reaction vessel in some as-yet unidentified species.) ess)2"5 The effects of solvent and diluent degradation on The factor for separating methyl nitrate from nitric solvent extraction systems have been widely investi acid solutions by fractional distillation was found to be gated." The deleterious effect of traces of organics on about IS. Distillation is not practical for separating iodine separation has been less widely studied, but is longer-chain organic nitrates from the acid. We have we!! authenticated.1'* approached 100% removal of 0.1 M acetic acid, the most refractory of the known short-chain compounds. We studied the reaction of hyperazeoiropk nitric acid with short-chain aliphatic iodides, nitrates, and acids: these were added to nitric acid, saturated with iodic acid, and refluxed with air sparging to remove volatile 2. Chrm. TecfrnoL Div. Annu. Progr. Rep. Mar. SI, 1972, products. The off-gas was passed through cold traps and ORNL-4794; Ibid.. ORNL-4682. pp -i\ -62 (1971). 3. Staffs of the Chemical Technology and the Metab and a gas analysis train. Contents of the traps and the Ceramics Divisions, LVFSR Furl Cycle Studies Progress Report reaction vessel were analyzed for organic materials by No. 31. ORNl.TM-3807. p. 11 18 < April 1972). gas-liquid chromatography and for total carbon. The 4. J. C. MaBen and T. O. Tiffany. J. Inorg. Nud. Chem. 37. analyses allowed us to identify compounds and to close 127 32(1975). the material balance for carbon. 5. R. H. Rainey and J. C. Maikn, / Chem. tug. Date 19. 262-63(1974). Strong nitric acid converts aliphatic iodides to the 6. "Symposium on Solvent Extraction Chemistry. Gitlsn- corresponding nitrates.9 With methyl iodide in 20 M burg. Tenn.. Oct. 23-26. 1962." Nucl. Sci. Ing. 16. 381 -455 HN03, the conversion was 100% within the limits of (5963); 17, 234-308. 557-650 (1%3). analytical accuracy. Only traces of CO2 and CO were 7. Health Physics and Medical Division, UKAEA Research found. Except for the acids, longer-chain aliphatic Group, Harwell. UK. AERF-M-12II (May 1963). 8. W. A. Rodger and S. L. Reese. Reactor and Fuel Processing compounds suffered considerable attack. Ethyl nitrate Technd. 12(2). 173(1969). was converted into COj to the extent of 70 to 80%, 9. N. V. Sveuakov et al., /. Org. Oiem. (USSR) 4,1829-33 with acetic acid accounting for roort of the remainder; (1968). TsMe 16.2. Oxidation products of etpMici m 20 M HNOj Compounds found in products (% of total C added) Starting Organic %carbon compound Unchanged CO, CO OhVf adds accounted (or Methyl nitrate -100 Trace Trace -100 Ethyl nitrate 73 17, acetic 90J n-tBtyl nrtnte 0 41 0 11, acetic; 17.1 FISSION PRODUCT RELEASE during font periods of normal reactor operation. While FROM LWR FUEL additional information at even higher temperatures (1500 to 25O0*C) is of interest, no experiments at this This program was initiated in FY 1975 to provide a level are currently planned. more detailed understanding of fission product behavior The initial effort in this program included a literature under LWR accident conditions. Safety analyses have survey of existing data, previously used experimental emphasized the need for improved information in order techniques, and avauabh methods for characterizing the to evaluate more accurately the consequences of radio chemical and physical forms of the fission products activity release and to ensure conformance with eOab under test conditions A work plan summarizing the lished guidelines concerning radiological dose to indi state of the art and outlining the proposed experimental viduals near a power reactor. Determination of the progiam was prepared and submitted to the Nuclear chemical and physical forms of the released fission Regulatory Commission (NRC) in draft form for products will be given particular attention. review. The revised work plan, incorporating comments Two types of accidents - both involving steam i.iade during t*e review, was transmitted to the Office atmospheres - are of interest in this study: spent-fuel of Nuclear Regulatory Resets (ONRR)-NRC on transportation accidents might result in rod failures in March 7,19' '.. the 500 700°C temperature range, and m-reactor In preparation for the experimental studies, a con loss-of-coolant accidents might cause rod failures (and taminated hot cell was cleaned and repainted, and the fission product release) a: higher temperatures (up to necessary equipment was insulted. A schematic diagram 1500°C). At these temperatures, the source of released of the apparatus Is shewn in Fig. 17.1. All component: fission products is almost entirely that inventory of the experimental system were checked for proper accumulated in the pellet-clad gap region of the fuei rod operation and found to be satisfactory. A series of "**L C*G ?«- I2«4« STEAM GEl»C»»TOf» TMCKIML CONDUCTIVITY LM»£B »CTt» «0TA«ETC*| Kv\«i*. T;^7^LA i I ' J I I •LJ VACUUM e*rr,i» COM0CMC* l-T««C) to«ci 3WM »AV CTMMKTC* f'%. 17.1. Apparatiu for studying fnwon product ideate from irradiated LWR fad rods. 86 87 control tests will be conducted to ensure accurate stimulant, and parallel underwater and undersodium calibration and interpretation of the characterization efforts to study the behavior of. and possible attenua techniques, such as deposition In a thermal gradient, tion effects within, the vapor bubble itseif. particle size classification in a cascade impartor. chemi The release experiments will make use of several cal analysis of the steam condensate, and gamma-ray different vessels of various sizes. The primary fuel spectrometry of all samples. Electron spectroscopy and aerosol vessel, which has been designated as CRI-III. b x-ray diffraction will be utilized for compound identifi being fabricated. Because fuel aerosob must be second cation where appropriate. Both irradiated and unirra arily contained and the tests must "w conducted in a diated (with fission products implanted) fuel specimens hot eel. CRI-III is necessarily relatively small (ix., 88 OPNL-OWG 75-2T9RI 100 Tl r=300K 5; — 4 - - — U- VOL-7* tO . ._ . i f-- FLOOR/VOL = t.8 « 102 I 2 H"~ \«KVLU SURFACE/VOL = U81 x K)"' 10' O2 2 5 103 KJ» TME(sec) F«.I7.2. Effect of U}0, bvHAA-JS. Toward this end. arrangements were made to use the weight of the fin* successful shot. Therefore, existing equipment at the Arnold Engineering Develop additional energy was wheduled for the final trial, ment Center (AtDC) for scoping tests on fuel vaporiza which was made with a different fuel loading. This lest. tion. Their von Karman facility was reactivated, and the No. 6. was rreich more successful, since about 10% of required changes were made to adapt the capacitor the pellet stack was vaporized. During this test, some banks for our project. rather significant observations concerning aerosol The first three of a planned series of four groups of behavior were made, including the measurement of tests were completed. These t«sts were designed to both agglomerated and primary particle sizes. study the effects of preheat temperature, capacitor Five additional fuel vaporization tests were conducted power and voltage, and system resistance to rupture by at AEDC. Descriptions of fuel assemblies used for all of pressure buildup. While not all of the tests were the AEDC tests of interest, along with the data successful with regard to vaporizing a significant collected for each test, are given in Table 17.1. (Note amount of fuel, sufficient information war obtained to that all conclusions reported here are preliminary and give reasonab!? assurance of the viability of the CDV subject to change after further assessment.) technique for energy deposition and subsequent fuel Test 6 was housed in a quartz containment sleeve of vaporization. 2-mm wall thickness. The setup gave a good aerosol The three scries of tests were expected to emphasize, yield which we hoped lo increase in tests 7 and 8 by successively, the effects of (I) U02 preheat tempera using quartz containment of 4-mm wall thickness. ture. (2) capacitor energy and voltage, and (3) sleeve These tests differed from one another only in that lesl resistance to rupture by pressure generation. With 7 employed 40 wt % UO, pellets along with micro somewhat surprising ease, the first series performed spheres, whereas tesl 8 utilized only UOj microspheres gave encouraging results: and a significant yield (--2% of as fuel simulant. In each case, disassembly was observed the fuel pellet weight) of submkron UOj particles was within about the same lime and energy input range as in obtained, although the energy deposition in the fuel test 6. but the new tests appeared lo yield less aerosol. was relatively inefficient. The AEDT series included preliminary tests to deter In the second series, the initial tests gave highly mine what effectfs) the cladding material might have efficient energy deposition (75 to 80%) but. disappoint during fuel vaporization. For this purpose we added ingly, no disassembly or aerosol. After some considera stainless steel to the UOj microspheres in test 9. |r this tion we concluded that, in addition lo enhanced case, the energy input before disassembly was . jre thermal conductivity due to the type of fuel, the than twice the highest input experience previously, and samples were probably loo massive, being about twice the aerosol yield appeared lo exceed that obtained in ,»,*•.. VS*»*V I' i ' Table J7.1. Teal iimdllton» and preliminary reaulli for AUX' fuel vaporiiaflon experlmenu CapircUttr bank Sleeve Deposited Dimaaembly Shot KO) MUM tnetyy Voltage II) energy lime Hewitt number Material IkJ) IkV) Imml (mm) (kJ) (nwecl 2 47 2 Aljl).i 9 12 <• 9.1 -I.I About 200 my ol UOj vaporized SA 42 ^ Quurmi? liquid expelled b H4 28 Quurti II 15 ill -9.7* «IH>** -0.7 -1 in 2 K vaporised 7 71 2.6 Qu.tr 1/ 10 IH 15.2 9.2 0.65 -0,5 y vuporixed a 71 2b Quart* Id IH 24,6 10.7 O.H -0.5 tl vaporlited \* •»! 2.6 Quail z 10 IN 16.5 22,';* 1.5 -1 to 2 t vaporlted 10 51 2.2 Quart* b ID 14.6 11.7 I.H -0.5 |i vaporized it 71 J.6 Omni H 37 25 3 12.3 1 5 -0.1 n vaporized "hffkierwy of poaldbauembty energy drpotltum U unceiluln ^Contained 2.6 g ol" alainlcu iteel flllnt» nixed with NOj mivrotphere*. 90 test 6. The observed improvement is thought to be due the front 60 mm of the assembly. The thickness of the to a lower resisrjvity-teinperaiure coefficient resulting quartz containment was reduced to 1.5 mm for the last from the presence of the stainless sted. This would tend 20 nun of length at the iow-voltagc end of Jte to fatten the radbl temperature profile and signifi assembly. The intent was to cause the sMn-waned area cantly reduce the power density along the center line of to rupture first, alowiag the current at the raptured the fuel during the electrical discharge. end of the assembly to be carried by a low-impedance Test 10 represented an attempt to reduce the healing are. The results were disappointing in that complete power level without significantly decreasing the voltage disassembly apparently occurred after about the same and the stc~d energy in the capacitor tank. Hence, to energy input as in test 10. and with a lower aerosol increase tl* electrical resistance of the assembly, a yield. longer and nnilW-dnir.»i«.r fuel assembly was em Additional tests at AEDC wul be conducted with ployed. Although a reduction K total power kvd was various material and voltage combinations in an effort observed, ore aerosol production appealed to be about to further impion die efficiency of the CDV process. the same as that observed during test S. Design and construction of the comparable ORNL The sample of fuel smmlant used ir test II was high-ioltage facSty were initiated. contained in a heavy \ 14-men-thick) quartz tube along 18. Nuclear Regulatory Commission Programs 181 DEVELOrMENTOF-ASLOWAS l%2 SAFETY REVIEW OF NUCLEAR FAOLniES PRACTICABLE" (ALAP) GUIDES FOR THE ffUCLEAR FUEL CYOJE The Chemical Technology Division, with support from the General Engoeering. Health Physics, and Engineering survey studies were conducted to provide Instrumentation and Controls Divisions, is piuvidmg the OtTice of Standards Development of the VS. technical assrstamc to the NRC. Drrisisn of Materials Nuclear Regulator/ Commission (NRC) with the tech and Fuel Cycle Facility Licensing, in assessing the nical information required to formulate appropriate safety of fud cycle faculties and hi preparing generic ALAP guidftiurs for the release of radioactive materials reports on these faculties. from al segments of the nuckar fuel cycle. Three draft During this report period, we participated in the reports are expected to be submitted to the NRC in review of safety analysis reports accompanying license July and August 1975. as follows: Correlation of applications for a construction and opening permit to Raammxthe Waste Treatment Costt and the Environ- mental Impact of Waste Effluents m the Nuclear Fuel Crrte for Use im Esmbtidmmi "As Low As hmctkahk" I. The p»c»iu» icpom •» tkn scries at: B. C. Finney. R. E. Guides Conversion of Yellow Cake to Uranism MMKO. R.C. PiMmin. F.G. Kim. ant J. P. Wmmnmoom. Hexaftuoeide: Reprocessing of High-Temperature Cms- Conrlmttom of Rsdkmctne Waste Tnmomnt Com and die Emm mm mad Impact of Waste Effmmts m die Smdear Fmtt Cooled Remctor Fuel Containing Urmmm-233 and Crete for Use m Fiiabtimmg "As IJOW AS nmrlicame " Gmdes Thwmm: and Fabhcmtkm of High-Tcmperatmre Gas- .Smctemr Fuel Reptocrssmx. 0RNL-T»M9ni (|fay 1975): W. H. Cooled Reactor Fud Containing lfrmnmm-2'. 3 and ftcm*. RE. HHM». R.C. BuMwii. B.C. Fianey. R-B. Thorium. These reports are expected to be issued to the UMBUCT. anu J. P. wuuenuoou. Coneta&on of nMRMrMf nuckar industry, governmental agencies, and die public Waste Treatment Costs end the Enrwonmemat Impact of mole Effmmts m the \miear Fmtt Crete for Use m Estamtahmw "As for comment in FY 1976 after they have been reviewed Low As rmctKaUe" Guides - FuaeicaHom of Ugkl-Water by the NRC and revised at ORNL. Four previous Kewelor Fmi from Enriched Urmwmm Dioxide. ORNL-TM4902 reports (one o( which contains two volumes) in this (May I97S>: M. R. Sean. R. E. Rbnco. R. C. Pawl—. G. S. series' were prepared fix issue as ORNL TM documents MR. A. D. Ryan, ana I. P. WtOntspoom. Correlation of Radio in May 1975. The engineering reports present incre acme Waste Treatment Costs and the Emmmmmtal Impart of Waste Effluents m tne Smciear Fuel Cycle for Use in Esseahsh- mental capital and operating costs for changes and MJT "As Ixnr As Prm iktHe" Gnnlti Mmmt of Uranium Ores. additions to systems and develop corresponding source ORNL-TM-4903. «ol. I (May 1975): A. D. Ryan and R. E. terms for radioactive emissions and noxious effluents. Maaco. CorreUhun of RaJuachwe Waste Treatment Costs and These systems cover the range from present practice to the Enrwonmenm Impact of Waste Effluents m the ttucteme the foreseeable limits of available technology on the Fuel Cycle for Use m Estahhshmx "As lorn As FtacncaHe" Guides Appendix A. Frcfsratwm of Cost Estimates for basis of expected typical and normal operation orer the Volume I. Mmune of Urmwmm Ores. ORNL-TM 4903. rai. 2 life of the facilities. Estimates of errors inherent in the rtbr 1975): W. S Gromter. R. E. Rtanco. R. C. DOmmmx B. C. development of these data are stipulated. The environ rmncy, A. H. KiMicy. and J. P. Witucrsuooii. Cmtttation of mental pari of each study describes the behavior of Rmwoaclhe Waste Treatment Costs and the Eniiroomtntal radionuclides and other noxious materials in the emi- Impact of Waste Effluents m die Unclear Fuel Cycle for Use in Estahnshmt "As Ixrw AS FrarncaMe" Guides - Fabrication of ronmenl and quantitaliwly estimates the radioactive lj%htWater Reactor Fuels Contaimng Fmtonmm. ORNL-TM- exposure to the public. 4904 (May 1975). 91 92 perform major raodifications at the Nvdear Fad mast be reviewed md approved by me Transportation Services. (NFS) Wen Vaky Fad Reprocessing FUat awl Sranch of the NRC. The NRC review covers aV areas of to operate the modified NFS plant, aad optutmg cask design and analysis. On occasion, the Transporta permits for the AHed General Nadear Services Banv- tion Branch whi reonest that ORNL renew certain parts wd Fad Reprocessmf Pram awl the AKed Genera? of these safety aaatyas reports for packaging and Nvdear Services BamweM Fad Receivmg awl Storage tr in—it the renrttmg evahmtioa to them. Deing this System. Specific areas of review were: (I) ventaalioa report penod. we made a review of the presnwe refaef ml off-gas treatment. (2) iwhoiodrnt coatrai. (3) device on the CE IF 300 spent-fad napping cask. In mstnmeatatioa ami controls. (4| no/ml- and soha- addition, we compfcicd a detaied cmnpater analysis of waste treatment. (Si process. (6) rawiolanjcal protec the awdam capabimies of concrete aad a Chenvtree tion. (7) accidents, and (8) normal and emergency compoand* for a given sonrce of nentrons and ramwa utility support systems. rays. ISJ SAFETY REVIEW OF nUflSTORT CASKS The design of each Japping container expected to transport significant qnanutses of radioactive materia.' m, Ctmtat Vjaky. N.Y. I99I7. 19. Diffusion of Adsorbed Species in Porous Media TV Mtflft pat of IHS •aliriflaajoftfg, im of ilroqajy Daffasioa of cessa* thrwagb graphite n—anatati of reactors is aa exaaaak. sjace aaoH of da: i activity at HTGH osobag aacaats' resails frnaj i isotopes dm leak oat of coated had portieres2 - »throaah graphites iiiiiaaaaf da?fad regjuau. tcraperar*r»!s raagjag rroai 600 to I000"C. vArrcsa oenaai coahf exist at least adtidty as a aartaak vapor. J*rfy as a nobde ad»sbed ssrfacev One objective is to approxaajaie vapor-phase to adsorbed-phaw iraaspun ratic. Another objectm- concerns the dndopajeat of a pheaommulopcat modii tiiaf wdl aid ta the aaatysB of roths from varioas HTCR sarwdb'xc ptvymmi. Cam* asajmiutt atodes have beat foaad to be stroagty depeadrat oa tar type of Some ccaapautrve rcsarts are show* m F^. 19.1 Cane I on die figsre prcaeats data for a low-fat penajeabdrty graphne resataag from fbrfrvaJdabyds g_ -X*t/4Dt i of a base stack ajaKrv. < ItavAcr-Sideetey C_«x./|« ^^ f (2) t). Carve II preseats dau for a pmrnakmy graphite fGreat Lakes H-327, The prerxpoaeMajf term is stractaol graphite in the Fort St. Vraat HTCR. caC^O.fVC to The tratsieM sttaatioa atiford at a portioii of aaatyses derives froai the drffeseauaJ m to* E* (2) bye. iby itra- AM profihs dwedy JM be aa extremely I. H J. or J. O. Mb. F. F. Djiw. r.j. and coSect oajaatiraB of n| I, • I dast. We prefer to section by a mc*r 'xx /rear. ftp. Onr. J/. of die specaajem (ssmg keroanrc as a csttiajg 1972.0RNL49II ftfafeft 1*74). 2- R. •>. EIVM In sBv M. T. MMpM* JMHYiRvrvVaW Qncftp >> and aaeybaj «*\ the fraction of total activity Hon #jf/fiwiPPi fVodbr f TlVM^aWf M CaMVw npflnfiry nvny as a ftmctioa of friadaag amtaace. The ftmHadaiian /taraY OKML4W9fJaat i«74V I enasatioRai J. M. T. MMBM. H. J. avHwa'aab.—O. L. Towas. JTWMMT Nrtktet Dmrtmg fjmai—Mriim 4 93 94 oan. M6 •%-MZTWI A plot of das f—Kimm appeari as aje r*Ocwr*eon OB the sarface iaMaRy. dnTaaed arto the apecanea; die F» 19.1 to the right hand side of Eq. (I) mi then lo cxaauae 4. R. $. Ruaatft. Thr Effect of Flow on iff apfdkabaaty of die imegrased rearits. line. rt n die m Ammtmg Rawanriwi Jjnnrin m m Ana thasaJ final a CfC» Raaan. RDfa7N237S. 2T: 12479 I972>. «. R. R. Eaaa Rl. I. L. jadA.r. 5. Cam. Tata. Dw. lawiaal Cu—aannriia. R. t. Cm nrnmrnm m MRRf II, IH to R. ». Evaa>m aaoMhrf 1974). 0RML-4JR9. p. 12. Faj. 13 (May 19m 95 mt. i«*F«.i*i Cm »H-327> 12*0 70 0.093 04H 1.2 x :o"-1 7.9 x 10"* 34* x 10' -J I1J3 x 10"V -1 1 2-10 x 10' I.M x 10" i2J7x 10" trapping fur pbte-oul ) rate, ami AC, represents a ""back both immobie and mobae fractious: so the total pressure" tens. Cuas*krai»>ns of long-term results concentration was computed va suggest that the biter nneVi te neghgmk. Accordmgty. the uriegratiun was carried out using onh thefirst term . kt kr TV result for Cp was merry tq. (2) imritiphed by C^.t) = eCpe * (k (' Cje di'. <4e) c *' /« Cjtx.n * '"2 *,:'*IV*i-»r|' "''' «*«- •» r> e*I,,Terfc(«*Tp| (46) C^O./') e -2*fV»V|l erfcfxH fercM boundary condrttous.' However, a rather poign ant feature of performing long term experiments with • »(x/2»V«;**i- H-327 graphites should be noted. After a rctativery r»V& short time, the value of r omwhehm the value of * Cowudemtntary error functions Use erfc (r t v) fade Ttte cunespoudtng fraction-renaming f ipuimm for away at r > 2.0. OUTUSMH information from discrete « oar sectiiinmjL tjroccdnre B is km. and the only information that can be in ihts esse is a value for the gruuping. 2nr/x. fjf = «- »" + (%) If2"'erf<(r+«) which is obtained from the slope of the curves on Fig- 19.1 at high r values (see also first term of Eq. (5)| r J*rerfc|r n)| . (5> The value of tins group is i/ek/D. Whne this valne may cumprise adequate Information for reactor analyses, it is not sufficient for mechanistic studies. It would Figure 19.1 shows that data for H-327 graphite give a that a complete picture of cesium difrssioB in food corrctaiNM when one amumn a TSM of T * 1.25 permeable graphites can only be gained through (carve II) for ihi\ particular experiment. Tint aim a properly tuned laboratory experiments. pnowvf indication thai the trap model, as explained above, is an adequate representation of cesium migra tion behavior m the H-327 material. The same mode) 7. C. F. Wavotfc. N. L. ••rniia. C. i. Scon. wtLt Zaiuwnu. rvrnrmdUFniw JunmniffNm of r\w A Bonont Fwti h2s been wed by General Atomic to correlate long-term TrU Bemrml FIE 3. 1>SAEC Report GA-AI30M (Aqtast m-paV experiments, using the same graphite but dif 1*74). 20. Miscellaneous Programs 20.1 RESOURCE STUDIES The purpose of these studies i> to seek out areas where there ss an earty need of resource conservation, im The Chemical Technology Division cuntmud to proved recycling of metals and development of substi contribute to ORNL mterdmsional efforts on resouiccs tutes for those dements in jeopardy of exhaustion, and and energy analyses. Preparation of a 400-page book. to derr^nine when; ORNL expertise and faculties may World Energy Conference Survey of Energy Resomcet. or sequestet^d to provide needed research and develop 1974. was completed ui August 1974 by H. E. GoeHer ment. and W. L Carter. THB work, sponsored by the AEC H. E. GoeBer B also panicipaiing m a study on the Office of Phoning and Analysis, included a world rational use of potentially scarce metals bemg con review of coal. on. gas. oil dale, hydraulic, nudear. and ducted by the Scientific Affairs Dn-isiua of the North renewable (solar, wind, tidal, geothermal. and ocean Atlantic Treaty Orgamzatiuc (NATO). The* study is thermal gradient) energy resources with new es.'imatcs examining the present world demand, production, from 7C ration; that cooperated in the effort. About consumption, and uses cf about a dozen scarce metals 5000 copies of the book were printed by McGregor and and is appraising die powMiiKS for increased recycling weraer. Washington. D.C.: 2500 copies were distributed and substitution, particubiry for dtssipatrve uses. A to attendees from nearly 100 countries at !he World substudy on mercury has now been completed. The Energy Conference held in Detroit in September 1974. findings of the NATO study group vnP be summarized and the reniamdei are on sale by die Joint Engineering m a report scheduled to be completed by the end of the Council. New York, and the World Energy Conference calendar ye?r. Central Office in London. ORNL wil in all nkeuhood continue in the prepare Jw2 STUDIES INVOLVING TESTS Don of future surveys provided that funding can !-e OF ORSOUTTE CASKS arranged. Members of the World Energy Conference are anxious that we continue this work but are also In recent years there has been a treat deal of interest entertaining proposals from other national committees. in safety aspecis of nuefcar-rebted programs. The The Division, represented by H. E. GoeHcr. also transportation of radioactive materials produced in the partkipaied in the LMFBR Program Review Group at nuclear fuel cycle has generated considerable discussion, AEC Headquarters during the fail of 1974. particularly since some of these highly radioactive matenab are with regard to a Revaluation of US. and world reserves moved through the puMic sector, these movements and resources of uranium and thorium and their must be accomplished with a high degree of safely and adequacy for a nonbreedcr energy industry. It was generaBy concluded that without the introduction of At present, the proof that containers used to trans commercial breeders in the early 1990s. VS. and world port radioactive material wil be safe, even m severe resources of nuclear fuels win be insufficient to sue ply accidents, is based on engineering calculations and. in a a nonbreeder industry beyond the early decades of the few cases, model testing. Large, fidl-size casks are being next century. This work is summarized in ERDA-I. destructively tested to develop the necessary data base Report of the Liquid-Met* Fen Breeder Reactor in an effort to convince the public that the parkage frngrmmRenm Croup (January 1975). behavior can be predicted with confidence. The ERDA Early m 1975. H. E. GoeUer became a member of the Division of Waste Management and Transportation ORNL Proguir Planning and Analysis Office and is (WMT) has organized an advisory committee to provide continuing general studies on nonrenewable resources. guidance for die program. % 97 In the post year, a 7000* cask was tested twice by process. In :hi» process, the waste solution is icixed dropping it from 30 fi onto an armor-plate surface of a with cement and injected into an impermeable shale reinforced concrete impact pad at the ORNL drop test formstior. at a depth of about 800 ft There the waste facility. These dr«^s provided engineering data and grout *ts. fixing the radionuclides in the center:, mformalioQ -m the adequacy of the instrumentation matrix. Subsequent injections form new grout sheets used to record dynamic data throughout the test adjacent and parallel to the earlier grout sheets. program. The existing Shale Fracturing Disposal Facility has Drops of heavier casks will take place at the Tower worked quite well for the disposal of intermediate-level Shielding Facility ITSF). which has a great lifting waste but cannot handle either slurries or wastes with a capacity but has lacked a surface upon which to drop specific activity higher than 2 Ci/gai. The need for a casks. A study of the capacity of die TSF indicates that disposal system for these types of waste is mumnent. casks possibly weighing as much as 40 tons couM be and a aew shale fracturing facility is being proposed. A Jroppcd from about 240 ft. Results of the study were part of the prelimuury planning for the facility is submitted i» an •Hemal I ORNL • safety review com verification of the suitability of the selected site by a mittee and approved. Based <*> this study, a complete demonstration that the strata are suitable, that injection safety analysis was written and is being submitted to pressures will not be excessive OS000 pa), and that the the Oak Ridge Operations Office <•! FRO A tot ap fractures formed by the injection wffl conform to the proval. beddmg planes (essentially horizontal). Demonstration A 23-ton Heavy-Water Components Test Reactor of these criteria requires a "site proof injection of (HWCTR) cask was received from the Savannah River 50.000 Vi 100.000 gal of water or grout tagged with a Operations Office. A test plan was then written and radMnucndc tracer that can be detected at observation submitted ><> the WMT adveory comimtiee. Based on wefls several hundred feel from the injection well. The their comments, the plan was updated and the cask was orientation of the fractu'c can then be verified by the modified. comparative depths of the injection and point of A temporary impact pad. weighing aboi'i 110.000 lb. detection. was designed and natalled at lite TSF to accommodate Four observation wells and an injection weD were some interim testing. We expect to nuke several drops drilled, cased, and cemented at the site of the projoseri of J 7000-P> cask :•« study the behavior of the new disposal facility which is about 800 ft southwest temporary imp*.: pad and the lowers under drop o» the existing shale fracturing site The observation conditions The Paducah release mechanrsn. will he used wcth were located 200 ft north, south, east, and west of to make these drop* This mechanism was redesigned the injection well. All of the wells deviate considerably and remodeled to increase its lifting capacity to more front vertical however, in general, the five wefts form a nearly match the capability of the towers. Following paraflel system quite suitable for determining the these initial tests, the HWCTR casi wdl he dropped 30 orientation of injected grout sheets. The overall trend ft at an oblique angle onto the temporary impact pad in of the wefts is to the north-northwest (local north) accordance with the approved test plan. Both the cask updip to the southeasterly dipping rocks. and lowers will be instrumented to monitor their The two methods considered for making the injection behavior. were: mixing and injecting the grout at the new wellhead, or mixing the grout at the exrsimg facility and purnpmg it overland to the new well. The second 203 MSrOSALOFORNLRAMOACtTVE WASTE BY HYDRAULIC FRACTURING method was chosen because better control of the grout mixture could be achieved by making use of the A study was conducted in FY 1974 to verify that a instrumentation at the existing facility In the first site proposed for a new Shale Fracturing Disposal option, the formidable logistical proWeTi of supplying Facility at ORNL was surtaMc for hydrofracture opera blended solids to the mixer at a fast and constant rate tions. An injection weH and four monitoring wells were could be avoided, and recently installed modifications drilled and cased, and a lest injection was made using a al the existing facility could be evaluated during an grout tagged with radioisotope tracer. The results of the injection iff essentially nonradioactive grout. A flow study indicate thai the proposed site B satisfactory. diagram of the equipment arrangement for the injection At ORNL. intermediate-level waste solution (waste is shown in Fig. 20.1. with a specific activity of between 1.5 X 10"* and 2.0 The injection proceeded smoothly. A total of 65.700 Ci/gai) is being disposed of by the shale fracturing gal of water was mixed with the stored solids ind 98 caai 0*» '*• TUT ^PRE-SCEIIO SOI.I0S y^ STORAGE Fig. 20.1. Flow dogma of equipment arrangement for injection. injected. The injected grout volume was 97.643 gal. The form (density = 1 g/cm3) and tanks (containing injection rate averaged 247 gpm at an average pressure borosilicate glass for neutron poisoning) that can store at fhc facility of 2900 psi. 900 kg of 233U in the form of uranyt nitrate solution The results of the test injection were entirely favor at 233U concentrations up to 250 g/liter. The Building able. The injection pressures were slightly less than had 3100 vault, designed for storage of unirradiated fissile been anticipated. The fracture moved out parallel to the materials according to the latest A EC sp> ^ifirations.1 bedding and to the structure of the area by advancing was placed in service during this report period. to the three observation wells in which it was detected. The storage facility accepts *j3U in the form of This means that there can hardly be any important uranyl nitrate solution or as properly packaged solids. folding in the Pumpkin Valley shale, at least at the The solids may consist of uranium metal or uranium depth of the tes?. The completed investigations and compounds that can be readily and safely dissolved in tests show clearly that the proposed new site is well stainless steel equipment. suited to waste disposal by h, draulic fracturing, as had The purification facilities include a single-cycle sol been anticipated from earlier experiences in the general vent extiaction system capable of purifying J 3 3 U at the area. rate of 25 kg/week. An ion exchange and nitrate-to- oxide conversion line, with a capacity of 22 kg of 733 U 20.4 STORAGE, PURIFICATION. AND DISTRIBUTION OF 133U Oak Ridge National Laboratory serves as a national I. R. W. Morton and J. R. Parrot I. Oilicaliry and Safely 233 distribution center for U. The facility includes Analysis: Building 3100. A Slorazr Vault for Uranium and shielded wells for storing up to 454 kgof i3,U in solid Plutonium. ORNL-TM-3929 (February 1973). 99 per week, was placed in operation for the Light Water A possible mechanism for tritium contamination of Breeder Reactor (LWBR) support program.2 shale oil is penetration of tritiated water vapor into the Receipts oi233U during this report period other than pores and fractures of the shale, followed by incorpora those involved in lite LWBR program (Sect. 7.1) tion of part of the tritium into the hydrocarbon consisted of I.I kg of uranium as 233U oxides. 0.6 kg structure of the oil when the kerogen breaks down of "'UOj-PuOi iU/Pu * 5) fuel and 0.5 kg of normal during retorting. Whereas tritiated water on or near the uranium metal in five shipments. shale surfaces can be removed before oil recovery by As of March 31. 1975. 859.1 kg of 233U and 8QI.7 washing the shale with water or by injecting water into kg of 23SU were stored at the facility. Of these. 101.6 the system during retorting3 tritiated water that kg of 233U and 800.2 kg of 235U as uranyl nitrate penetrates into the shale is less easily removed. Tritiated solution were stored in the Thorium Reactor Uranium water penetrated to the center of a 7-cm cube (500 g) Storage Tank facility. After storage for six years, the of oil shale in a 43-day exposure to 0.25 g of water uranium concentration remained constant. During the vapor containing 95 yC\ of tritium, at 85°C. The past year, the soluble neutron poisons, cadmium and tritiated water entered the shale from ail directions, but gadolinium, apparently decreased to about two-thirds slightly more along the bedding planes than across of the required concentration: therefore, mine had to them. Analyses of core samples taken along the major be added. axes through the center of the cube showed that tritium In addition to the 233U and 23SU, a total of 2.7 kg contamination of the shale decreased with depth, from of plutonium in the form of nitrate solution, oxide, and 0.137 pCi/g near the surface in the two cores taken mixed oxides of thorium and uranium is also stored in along the bedding planes and 0.115 uCi/g in the core the facilities. taken across the planes, to 0.054 pCi/g at the center. 20.5 CHEMICAL APPLICATIONS OF 20.6 PREPARATION OF TRAINING GUIDES NUCLEAR EXPLOSIVES FOR NUCLEAR FACILITY PERSONNEL The Chemical Technology Division has participated in The Guide to the Selection. Training ard Licensing ur the Plowshare Program for several years by studying the Certification of Reprocessing Plant Operators was pre potential behavior of radionuclides in underground pared for distribution by the ERDA Division of applications of nuclear explosives. Our participation in Operational Safety (DOS). The rough draft was sub the program was terminated during the past year. mitted for review to the DOS and to a number of Experimental studies were completed of tritium be training coordinators in the commercial sector as well as havior during in situ recovery of oil from oil shale, and in government installations. The review comments were a paper describing our studies of radionuclide behavior very favorable, and it appears that the final draft can be in copper recovery from ores was submitted for presented to DOS with very little alteration. publication in the Transactions of the Society of Mining At present, a guide for fuel fabrication plant opera Engineers ol AI ME. The abstract follows: tors is being written and is scheduled for completion in "Radionuclide Behavior in Copper Recovery with Nuclear rough draft form during the first quarter of 1976. Explosives." by W. D. Arnold and D. J. Crousc. Atntrccl The Similar guides are planned for milling and mining. feeJ potential behavior of radionuclides released in an underground preparation, enrichment, fuel storage, and transporta nuclear detonation to fracture copper ore for subsequent in-silu leaching and copper recovery was studied with regard to tion sections of the i.uclear fuel cycle. contamination of the copper product and hazards to operating Proposals for FY 1976 include production of video personnel. The laboratory test results indicate that only small tapes and brochures for training operators in many fractions of the radioactive fission products would be dissolved sectors of the nuclear industry. Tiic tapes and brorhures on leaching the ore. Tritium (as tritiated water) would be the dominant radionuclide in the circulating leach liquor, assuming would be produced nuinly by Chemical Technology use of a fusion explosive. The test results showed solvent Division personnel for distribution by the DCS and extraction to have important advantages over cementation for would be available as an aid for training programs in use recovering copper from the leach liquors. While the radio activity of the copper metal product produced by either method should be extremely low, the solvent extraction process 2. Oirm. Tcchnnl. Di.. Annu. Prop. Rep. Mar. 31. 1972. provides a more effective separation of copper from 'he ORNI.-4794.pp. 52 53. radioactive ontaminants and entails fewer radiation protection 3. Chcm. Trchnnl. Div. Annu. Prop. R'P- Mar. 31. .'974. problems. IV r these reasons, it is the preferred procesv ORNL-4966, p. 71. 100 by commercial processors and rcprocessors of nuclear the operation of fuel fabrication plants under normal fuel. and accident conditions. Plants fabricating fuel for 20.7 ENVIRONMENTAL IMPACT STATEMENT light-water-cooled reactors with and without piutonium ON THE US. NUCLEAR POWER recycle and for high-temperature gas-cooled reactors are EXPORTPROGRAM considered. The section on the nuclear fuel cycle will wppty as much detail as necessary to give the lay reader An environmental impact statement (EIS) on the U-S. a grasp of the technical nature of the cycle. The nuclear power export program is being prepared by the sections on fuel fabrication will describe the en Division of International Programs. The EIS will cover vironmental, economic, social, and other secondary the existing program, including all activities and com impacts of yteats committed to fulfilling foreign re mitments to date, as well as a range of estimates quirements. Environmental considerations include the projected through the year 2000. Portions of this EIS radionuclides released by the plants and the associated being prepared by the Chemical Technology Division dose commitments of the general population. Nc nradio- include the section that provides a general description active effluents or wastes produced by the plants and of the nucleai fuel cycle and the sections that describe their effect on the environment are also considered. Publications, Speeches, and Seminars BIOCHEMICAL TECHNOLOGY Bostkk. W. D., M. L Bauer.1 and C. A. Burtis, "Coagulation Time Determination with a Miniature Centrifugal Fast Analyzer," presented at the Seventh Annual Symposium on Advanced Analytical Concepts for the Clinical Laboratory. ORNL, Mar. 13-14, 1975. Bostick, W. D.. and P. W. Carr,2 "Feasibility of Recording Clot Lysis with the Thermometric Clot Detector," CUn. Chem. 20,1435(1974). Bostick. W. D., and P. W. Carr,1 "Plasma and Blood Coagulation Time Detector Based on the Flow Sensitivity of Self-Heated Thermistors,*' Anal Oum. 46(8), 1095 (1974). Bostick, W. D., and P. W. Carr,2 "Thermometric Detection of Blood Coagulation and Clot Lysis," presented at the 29th Annual Calorimetry Conference, Knoxvilte, Tenn., July 26,1974. Burtis. C. A. "Analytical Instrumentation," in The Study of Injured Patients, A Trauma Conference Report. Feb. 26 27, 1973, DHEW (NIH)-74-603 (1974). Burtis, C. A., "Demonstration of the Miniature Centrifugal Fast Analyzer," presented at the Medical Administrators Conference, Washington, D.C., June 20, 1974. Burtis, C. A., "Introduction and Historical Development of the Centrifugal Fast Analyzer," presented at the Workshop on Centrifugal Fast Analyzers, Fall Meeting of the American Association of Clinical Pathologists, Washington. D.C.. Oct. 10, 1974. Burtis, C. A., "Multiple Optical Configurations of Centrifugal Fast Analyzers," presented at the Annual Nketing of the Fiorida Section of the American Association of Clinical Chemists, Tampa, Fla., Nov. 16,1974. Burtis, C. A.. "R'.cent Developments in the Centrifugal Fast Analyzer Program at the Oak Ridge National Laboratory." presented to the Department of Analytical Chemistry, Michigan State University, East Lansing, Mich., May 13,1974. Burtis, C. A., 'The Centrifugal Fast Analyzer: A New Concept in Automated Analysis," presented at the Burroughs Wellcome Company, Research Triangle P*rk, N.C., Oct. 4, 1974. Burtis. C. A., 'The Centrifugal Fast Analyzer and Its Use in Clinical Analyses," presented at the 26th National Meeting of American Association of Clinical Chemists, Las Vegas, Nev., Aug. 18-23,1974. Burtis. C. A., "The Centrifugal Fast Analyzer: Fact or Fancy," presented at the Breakfast Rour.dtable Discussion. 26th Annual Meeting of the American Association of Clinical Chemists, Las Vegas, Nev., Aug. 18-23, 1974. Burtis, C. A., 'The Use of a Centrifugal Fast Analyzer for Automated Analysis," presented a; 'Jie National Center for Toxicologic*! Research, Jefferson, Ark.,Oct. I, 1974. Burtis, C. A.. "The Use of Centrifugal Fast Analyzers for Clinical Analyses," presented at the National Aeronautics and Space Administration, Johnson Space Center, Houston. Tex., Sept. 30,1974. t. Instrumentation and Co-,tro|j Division. 2. Department of f heirUtry. University of Cicorfpa. Athens. 101 102 Burtis. C. A.. W. D. Bostick. and W. F. Johnson.1 "Increasing the Versatility of the Miniature Centrifugal Fast Analyzer by the Use of Multiple Optical Configurations." presented at the Seventh Annua! Symposium on Advanced Analytical Concepts for the Clinical Lai-oratory. ORNL. Mar. 13 -14. 1975. Burtis. C. A.. W. F. Johnson.1 and J. B. Overton. "Autonvucd Loading of Discrete. Microliter Volumes of Liujuids into a Miniature Fast Analyzer." AnaL Chem. 46. 78o11°74). Burtis. C. A., W. F. Johnson.1 J. B. Overton. T. O. Tiffany.3 and J. C. Mailen. "Optimization and Analytical Applications of the Technique of Dynamic Introduction of Liquids into Centrifugal Analyzers." Clin. Chem. 20. 932(1974). Burtis. C. A.. W. F. Johnson.' C. D. Scott, and N. G. Anderson* "The Centrifugal Fast Analyzer - A New Concept in Automated Analysis." presented at the 59th Annual Meeting of the Arri*rican Association of Cereal Chemists. Montreal. Canada. Oct. 20-24.1974. Burtis, C. A.. W. F. Johnson.1 and T. O. Tiffany.3 "The Development of Rotors Having Separate Sample and Reagent Transfer Channels for Use with Centrifugal Fast Analyzers," AnaL Lett. 7,59I( 1974). Burtis. C. A.. W. F. Johnson.' T. 0. Tiffany.3 and C. D. Scott. "Techniques for Loading Liquids into the Rotor of the Miniature Centrifugal Fast Analyzer," presented at the Spring Meeting of the Southeast Section of the American Association of Clinical Chemists. New Orleans, La., Apr. 18-20.1974. Burtis. C. A.. W. F. Johnson.1 T. O. Tiffany.3 and C. D. Scott. "Techniques for Loading Liquids into the Rotor of the Miniature Centrifugal Fast Analyzer." presented at the 26th National Meeting of the American Association of Clinical Chemists. Las Vegas. Nev.. Aug. 18 23. 1974. to be published in Clin. Chem. Carr. P. W..J L. D. Bowers.' W. D. Bostick. and E. B. Smith,2 "Novel Applicatians for Temperature and Row Sensitivity of Thermistors in Analysis and Hematology." presented at the First Annual Meeting of the Federation of Analytical Chemistry and Spectroscopy Societies. Atlantic City. N J.. Nov. 20. 1974. Chilcote. D. D., "Column-Chromatographic Analysis of Naturally Fluorescing Compounds: III. Rapid Analysis of Serotonin and Tryptamine." Clin. Chem. 20,421 (1974). Chilcote. D. D.. "Guidelines for the Development of a Computer Scheme to Identify Chromatographic Peaks." presented at the Ninth International Symposium on Advances in Chromatography. Houston, Tex.. Nov. 4-7. 1974. Chilcole, D. D.. "Guidelines for the Development of a Computer Scheme to Identify Chromatographic Peaks." J. Chromatog. 99. 243 (1974). Chilcote. D. D.. J. E. Mrochek. and S. Katz. "Recent Advances in the Use of Liquid Chromatography for Carbohydrate Analysis." presented at the 59th Annual Meeting of the American Association of Cereal Chemists. Montreal. Canada. Oct. 20- 24. 1974. ' Chilcote. D. D.. J. E. Mrochek. C. D. Scott. J. M. Jansen.' and A. F. Johnson. Jr..' "A Computer System for Acquisition and Analysis of Analytical Data: Applications to Clinically Oriented Liquid Chromatography." presented at the Ninth Annual Meeting of the Association for the Advancement of Medical Instrumentation. New Orleans, La.. Apr. 18-20,1974. Gehrs, C. W..s L. D. Eyman.5 R. L. Jolley. and J. E. Thompson. "Effects of Stable Chlorine-Containing Organics on Aquatic Environments," Nature 249,675 f 1974). Hancher, C. W.. A. D. Ryon, A. D. Kelmers, and R. F. Hall.6 "Recovery of Erythropoietin from Anemic Sheep Plasma." Biotech. Bioeng XVI. 1069(1974). Hancher. C. VY.. L H. Thacker.' and E. F. Phares,7 "A Fiber-Optic Retroreflective Turbidimeter for Continuously Monitoring Cell Concentration During Fermentation," Biotech. Bioeng XVI, 475 (1974). i. taihokify Associate*. Inc.. Spokane. Wash. 4. University of Sooth Carolina. Charleston. 5. Environmental Sciences Dnifion. 6. University of Teiwienee. KnoxvUk. 7. BMogy Dmsinn. 103 Joky. R. I_, "Application of High-Resolution Liquid Chromatography to the Analysis of Dissolved Organics in Natural and Process Waters." presented at the 13th Annual Meeting on the Practice of Chromatography. Committee E-19 of the American Society for Testing and Materials, ** Jadeiphia, Pa.. Oct. 13-16.1974. Jofiey, R. L Xhiorine-Contaning Organic Constituents in Chlorinated Effluents,"/. Merer totka. Control Fed. 74(3). 601 (197S). Jottey, R. L. "CMonne-ContaBung Organic Constituents m Chlorinated Effluents from Sanitary Sewage Treatment Plantt," presented at the 47th Annual Conference of the Water Pollution Control Federation, Denver, Colo.. Oct. 6-11,1974. JoUey, R. l_. "Determination of ChJorination Effects on Organic Constituents in Sewage Treatment Plant Effluents: A Coupled "CI Tracer-High-Resolution Chromatographic Technique," presented at the 167ih Meeting of the American Chemical Society, Los Angeles. Calif.. Apr. I-S, 1974. JoJJey, R. L_. "Determination of Chiorine-Containing Organics in Chlorinated Sewage Effluents by Coupled 3*G Tracer-High-Resolution Chromatography." Emaoa. Lett. 7(4), 321 (1974). JoUey. R. l_. "DeternuruUot. of Dissolved Organic Constituents in Sewage Effluents and Natural Waters," presented to the Sanitary Engineering Dept. University of Tennessee, Kncxvule. Oct. 31,1974. Joiiey, R. L. W. W. Pitt. Jr.. C. D. icott, and M. D. McBride.* "Determination of Trace Organic Contaminanu in Natural Waters by High Resolution Liquid Chromatography," in Proceedings of the First Annual ASF Trace Contaminants Conference. ORXL. Aug. 8-10. 1973. compiled by W. Fulcerson. W. D. Shults, and R. I. Van Hook. CONF-7308O2 (March 1974). Katz, S.. W. W. Pitt. Jr.. and J. E. Mrochek, "Comparative Serum and Urine Analyses by Dual-Detector Anion-Exchange Chromatography,"/ Chromatog. 104.303 (1975). Kat/.. S.. W. W. Pitt. Jr.. J. E. Mrochek, and S. R. Dinsmore, "Sensitive Fluorescence Monitoring of Carbohydrates Eluted by a Borate Mol Je Phase from an Anion Exchange Column."/ Chromatog. 101. 193 (1974). Mrochek. J. E.. "Applications of High-Resolution Liquid Chromatography to Studies of Drug Metobolism and Cancer in Humans." presented at the Symposium on High Performance Liquid Chromatography, Little Reck, Ark.. Feb. 20-21,1975. Mrv^hek, J. E., "Application of Integrated Gas Chromatographic and Mass Spectrometric Methods in the Identification of Urinary Constituents Isolated by Liquid Chromatography." in Selected Approaches to Gas Chromatography Mass Spectrometry in Laboratory Medicine. R. S. Melville and V. F. Dobson (tds.), DHEW (NIH) 75-762 (1975). Mrochek..'. E.. S. R. Dinsmore. and T. P. Waaikes.* "Analytic Techniques in the Separation and Identification of Specific Purine and Pyrimidine Degradation Products of tRNA: Application to Urine Samples from Cancer Patients,"/ Natl Cancer Ln:. SJf6>. 1553(1974). Mrochek. J. E.. S. R. Dinsmore, and T. P. Waaikes.' "High Resolution Liquid Chromatography of Neutral Carbohydrates in Serum Glycoproteins." presented at the Seventh Annual Symposium on Advanced Analytical Concepts for the Clinical Laboratory. ORNL. Mar. 13-14.1975. Mrochek, J. E.. S. Kau. W. H. Christie.14 and S. R. Dinsmore. "Acetaminophen Meuboiism in Man. as Determined by High-Resolution Liquid Chromatography." Clin. Chem. 20.1066 (1974). Pitt. W. W., Jr.. and R. L. Jolley. "High-Pressure Ion Exchange Chromatography for Analysis of Water Pollutants." presented at the Symposium on Identification and Transformation of Aquatic Pollutants. Athens. Ga.. Apr. &-I0. 1974. Pitt. W. W.. R. L Jolley, and S. Katz. Automated Analysis of Individual Refractory Orpmics in Polluted Water. EPA-660/2-74-076 (August 1974). 8. Umvcmiy of TenncMte Sdmol of Medicine. Mempms. 9. National Inxifatn of Health. BrUmda. Ma. 10. Analytical Otnaniry DmwMi. 104 Pitt. W. W_. C. D. Scoft. and M. D. McBride.5 "Determination of Trace Organic Contaminants by High-Resolution Liquid Chromatography." pp. 323-28 in Trace Subaan.n in Environmental Health VII. If/4. A Symposium. D. D- Hemphill (ed.). University of Missouri. Columbia (May 1974). Scott. C. D.. "Automated Elution Electrophoresis. A Potential Clinical Tool." presented at the 20th National Meeungofihe American Association of Ctakal Chemists. Las Vegas. Nev.. Aug. 18-23.1974. Scott. C. D.. "Centrifugal Fast Analyzer Systems." presented at the Medical Administrators Conference. Washington. D.C June 20.1974. Scott. C. D.. -Chemical Profile of Man." presented at the ORAU "Jan Plan" Science Students Lecture Series. Oak Ridge. Term.. Jan. 21. 1975. Scott. C. D.. "High-Pressure Ion Exchange Chromatography." Science 186,226 (1974). Scott. C. D.. "High-Pressure Ion Exchange »"hromatography as Applied to the Separation of Complex Biochemical Mixtures,'* pp. 263-97 in Separation anJ Purification Methods, E. S. Perry. C. J. Van Oss, and E. Grushka (eds.). Marcel Dekker. New York, 1974. Scott, C. D.. "High-Pressure Liquid Chromatography for the Clinical Laboratory." Science 186, 226 (1974). Scott. C. D.. "Recent Advances in Biochemical Technology," presented to the Knoxviiie-Oak Ridge Section of the American Institute of Chemical Engineers. Apr. 25,1974. Scott. C. D.. "Recent Advances in the Application of High Resolution Liquid Chromatography to the Separation of Complex Biological Fluids." presented at the 8th Great Lakes Regional Meeting of the American Chemical Society, Purdue University. Lafayette. Ind., June 3-5. 1974. Scott. C. D.. "Some Recent Advances in the Development of Liquid Chromatography for the Analysis of Complex Biological Mixtures," presented at the American Chemical Society Regional Meeting, Akron. Ohio. Mar. 20. 1975. Scott. C. D., C. A. Burtis. W. F. Johnson.' L. H. Thacker.1 and T. 0. Tiffany,3 "A Small Portable Centrifugal Fast Analyzer System." Clin. Chem. 20,! 003 (1974). Scott, C. D.. and N. E. Lee, "Automated Elution Electrophoresis. A Potential Clinical Tool." presented at the 26th National Meeting of the American Association of Clinical Chemists, Las Vegas, Nev., Aug. 18-23, 1974. Scott. C. D., and N. E. Lee, "Automated Elution Electrophoresis. A Potential Clinical Tool," presented at the Seventh Annual Symposium on Advanced Analytical Concepts for the Clinical U'horatory, ORNL, Mar. 13-14, 1975. Scott, C. D., and R. S. Melville,1' "Introduction to the Proceedings of the Sixth Annual Symposium on Advanced Analytical Concepts for the Clinical Laboratory," Clin. Chem. 20,931 (1974). Scott, C. D.. W. W. Pitt, Jr., and W. F. Johnson,1 "Centrifugal Elution Chromatography with Eluate Monitoring," presented at the Ninth International Symposium on Advances in Chromatography, Houston, Tex., Nov. 4 7, 1974; published in/. Chromatog. 99.35 (1974). Tiffany, T. 0..J "Centrifugal Fast Analyzers in Clinical Laboratory Analysis," p. 129 in CRC Critical Reviews in Clinical Laboratory Sciences, The Chemical Rubber Company, Cleveland, Ohio, 1974. Tiffany, T. O.,3 W. F. Johnson,1 and C. A. Burtis, "The Feasibility of Direct Kinetic Specific Protein Analysis by Light Scattering with Centrifugal Fast Analyzers," presented at the Spring Meeting of the Southeast Section of the American Association of Clinical Chemists, New Orleans, La., Apr. 18-20, 1974. Tiffany, T. 0.,J W. F. Johnson,' and C. A. Burtis, The Feasibility of Direct Kinetic Specific Protein Analysis by Light Scattering with Centrifugal Fast Analyzers," presented at the 26th National Meeting of the American Association of Clinical Chemists, Las Vegas, Nev., Aug. 18-23, 1974; to be published in Clin. Chem. Tiffany, T. O.,3 N. E. Lee, W. F. Johnson,1 and C. D. Scott, "Automated Plasma, Red Blood Cell, and Hemolysate Preparation," presented at the Spring Meeting of the Southeast Section of the American Association of Clinical Chemists. New Orleans, La., Apr. 18 20, 1974. II. Nanoral iMtmrtc of General Medical Sciences. Bethesds. Md. 105 tiffany, T. O„3 N. t. Lee. W. F. Johnson.' and C. D Scott. "Automated Plasma, Red Blood Cell, and Hemorysate Preparation," presented at the 26th National Meeting of the American Association of Clinical Chemists, Las Vegas. Nev.. Aug. 18-23,1974. TuTany. T. O..3 J. M. Morton,'* E. M. HaU,' * and A. S. Garrett. Jr..'' "Kinetic Enzymic Fixed-Tine and Integral Analysis of Serum Triglycerides: A Clinical Evaluation." dm. Chem. 2t. 467 (1974). Vttfaiy, T. 0„3 J. M. Parela, C. A. Bums, W. F. Johnson.' and C. D. Scott, "Blood Grouping with a Miniature Centrifugal Fast Analyzer." dm. Chem. 2t, 1043 (1974). Tiffany, T. O.,3 J. M. Patella, W. F. Johnson.' and C. A. Bums, "Specific Protein Analysis by Lgti-Scatter Measurement with a Miniature Centrifugal Fast Analyzer," Oat Chem. 2*. 1055 (1974). COAL TECHNOLOGY Chemical Technology Division. Prvspecthe Projects for Supporting Research. Development, and Engineering in Coal Conversion A Proposal to the Offux of Coal Research i¥tb.%,\914). Cochran, H. D.. "Experimental Engineering Development of Coal Hydrocarbonization," presented to the Department of Chemistry. University of Tennessee, Knoxville. Mar. 4,1975. Edwards, M. S.. B. R. Rogers, and R. Salmon, Supporting Research and Development on Separations Technology: Phase I Report. ORNL-TM-4801 (March 1975). "Fossil Fuels for Central-Station Electric Power Generation," pp. 6A.2-1-6A.2-76 in Liquid-Metal Fast Breeder Reactor Program Proposed Final Environmental Statement. Vol. Ill, Sect. 6A.2, WASH-1535 (December 1974) (W. R. Gambill, contributor). Gambill, W. R.. "Coal Utilization," presented for the Teacher-Demonstrator Summer Training Program, ORAU, Oak Ridge, Term., July 10,1974. Gambill. W. R.. invited participant in NSF Research Workshop on Augmentation of Convectivc Heat Transfer (organized by Iowa State University. Department of Mechanical Engineering), OUarc International Airport. Chicago. 111., Apr. 22 23.1974. Holmes. J. M., "Coal Liquefaction," presented at the KnoxviUe-Oak Ridge Section of the American Institute of Chemical Enpneers, Oak Ridge, Tenn., May 22.1974. Holmes, J. M.. "Coal Liquefaction." presented at the Special Training Division Symposium on Energy Sources for the Future. ORAU. Oak Ridge. Tenn.. Aug. 14.1974. Holmes, J. M., "Coal Liquefaction." presented at Analytical Chemistry Division seminar. Nov. 12. 1974. Holmes, J. M., participant in panel discussion on Gaaf Conversion Materials and Effluents. Mutagenesis Program Meeting, ORNL Biology Division.Oct. 15,1974. Holmes, J. M.. R. Salmon, and R. P. Wichner, "Study of Options for Control of Emissions from an Existing Coal-Fired Electric Power Station." presented at the Coal and the Environment Technical Conference and Equipment Exposition. Louisville, Ky.,0ct. 22-24,1974. to be published in the Proceedings. Salmon, Royes. "Energy Resources." presented at Energy Division seminar. September 1974. Salmon. Royes. "Petroleum Economics," presented at Energy Division seminar. October 1974. Salmon, Royes. and J. P. Nichols.'3 "Study of Options for Control of Emissions from an Existing Coal-Fired Electric Power Station." presented at the Second Atomic Energy Commission Pollution Control Conference. Albuquerque, N.M., Apr. 16- 19.1974; to be puMisheJ in the Proceedings, 12. Health Omskm. 13. Director's DMnnn. 106 DEVELOPMENT OF THE THORnM FUEL CYCLE Brooks. L. H..14 R. G. Wymer. and A. L Lotts.15 "Progress in the Thorium-Uniiium-233 Reprocessing-Refabrt- cation Technology." presented at the American Nudear Society Topical Meeting on Gas-Cooled Reactors - HTGR and GCFBR. Gathnburg. Tenn.. May 7-10.1974; to be published in the Proceedmgs. Fitzgerald, C. L. and K. J. Notz, "Radioactive Nuclides in the OfT-Gas Stream of H^ad-End Reprocessing of HTGR Type Fuels." presented at the 13th USAEC Air Cleaning Conference, San Frandsco. CabX. Aug. 12-15,1974. Glass. R. W.. "A Guide to the UNOP OffGas Decoutarnmation FadUty." prepared for the ORNL Ti«r of the UNOP Off-Gas Decontamination Faciity for the American Nudcar Society Topical Meeting on Gas-Cooled Reactors - rfTGR and GCFBR, Oak Ridge, Tenn., May 7-10.1974. Glass. R. W., "Development of the Krypton Absorption in Liquid Carbon Dioxide (KALC) Process for HTGR Reprocessing Off-gas," presented at the 13th USAEC Air Cleaning Conference. San Francisco, Calif.. Aug. 12-15.1974. Glass, R. W., System Features and Component Descriptions for the Unit Operations Off-Ges Decontamination Faciity. ORNL-TM-4596 (February 197S). Glass. R W.. H. W. R. Beaujean,1 * H. D. Cochran. Jr., P. A Haas, D. M. Levins,17 and W. M. Woods, "Development of the Krypton Absorption in Liquid Carbon Dioxide (KALC) Process for HTGR Reprocessing Off-Gas," presented at rhe 13th USAEC Air Cleaning Conference, San Francisco, Calif., Aug. 12-15, 1974. Haas, P. A., HTGR Fuel Reprocessing: A Whole-Block Burner with Recycle of Cooled Gas for Temperature Control. ORNL-TM-4519 (August 1974). Notz, K. J.. "An Overview of HTGR Fuel Recycle," presented at Tennessee Industries Week, Univershy of Tennessee, KnoxviUe, Sept. 10,1974. Notz, K. J., J. H. Shaffer, and C L. Fitzgerald, "Loading 2"U „. Ion Exchange Resins for HTGR Fuel Kernels." presented at the Joint Fall Meeting of the Nuclear and Basic Sciences Divisions of the American Ceramic Society. Williamsburg, Va., Sept. 29 Oct. 2,1974. Snider. J. W., and D. C. Watkin, An Evaluation of HTGR Primary Burning. ORNL-TM-4520 (November J 974). HTGR TECHNOLOGY AND SAFETY PROGRAMS Compere. E. L, S. H. Freid,' * and C. W. Nestor,1 * Distribution and Release of Tritium in High-Temperature Gas-Coded Reactors as a Function of Design. Operational, and material Parameters, ORNL-TM-4303 (June 1974). Compere, E. L. M F. Osborne, and H. J. de Nordwall," Iodine Behavior in an HTGR. ORNL-TM-4744 (February 1975). de Nordwall. H. J.,2* "Safely Limits on Fuel for Gas-Cooled Reactors,'' presented at the 76th Annual Meeting of the American Ceramic Society. Chicago, III., Apr. 2S-May 2,1974. de NordwaH, H. J..1* and W. E. Bell,21 "Fission Product Control in HTGR Hants," presented at the American Nuclear Society Topical Meeting on GasCookd Reactors - HTGR and GCFBR. Gatlinbuiz, Tean., May 7-10, 1974; pubusbed m CONF 740501 (1974). Evans, R. B.. Ill, and M. T. Morgan, mathematical Description of Foskm-Product Transport m Coated Particles During Pott-nrmtiatitm Anneals. ORNL-4969 (June 1974). 14. Geaaral Atomic Co.. Sen Mas*. Cant. 15. mttam and Owiann PMnan. I*, tint wrniiaajnilnUKFAKJIcsi mwtCirwiay. 17. Minima Atamk Ernn C •minim, fttovtt ftM ma, Utnmtmd. 2232. M&.W. Amttam. IS. wsOnatCom.. U» »nanlin. CaW. 9 wm V4^maajmnjBwBjn ^Pfj^mmj^mm) n^avm'vjmjmmj* 30. faipB**nofwt , A*£X. wWyfffc, DoflclMiftY, 0otwt, KI^HMI. 2i. Cmnmmi AM* Co., WmHkmpm. DJC. 107 Lmdemer. T. B.. "rugh-Temperaiure Chemistry and Kmefic Measurements in Siscfeaf Fad System*.1" presented as seminars. Materials Research Laboratory. Pennsylvania Slate liwrersiry. University Park. Feb. 17-20. I97S. Lmdemer. T. B.. and H. J. de Nordwali.2* Theoretical Analysis of PussMe Rate-Coatroujne Mfihaniimi for Mass Transport m HTGR Oxide Fud Parudes." presented at the 76th Annual Meeting of die American Ceiam< Society. Chicago. IU.. Apr. 2* May 2. 1974; abstract pubbsnerf m Am. Cermm. Sic. RuJL 5314). 370t 1974). Lindemer. T. B.. II. J. de NordwaU.2 * and R. A. ObtaJ.2' "Analysis and Measurement of Mass Transport in Coated UO; and Other HTGR Oxide Partides." present-d at the Symposnirn on Thermodynamws of Nuclear Materials. Vienna. Austria. Oct. 21 25. 1974: to be publish rd m the Fruceedmrs. Lmdemer. T. B.. and R. A. Oktad.2' HTGP rurf kernel Migration Date fur the Th-l'-C-O System as of April I. 1974. ORNL-TM-4493 (June 1974). Lmdemer. T. B.. and R. A. Obtad.J' "Quantitarve Correlation oi Observed Fuel Migration in Irradiated HTGR Fuel Particles." presented at the 76th Annual 'Veeimg of the American Ceramic Society.Chicago. IU_ Apr. 28-May 2. 1974: abstract published in Am. Ceram. Site. Bull 5344). 57| 11974). Lindemer. T. B-. and R. L. Pezrson. 'Apparatus for Measuring Gases from Irradiated Fud Particles."/ Surf. Mater. 55.359(1975). Morgan. M. T., H. J. de Nordwall.2* and R. L Towns. Releme of Fission Products from Prrocnrbtn+Coated HTGR Firel Fknida Lmaing Hntwmdiatkm Anneals. ORNL-TM-4539 (December 1974). Morgan. M. T.. and R. B. Evans III. The Use of Models to Determine Parameters Controlling Cesium Release from Coated Particles." presented at die Fall Meeting of the American Ceramic Society. Wjfliamsburg, Va.. Sept. 29 Oct. 2. 1974. Obiad. R. A..21 A. R. Oisen.15 R. B. Fills." t. L Long. Jr..'5 and T. B. Lmdemer. An Irmtiatum Teu of Candidate HTGR Recycle Fueb mtheh-land H-2 Capsules. ORNL-TM-4397 (July 1974). Osborne. M. F-. t. L. Compere, and H. J. de Nordwali.2* "Iodine Adsorption on HTGR Coolant Circuit Materials.'" presented at the American Nuclear Society Meeting. New Orleans. La.. June 8 13. 1975: abstract published in Trans. Am. Mud. Sw. 21.330 (June 1975). MISCELLANEOUS Aisnuner. R. G.. Jr..2 2 G. T. Chapman.2 2 J. W. Waditer. and J. Baron.' * Photon Spectn from Induced Artmty at anOrtntmg Spacecraft. ORNL-TM-4345(May 1974). Blanco. R. fc.. "Control of Effluent Releases to Meet Environmenial Requirements." presented for the Teacher-Demonstrator Summer Tranung Program. ORAL'. Oak Ridge. Tern.. July 19.1974. Blanco. R. fc.. "Control of Effluent Releases to Meet Environmental Requirements.'' presented to Energy Division Social Scientists. 0RN', Sept. 11.1974. Blanco. R. fc.. "Fud Cycle Environmental and Safely Considerations.'" presented to visitors from the Muskogee. Oklahoma Chamber of Commerce. ORNL. May 3.1974. Brooksbank. R. E.. "Statu* of Irradiated Fud Processing and Shjppmg. 1974." presented at the Advanced Operations Planning Meetmg. Oak Ridge Gaseous Diffusion Plant. Oak Ridge. Tenn.. May I 2.1974. Brooksbank. R. L. "The Nudear Fud Cycle." presented at ORAU. Oak Ridge. Tenn.. Mar. 28,1974. Brooksbank. R. E . The Nuclear Fud Cycle." presented at die Syrnponum on Energy Sources for the Futkie. ORAU. Oak Ridge. Tenn.. Aug. I \ 1974. •rooksbank. R. fc.. J. R. Parrot I. E. L Youngblood. and W. T. McDuffce. The Conunwirni of a"U in the Processing Facilities of the ORNL PHot Plant." presented at the VII International Congress of the Sodete Francais de Radioprotection. Versailles. France. May 28 31.1974. 22. NffVlVkMJI fltVallO MVinTQll. 108 Dare. W.. Jf.. Hgh^ffidemcy /Vrirafarr- Air Filers S—te of the Art SMIIHMU fienmmmg to Hekmrn Aerosols. ORNL-TM*M6J(Apri: 1974). Endelman. F. J.. G. E. P. Box.23 J. R_ Boyle.'3 R_ R_ Hughes.23 D. R. Keeaey.23 M. L Notlhup.23 and P. G. Saffian.23 TftrJta/kviaTKa^UjdUnv^^^ 1974). GueBer. H. E_ ~Aa Optnmstk Outlook for Mineral Resources." presented at the Socio4:ngmeerm£ Coaoqaaun. Vandermlt University. NasbvmV Tewu. Feb. 2b. 1975. Godkr. H_ F_ R_ S, Cwbwuth.2* W. l_ Carter. E. L. Neboa.2* J. A. Patterson.2* 2). fanwaiy of wkmii. Maamtm. 24. Eanav Dnnnia. 25. FKPA.Wjiliinnii.DX-. 2t» DcfartntM of Gaohay. iJaaaraly of Teaman*. KaomMk. 27. Timimn Vamy Aanmnry. CIMnaaam. 2*. Mmfbttf FjMjammj Poilusaum Lmarawry. RJCMMMI. Warn. 29. Varna* tcitariw from NAIG. Nador Rcuarcfc Laaora«ary. fcaamki. Jam*. JO. ,Mnrj Gem** Wmhw SCTWW, fcmwHI. S.C. Jl. laaaiaaa: offmaa.il Faaauin*,. Vmtumy of Tcmaaat. Kmnxrmc. H. Oacrjiiuai Dttaina. JJ TV A. Kaosriat. Tea*. 34. ( ncipwiffy DMa«vNi. 109 Thonn. R. tj* H. ludey.J* *•* C- D- Brawoo. -Condoned hfwnbna m the Uraniumtlll)4Jranni mt.iV) Fluoride System."/ tewy. AwdL CArm. 3». 1095 I1974). Hymn. R. G_ "Chenucal Eajmeerwe. Operations ai Nudea* rower Plants." p^senled at the 67* Annual Meeting of ike nmcim Institute of Chemical Emjnvers. WuhingtfiB. DC, Dec. 3.1974. MOLTEN-SALT REACTOR PROGRAM Bars. C. F.. Jr.." R. P. Vk-hnrr. C. E. Bamberger." and B. F. Freane-»• -Remowrl of Iodide from LiF-BeF, Melts by HF-H, Sparging An Application to Iodine Removal from Molien Sail Breeder Reactor Fuel." And. Set Fng. S*. 399(19751. Bamberger. C. E.." B. F. Hitch." and C. F. Baes. Jr..JS "Determination of the Free Energy of Formauor of SaXiF, and SaFeF,."./. lm Bamberen. C. E.." J. P. Young.* * and R. G. Ross. The Chemistry of Teflvrinm in Molten Li,BeF4."7. Imorg. SnA Chem. 3*. 11581I974|. Bennett. M. R.." and L. M. Ferris." -Formation of UV) m a Molten fluoride Salt at 550-*50*C by Reaction of Gaseous LT» with Dissolved CF«.~/. Imorg. Mid Chem. 3». 1285 (1974). Mahnauskas. A. P.. and D. M. Richardson.15 "The Sombibues of Hydrogen. Deuterium, and Helium in Molten Li:BeF4.~/f*i Fng, Chan.. FunJtm. 13.242(1974). TJIeni. O. K-. and L M. Fetr*»." "Equilibrium Precipitation of Protactinium Oxide from Molten LiF-BeF2- ThF4-UF4-PaFs Mixtures Between 535* and (rff/CV. Imotg. XucL Chem. 3*. 1277 (1974). PATENTS AmVrMW. N. G..4 C. A. Burn*. W. F. J.ihnton.1 J. C. Matten. and C. D. Scott. "Compact Dynamic Multistation Photometer Ctrii/in* Disposable Cuvette Rotor." VS. Patent 3/'98.459 (Mar. 19.1974). Bums. C. A.. W. F. Johnson.' JP.J V. A. WaJk-r.iT "Automated Sample-Reagent Loader." US. Patent 3.854.508 (Dec. 17. 19741. Cathers. G. I. and C. J. Shipman." "Method for Removing Iodine from Nitric Acid." VS. Patent 3.803.295 (Apr. 9. 1974). Giesfcy. A. T.. J. E. Savobraen." R. P. Wischow." and W. T. McDuffee. "Process for Separation of Protactinium. Thorium, and Uranium from Neutron-Irradiated Thorium.'' VS. Patent 1X15.649 (July 23.1974). Grimes. W. R.. J. IL Shaffer, and F. A. Doss." "Removal of Fluoride from Chloride or Bromide Melts." VS. Patent 3.806.581 (Apr. 23. 1974). Hurst. F. J..JS and D. J. Crousc. "Oxidative Stripping Process for the Recovery of Uranium from Wet-Process Phosphoric Add." VS. Patent 3.335.214 (Sept. 10.1974). Irvine. A. R.. "Shipping Cask Neutron and Heat Shield.'' VS. Patent 3.851.179 (Nov. 26.1974). Leilnaker. J. M..'* and T. B. Lmdemer. "Oxy nitride Fuel Kernel for Gas-Cooled Reactor Fuel Particles." VS. Patent 3.878.041 (Apr. 15. 1975). Lmdemet. T. B.. "Nuclear Fuel for HnjJt-Temperaiure GatCooied Reactors," VS. Patent 3.798.123 (Mar. 19. 1974). MaMman. H. A..4* and W. G. Swan. "Cross-Flow Filtration Process," VS. Patent 3,835.040 (Sept. 10.1974). 35. OmWHttttf MviKWH; UiimWity vMi ClmWmWsl TcdMolBfy MVMMI. J9, IVOVmnnnfml TVffWCmmWC \JW9Wnmj, MnMM- 37. P*Mt JJjJ F-nfmiyJWWW PvlfcmWW 38- ItnttnVVnt 40. r ofiHmvft of flu OnViMMry DtvUmi. 110 McNeese. L el." L M. Ferra.M and F. J. Son*.'* -Method fur Removing Ran Latins from Spent Molten Mciafe. Fluoride Salt Matures." US Patent 3.*53.979 (Dec. 10.1974). Parkinson. W. W.. Jr..41 M. J. Kelly. B. J. Sturm42 and W. J. Martin. "Novel Pohstyrebc Product Having Rapid Post-Irradiation Decay of Conductivity and Process of Making Same." VS. Patent 3.835.122 (Sept. 10. (<*74>. Sdunitt. J. M..** D. J. Crouse. Jr.. and W. B. Howerton. "Method for Removing Alkyl Iodides from Air by Mercuric Nitrate Sofcibon." VS. Patent 3.852.407 (Dec. 3. 1974). Scott.C.D..-ImpregnatedChenucalSeparationParticles,"US.Patent 3 J»27.989(Aug.6.1974). Scott, C. D. "Rotor for Ffciorometnc Measurements in Fast Analyzer of Rotary Cuvette Type." U-S. Paten: 3.804.533 (Apr. 16. 1974). Scott,C. D., and W. W. Pitt. Jr.. "Diffeiential Chromatographic Method." VS. Patent 3.847.550 (Nov. 12, 1974). Tiffany. T. O..3 J. C. MaMen. W. F. Johnson.' C. D. Scott, and W. W. Pitt. Jr.. "Multiple-Sample Rotor Assembly for Hood Fraction Preparation." VS. Patent 3,864.089(Feb. 4.1975). POWER REACTOR FUEL PROCESSING Ackfcy. R D. and R. J. Davis. Effect of Extended Exposure to Simulated LMFBR Fuel Reprocessing Off-Gas on Radknodme Trapping Performance ofSorbents (Final Report). ORNL-TM-4529 < August 1974». Chandler. J. M.. "The Recovery and Return to Service After a Transport Accident of the Peach Bottom Spent Fuel Element Snipping Cask," in Proceedings of the Fourth International Symposium on Packaging and Transportation of Radioactive Materials. Miami Bench. Florida. September 22 27. 1974. CONF-74090I-P2 (1975). Goode. J. H.. C. L Fitzgerald, and V. C. A. Vaughen. 77tr Dissolution of Unirradiated and Irradiated /£.'.PuK>2 in Nitric Add ORHL-5015 (February 1975). Groeruer, W. S., and H. J. Jenkins,43 The Evaporation of Sodium into an Inert Sweep Gas - An Evaluation of the Process Hawing Apptkatkm to the Deactivation of Internal Sodium ir. LMFBR Fuel Assemblies. ORN L-TM-4598 (October 1974). Irvine. A. R.. and L B. Shappert, "A Combination Neutron and Fire Shield." presented at the Fourth International Symposium on Packaging and Transportation of Radioactive Materials. Miami Beach. Ha.. Sept. 22-27,1974; published in CONF-74090I-P2. Jurgensen, M. C. The Vermkulite Shipping Package: Drop Tests on the Closure. ORNL-TM-1.U2. Vol. 15 (January 1975). Klima. B. B.. LMFBR-37-FuehFlcment Shipping Cask Simulation: Test Assembly Operation and Data. 0RNL- TM-3992 (August 1974). Mailen, J. C. "Equilibrium in the Oxidation of Iodine by Hypera/eo'ropic Nitric Acid." / Jnorg. Awe/. Chem. 37. 1019(1975). Mailen. J. C, and T. 0. Tiffany,3 "The Reaction of Iodine with Concentrated Nitric Acid." J. Inorg. Nucl. Chem. 17,127(1975). Parker. G. W.. "Calculation of Gap Release of Radioactive Fission Products." Appendix C: R. L. Rit/man44 and G. W. Parker. "Survey of Experimental Work on Fission Product Release from Molten U02." Appendix D: and 44 R. L. Ritzman and G. W. Parker. 'Summary of Data on Fission Product Release from U0} During Oxidation in Air." Appendix F. in Reactor Safety Study An Assessment of Accident Risks in U.S. Commercial Nuclear Power Plants. Appendix VII. WASH 1400. prepared by USA EC Staff (August 1974). 41. Health fhynci Division. 42. Formerly of the Chemical Technology Division. 43. Summer participant from Ohio University. Athens. 44. Battdk Laboratories. Columbus. Ohio. Ill Ramey. R. H.. and J. C. Matien. "Solubdity of Hl,0, sn' oncentrated Si'.nc Acid."/ Chem. Eng Data 1*3). 202 Uuly 1974). Shappen. L B.. "Shipment oi Radioactive Material*." pp. 151 76 in Human and Fcoiogkr Effects of Sudor Power Plants, ed. by Leonard A. Sagan. Thomas. Springfieid. III.. 1474. Shappen. L 3.. and J. II Evans. The Obsolete Cask Program: Initial Tests. ORSL-TM-1312. Vol. 14 (November 1974). Shapperc. L. B.. and W. C. lilrkh. Conceptual Design of Packares for Shipping Sohrions Cmtammg li*Pu ami lyiU. OR*L-TM-4720(February 1975). lif rich. W. C. "Designing Packages lor Shipment oi' Solutions Containing " * Pu and *3 3 U."* presented at the Fourth International Symposium on the i*aciugicg and Transportation of Radioactive Materials. Miami Beach. Fla.. Sep;. 22-27. £974. Walton. C. D.. "Ikad-End Processing." presented at the University of Wisconsin, Midrsoo. Apr. 25,1974. Yarbrc, 0. O.. J. C. Mailen. and W. S. Grocnier. "Iodine Scrubbing from Off-Gas with Concentrated Nitric Acid." presented at the 13th USA EC Air Cleaning Conference, San Francisco. Calif. Aug. 12-15. 1974; to be published in the Proceedings. PROGRESS RETORTS Bond. W. D., Mid K. E. Lcuze. Feasibility Studies of the Partitioning of Commercial High-Levti ¥iastcs Generated in Spent Nuclear Fuel Reproassm%- Annual Progress Report for FY-1974. ORNL-50i 2 (January 1975). Burlis C. A.. W. F. Johnson,1 and C. D. Scott, Gravity Zero r'GcV Analytical Clinical Laboratory System Annual Progress Report for the Period June I. 1973. to May 31. 1974. ORNL-TM-4594 (July 1974). High tower. J. R.. Jr.. Engineering Development Studies for Molten-Salt Breeder Reactor Processing So. IS. ORNL-TM-4698 (March 19751. King. L. J.. J. £. Bigelow. 3»d E. D. Collins. Transuranium Pntcessing Plant Semiannual Report of Production. Status, and Plan* for Ptnod Ending December 31, 1973. ORNL-4965 (November 1974). King, L. J.. J. E. Bigelow. and E. D. Collins. Transuranium Processing Plant Semiannual Report of Production, Status, and Plans for Period Ending June 30. 1974. ORNL-4991 (February 1975). McNeese, L. b..13 Engineering Development Studies for Molten-Salt Breeder Reactor Processing So. 10. ORNL-TM-5 35 2 (September 1974,. Sco.t. C. D.. C. A. Burns. W. W. Pitt. A. D. Ryon. and C. D. Watson. Experimental Engineering Section Semiannual Progress Repttrt 'Excluding Reactor Programs!. September I. 1973. to February 2.",, 1974, ORNL-4602 (December 1974). linger, W. E.. J. C. MsiUn. A. R. Irvine, and C. D. Watson. Aqueous Fuel Reprocessing Quarterly Report for Period •; Ending December 31. i V 73. ORIS L-TM-W88 (June 1974). g Ungcr. W. E.. V. C. A. Vaughen. A. R. Irvine, and C. D. Watson. Aqttemis Fuel Reprocessing Quarterly Report for § Period Ending March 31. 1974. ORNL-TM-4587 (September 1974). f I 1 SEPARATIONS CHEMISTRY | Bell. J. T..JS and S. R. BUXIIHI, "Photoreduction of the l.'raryl Ion with Laser Light and F.thanol I. Quantum * YicMs and Medium Eff.. cts." J. In»rg. Sucl. Chcm. 36.1575 f Iv»74). | Bell. '. T..J5 II. A. Frieunvan."'* and M. R. Billings.45 "Spectrophntometric Studies of Dioxourani'irrXV) in Aqueous Media I. The Perchloratc Medium."/ lnorg. Sucl. Chcm. 3*. 2563 (S974). 4.V Summer employee. I **~I $ 112 Harrington. F. E.. R. Salmon. W. E. Unger. K. B. Brown. C. F. Coleman, and D. J. Crouse. Cost Commentary <»i a Proposed Method for Recovery ojf Uranium from Seanvrer. ORNL-TM4757 (November l')?4). Hurst. F. J..,$ and D. J. Crouse. "Recovery of Uranium from Wet-Process Phosphoric Acid by Extraction with Octylphenylphcsphoric Acid." Ind. Ens, Chert.. Process Design Develop. 13.286 (1974). McDowell. W. J.. "High Resolution Liquid Scintillation Method for the Analytical Determination of Alpha-Emitters in Environmental Samples." IEEE Trans. Sucl. Sri. NS-22( 1), 649 (February 1975). McDowell. W. J.. "The Production and Chemical Study of Nebelrum. Element 102." presented at Tennessee Technological University. Cookeville. Oct. IS. 1974. McDowell. W. J., and C. F. Coleman. ""Combined Solvent Extraction-Liquid Scintillation Methods for Radioassay of Alpha Emitters." presented at the International Solvent Extraction Conference. 1974. Lyon. France. Sept. 8- 14. 1974; to be published in the Proceedings. McDowell. W. J.. "Determination and Identification of Alpha-Emitting Nuclides by Solvent Extraction and High-Resolution Liquid Scintillation Counting," presented at the 19th Annual Meeting of the Health Physics Society. Houston. Tex.. July 7-11,1974. McDowell. W. J.. "High-Resolution Liquid Scintillation Method for the Analytical Determination of Alpha-Emitters in Environmental Samples." presented at the 1974 Nuclear Science Symposium and 14th Scintillation and Semiconductor Counter Symposium. Washington. D.C., Dec. 13,1974. McDowell. W. J., D. T. Farrar.4* and M. R. Billings,45 '"Plutonium and Uranium Determination in Environmental Samples: Combined Solven' Extraction-Liquid Scintillation Method," Talanta 21.1231 (1974). Thorngate. J. H..4' W. J. McDowell, and D. J. Christian.4' "An Application of Pulse Shape Discrimination to Liquid Scintillation Alpha Spectroscopy," Health Phys. 27, 123 (1974). SOL-GEL PROCESSES Haas, P. A.. "Formation of Liquid Drops with Uniform and Controlled Diameters at Rates of I0} to 10s Drops per Minute." AlChEJ. 21(2), 383(1975). Lloyd. M. H.. "Studies on the Chemical and Colloidal Nature of PM(IV) Polymer." presented at a Material Science Seminar. Sandia Laboratories, Albuquerque. N.M., Dec. 17.1974. McBride. J. P.. L. E. Morse. J. F. Talley, and C. F. Coleman, "Oxidation Effects on the Electrokinetic Behavior of Urania Sols."/ ColloidInterface Sci. 51,443 (1975). STUDIES IN CHEMICAL ENGINEERING SCIENCE Clinton. S. D., "Mass Transfer of Water from Single Aqueous Sol Droplets Fluidized in a Partially Miscibi? Alcohol." presented at the International Solvent Extraction Conference, Lyon. France. S<*pt. 8-14,1974; published in the Proceedings. Snider. J. W., anu J. J. Perona,31 "Mass Transfer in a Fixed-bed Gas-Liquid Catalytic Reactor with Cocurrent Upflow." AlChEJ. 20(6), 1172(1974). V\ jtson. J. S.. and I. E. McNeese.13 "Hydrodynamic Behavior of Packed Liquid-Liquid Extraction Columns with Fluids of Different Densities." presented at the International Solvent Extraction Conference, Lyon, France. Sept. 8 14, 1974; published in the Proceedings. SUPPORT FOR CONTROLLED THERMONUCLEAR PROGRAM Fottester, R. C, III, and J. S. Watson, "A Procedure for Quantitative Analysis of Potassium for Tritium." Anal. Lett. 8(1), 63 (1975). 46. Department of Chemistry, Tennessee Technological University, Coot"-'1"' ••'.>.' wauwakjAjM^'inaarg'-*-- 113 Forrester. R. C. III. and J. S. Watson. "Tritium Recovery and Separation from CTR Plasma Exhausts and Secondary Containment Atmospheres." presented at the 13thUSAEC Air Cleaning Conference, San Francisco, Calif, Aug. 12 If. 1974. Grimes. W. R.. "Molten Salts in Nuclear and Thermonuclear P.eactor Applications.'' presented at the Fifth EUCHEM Conference on Molten Salts. Freising. Federal Republic of Germany. Sept. 8-13,1974. Smith. F. J.. J. D. Redman, and R. A. Sirehlow. "Current Tritium Chemical Studies at Oak Ridge National Laboratory." presented at the USAEC Workshop. Mound Laboratory, Miamisburg. Ohio, Oct. 1-2,1974. Watson. J. S.. "Chemical Technology in Controlled Thermonuclear Reactors - Analy .cal Chemfttry Needs." presented at the 18th Conference on Analytical Chemistry in Nuclear Technology, Gatlinburg, Term., Oct. 22 24, 1974. Watson, J. S.. "Engineering Studies on Tritium Recovery from CTR Blankets and Plasma Results." presented at the Symposium on Tritium Technology Related to Fusion Reactor Systems. Miamisburg.Ohio.Oct. 1-2,1974; to be published in the Proceedings. Watson, J. S.. "Fusion Technology" (Gzowski Lecture), presented at the University of Western Ontario. London, Canada. Mar. 24,1975. Watson, J. S.. "Tritium Containment and Recovery in Fusion Reactor Systems " presented at the American Nuclear Society First Topical Meeting on the Technology of Controlled Nuclear Fusion, Apr. 16-18.1974; published in CONF-740402. Watson, J. S., R. Cherdack.47 and R. C. Forrester. "Recovery of Tritium from Fusion Reactors - Recent Results." presented at the American Institute of Chemical Engineers Meeting. Pittsburgh, Pa. June 2-5,1974. Wymer. R. G.. "Fusion Reactors and Their Fuel Cycle: A Primer," oral presentation to the ANS Student Chapter at Arizona State University. Tempe. Ariz.. Dec. 12. 1974. TRANSURANIUM ELEMENT PROCESSING Baybarz. R. D.4* J. A. Fahey 4* and R.G.Haire,35 "The Preparation, Crystal Structures, and Some Properties of Californium Oxysulfate and Oxysulfide," / Inorg. Nucl. Chem. 36,2023 (1974). Bigelow. J. E., "Recovery of Berkelium Through Fermium," Chap. 5.7 in Vol. 7, Part A I Jl, Gmelin Handbook of Inorganic Chemistry. Transuranium Elements. Pan A: The Elements, Springer-Verlag. Berlin, 1974. Roddy, J W., "Americium Hydrides and Metallides." presented at the American Chemical Society Meeting. Los Angeles, Calif., Apr. 1-5,1974. Roddy, J. W., "Americium Metallides: AmAs, AmSb. AmBi. Am3Se4, and AmSe2," /. Inorg. Nucl. Chem. 36(11). 2531(1974). Vaughen, V. C. A., "Recovery of Americium and Curium," Chap. 5.6 in Vol. 7. Part A 1.11, Gmelin Handbook of Inorganic Chemistry: Transuranium Elements. Part A: The Elements. Springer-Verlag, Berlin. 1974. WASTE TREATMENT AND DISPOSAL Blanco, R. E.. "Storage and Control of Transuranium Wastes." Chap. 14.5 in Part A 2, Gmelin Handbook of InorganL Chemistry. Transuranium rllements. Part A: The Elements, Springer-Veriag. Berlin, 1974. Blanco, R. E.. "Treatment and Storage of Wastes from Reprocessing Plants." Chap. 5.3 in Vol. 7, Part A 1,11, Gmelin Handbook of Inorganic Chemistry. Transuranium Elements. Part A: The Elements. Springer-Verlag, Berlin, 1974. 47. Burns and Roe Corp., Newark, N J. 48. Deceased. 49. Bronx Community College. Bronx. N.Y. 114 Blomeke. J. 0.. "Management '" Radioactive Wastes." presented at the Nuclear Engineering Seminar. Georgia Institute of Technology. Atlanta. May 2.1974. Blomeke, J. 0.. "Management of Radioactive Wastes from Fuel Reprocessing." presented at the Program on Reprocessing of Nuclear Reactor Fuels. University of Wisconsin-Extension. Madison. Apr. 25 - 26.1974. Blomeke. J. 0.. "Nuclear Fuel Waste Disposal." presented at the Workshop on Electrical Power Generation Comparative Risks and Benefits. University of Wisconsin. Madison. June 2.1974. Blomeke, J. 0.. "Waste Disposal (General Aspects)." presented at the ORAU Special Training Course Energy Sources for the Future. Oak Ridge. Term.. Aug. 21.1974. Blomeke. J. 0. "Waste Management - The EvoK.ng Strategy." panelist at the Waste Management 74 Symposium. Tucson. Ariz.. Apr. 22-24.1974. Blomeke. J. 0.. and W. D. Bond. "Higb-Level Waste Management Research and Development Program at Oak Ridge National Laboratory." presented at the American Chemical Society Meeting. Los Angeles Calif.. Apr. 2,1974: to be published in the Advances in Chemistry Series. Blomeke. J. 0.. and C. W. Kee. "Projections of Radioactive Wastes from the Nuclear Fuel Cycle." presented at the Eighth Midyear Topical Symposium of the Health Physics Society. Knoxville. Tenn.. Oct. 21-24.1974. Blomeke, J. 0., C. W. Kee. and R. Salmon. Projected Shipments of Special Nuclear Material and Wastes by the Nuclear Power Industry. ORNL-TM-4631 (August 1974). Blomeke, J. 0.. J. P. Nichols.13 and Royes Salmon. "Trends and Projected Shipments in the Nuclear Fuel Cycle Industry to the Year 2000," pre ited at the Fourth International Symposium on Packaging and Transportation of Radioactive Materials. Miami Jeach, Fla.. Sept. 22-27.1974; published in CONF-740901-P2. Bond, W. D., "Methods for Removal of Actinides from High-Level Waste." presented at the Waste Management 74 Symposium, Tucson. Ariz., Apr. 22-24.1974. Bond, W. D., H. C. Claiborne, and R. E. Leuze. "Methods for Removal of Actinides from High-Level Waste." Nucl. Technol. 24,362(1974). Cheverton, R. D., H. C. Claiborne, and R. B. Evans III, In Situ Gas Diffusion Experiments Associated with a Radioactive Waste Repository in Bedded Salt. ORNL-TM-4569 (January 1975). Claiborne, H. C, "Effect of Actinide Removal on the Hazards of High-Level Waste," presented at the Annual Meeting of the American Nuclear Society, Philadelphia, Pa., June 23-27. 1974; summary published in Trans. Am. Nucl. Soc. 18.190(1974). Claiborne, H. C, Effect of ActiniJe Removal on the Long-Term Hazard of High-Level Waste. ORNL-TM-4724 (January 1975). ftaibome, H. C, and F. Gera.50 Potential Containment Failure Mechanisms and Their Consequences at a Radioactive Waste Repository in Bedded Salt in New Mexico. ORNL-TM-4639 (October 1974). Gera, F.,50 "The Classification of Radioactive Wastes," Health Phys. 27,113 (1974). Godbee, H. W., "A Description and Evaluation of Established Processes for Solidification of Intermediate-Level Radioactive Liquids and Sludges." presented to the USAEC Division of Waste Management and Transportation. Washington, D.C., Nov. 15,1974. Jenks, G. H„ E. Sonder,51 C. D. Bopp. J. R. Walton,10 and S. Lindenbaum," "Reaction Products and Stored Energy Released from Irradiated Sodium Chloride by Dissolution and by Heating."/ Phys. Chem. 79(9), 871 (1975). Lin, K. H„ invited participant at the 1974 Conference on Tritium Control (Sponsor, USAEC Division of Waste Management and Transportation), San Francisco, Calif., Aug. 15,1974. 50. Present address: Comitato Nazionale pet IT.nergia Nucleare, Roma, Italy. 51. Solid State Division. 52. Department of Pharmacology. University of Kansas, Lawrence. 115 McClain. W. C. and A. L. Boch.13 "Disposal in Geological Formations" presented at be Waste Management 74 Symposium. Tucson. An/.. Apr. 22 24. 1974. Met lain. W. C. and A. L Boch.' * "Disposal of Radioactive Waste in Bedded Salt Forms lions." Nud. Technol. 24. 398(1974). Staff of the Chemical Technology Division. Program for Improved Waste Management in Commercial Nuclear Fuel Reprocessing Facilities. ORNL-TM-4783 (January 1975). Weeren. H. O.. Shale Fracturing Injections at Oak Ridge National laboratory 1972 Series. ORNL-TM-4467 (June 1974). Weeren. H. 0.. G. D. Brunton. W. DeLaguna." and J. G. Moore. Hydro fracture Sit.: ProttfStudy at Oak Ridge National laboratory. ORNL TM-4713 (November 1974). Wymer. R. G. "Radioactive Wastes: Source?. Treatment, and Disposal." presented it the Lowell Technological Institute. Lowell. Mass.. Oct. 4. 1974. Wymer. R. G.. "Radioactive Wastes: Sources. Treatment, and Disposal." presented to the Engineering Department. Arizona State University. Tempc. Dec. 13. 1974. SEMINARS 1974 April 3 Reprocessing of LMFBR Fuel: Head-End Studies C. D. Watson Dissolve Studies R. B. Heimdahl lodox Studies for Removal of Iodine from Air Streams B. A. Hannaford April 10 Coal Liquefaction - Overview J. M. Holmes April 24 Fuel Reprocessing in the HTGR Fuel Cycle An Overview J. W. Snider May I Special Actinide Products J. E. Bigelow J. B. Knaucr. Jr. May 8 Rad>c=i(ive Materials in Process Effluents -- Removal of Radium from F.G.Seeley Uranium Mill Tailings Tritium Behavior During Shale Oil Recovery After a Nuclear Explosion W. D. Arnold May IS Waste Fractionation W. D. Bond May 22 Developmenl of the Centrifugal Fast Analyzer C. A. Burt is May 29 Chemistry of the Iodine Nitric Acid System G. I.Cathers J. C. Mailen 1975 January 8 Burner Off-Gas Cleaning The AKUT Process H.W.R.Beaujean" January 22 Conceptual Actinidc Transmutation Studies A.G.Croff Inn Exchange in Waste Partitioning D. O. Campbell January 29 Reactions of Organic Compounds with Concentrated Nitric Acid W.E.Clark February 5 HTGR Reprocessing in Europe J. W. Snider February 12 Recent KALC Facility Operations and System Performance for DM. Levins'7 COiOj-Kr February 19 Iodine Behavior in an HTGR E. L. Compere 53. Consultant. 116 Febrary26 Meatal Health m Mntry H.B.HHI,: MawkS LMFBRRqiRXCM«Sn*es W.E.U^r March 12 Twboton Maa Traaafct » Mtehawcaly Agitated Wwrfuptijag C. H. tram. Jr. liojMtd4JojaM Contactors Dndopneai of the Metal Traarfrr Process for Ram-Ear* Reasonl H.C. 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