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PNNL-12107
K BASIN SLUDGE CONDITIONINGPROCESS TESTING PROJECT
RESULTS FROM TEST 4, “ACID DIGESTION OFMIXED-BED ION EXCHANGE RESIN”
K. H. poolC. H. DelegardA. J. SchmidtB. M. ThorntonK. L. Silvers
June 1998
Prepared forDuke Engineering & Services Ha&ord
Work Supported bythe U.S. Department of Energyunder Contract DE-AC06-76RL0 1830
Pacific Northwest National LaboratoryRichland, Washington 99352
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Executive Summary
Purolite NRW37, a mixed bed ion exchange resin which consists of 40% by volume Purolite NRW-1OO(strong acid cation exchange resin) and 60% by volume Purolite NRW-400 (strong based anion exchangeresin) has been used to treat K Basin waters for 5 to 12 years. The anion resin is initially amber in color,and is a hydroxyl form trimethylamine functionalized polystyrene-divinyl benzene copolymer. Thecation resin is initially nearly black in color and is the hydrogen form sulfonic acid functionalizedpolystyrene-divinyl benzene copolymer. Accidental discharge of this resin is known to have occurredduring this time. These resin beads have been tentatively identified as components of sludge samplesretrieved from K East basin floor and Weasel Pit. The tests and results discussed in this report describethe fate of Purolite NRW37 during the nitric acid based sludge dissolution process. Specifically, thechange in chemical functionality of the resin (e.g., loss of ion exchange fictional groups and addition ofnitro or nitroso moieties to the resin matrix) was investigated. In addition, the thermal stability of therinsed product resins and their propensity to undergo rapid exothermic events when heated wereevaluated. The organic carbon concentrations of the digestion solution were also determined.
Significant changes in measured properties of resin beads were observed only at the most extremedigestion conditions (95 0 C; 7 and 24 hr). At less rigorous conditions, only very Small losses of ion”exchange fi.mctionality were seen. The extent of resin bead matrix disruption, as measured by TOC ofdigestion filtrates, was only significant at the most extreme processing conditions.
Radionuclides sorbed or associated with the organic ion exchange resins (OIER) can restrict disposal ofthis solid to the Environmental Restoration Disposal Facility (ERDF). Solids to be delivered to theERDF must meet Waste Acceptance Criteria (WAC) for radionuclide concentrations (ERDF WasteAcceptance Criteria, BHI-00139, Rev. 2, Table 4-l). The radionuclides most likely controlling theERDF acceptance of K Basins’ solid residues are 137CS(32 Ci/m3 or 32 pCi/mL) and the transuranics(TRU; 100 nCi/g). The transuranic isotopes have individual limits; ‘“Am is 0.05 Ci/m3 (50 nCi/mL),‘8Pu is 1.5 Ci/m3 (1,500 nCi/mL), and 23!Puand 240Puare each 0.029 Ci/m3 (29 nCi/mL). The effectiveuranium limit for disposal to ERDF, 0.0026 g U/triL’, may also foreclose ERDF disposal of certain KBasins residues. The radionuclide activities of OIER retrieved from the K Basins must bedecontaminated to these levels to allow ERDF disposal. The TRU content of rinsed OIER retrieved fromthe K East Basin (Sample KES-H-08) has been found to range from about 650 to 850 nCi/g dried resin.
“*37CSand 0.003 g U per gram of dried resin (Schmidt et al.The unrinsed OIER also contains 144 pCl1999).
Based on the above radionuclide concentrations in the actual OIER in KE Basin sludge and the levels of .defunctionalization achieved during the cold OIER testing (i.e., 3’XOto 34’?40defunctionization for thecation and 3°/0 to 13°/0for the anion resin material), acid digestion in 15.7 ~ HNO~ is predicted to beinsufllcient to decontaminate the OIER to the levels necessary to meet the ERDF WAC. However,
‘ The ERDF WAC limit for 23*Uand its daughters is 0.012 Ci/m3. With 8 alphaand 6 beta decaysin the 23SUdecaychainand a speciilc activityof 3.36x10-7Ci ‘W /g, the specificactivityof the 23*Uchain is 4.7x104 Ci/g. TheERDF limit for 23*Uthus is 0.00256g 238U/mL.The ERDFlimit for 23SU(daughtersnotincluded)is 0.0027 Ci/m3and the specificactivityof 23SUis 2.16x104 Ci/g. Thus the ERDFlimit for ZSUis O.OO13g ‘35u/mL.The Rktthe
limits of the two uranium isotopes,and the nominal0.7°Aenrichmentof the K Basinssludge,mean that ‘3*Uconcentrationlimits ERDF disposal. Therefore,the effectiveuraniumlimit for disposalto ERDFis 0.0026g U/mL.
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recent results from digestion of actual OIER from KE Basin sludge in 10 ~ HNO~ indicate that higherlevels of decontamination were achieved than predicted from the cold OIER digestion (Schmidt et al.1999). For sieved and rinsed OIER from sample KES-H-08, at ratios of about 1 g resin per 20 mL acid,about 80°/0of the uranium, 25% of the plutonium, and 70% or more of the americium activity wereremoved. Cesium distributions were not measured but high removals would be expected. Residualactivities in the acid-treated OIER were 160 to 340 nCi/gTRU(110- 190 nCi 239’240Pu/g,20-120
“‘37Ck/g(uraniumconcentrations were not detectable but likely were nearnCi241Am/g),and 1.5-34 pCl0.0003 g U/g based on & tests at higher loadings).
The differences in results obtained from the digestions performed on the cold OIER and the digestionsperformed on the hot OIER collected from KE Basin sludge can be partially attributed to the followingfactors: 1) the cold testing examined defimctionalization, whereas the decontamination achieved duringthe hot testing included the effects of both defimctionalization and displacement, 2) the initialradionuclide concentrations associated with the hot OIER may have included particulate mater that waseasily digested (i.e., possibly inflating the initial concentrations of the OIER), and 3) The ion exchange.capacity in the cold work was determined with Na+ (cation resin) and Cl- (anion resin). The binding
137cs DVJOpu,ad zAl~ differ from that of Na+and Cl-.affkity of OIER for ,
Based on the results obtained for the digestions of the hot OIER, it may be possible to remove cesium,uranium, and americium to meet ERDF criteria by performing multiple washing contacts of retrievedOIER with strong HN03. However, such an approach would be less successful for plutonium wherestrong anion exchange sorption occurs at high HNO~concentrations and strong cation exchange sorptionoccurs at low HN03 concentrations, especial considering that very little defunctionalization occurs toeither the anion or cation resin. Consequently, a more sophisticated leaching approach will likely berequired to decontaminate the OIER to the levels necessary to meet the ERDF WAC.
FTIR spectra of digested resins show evidence for formation of small amounts of nitroaromaticcompounds (nitrated resin matrix). Thermal analyses suggest that nitric acid treated resin beads canundergo exothermic decomposition reactions in the 160”C to 400 “C temperature range. The largestexothermic event (1015 J/g) was observed for sample C 100-3. These results indicate that some level ofsafety evaluation will likely be required if the OIER will be digested or leached with nitric acid. Afternitric acid leaching or digestion, it maybe necessary to contact the OIER with base to hydrolyzenitroaromatics and neutralize and remove residual acid.
iv
CONTENTS
Executive Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..iii
1.0
2.0
3.0
4.0
5.0
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...1-1
Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...2-12.1 Preparation ofIon Exchange Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...2-12.2 Nitric Acid Digestion ofIonExchange ResinBeads . . . . . . . . . . . . . . . . . . . . . . . ...2-12.3 Total Organic Carbon Analyses ofDigestion Supemates . . . . . . . . . . . . . . . . . . . . ...2-12.4 IonExchangeCapacityTests/Cation Resin Samples . . . . . . . . . . . . . . . . . . . . . . . ...2-22.5 Anion Resin Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...2-22.6 Differential Scanning Calorimetry(DSC) and Thermal Gravimetric
Analysis(TGA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...2-32.7 Fourier Transform InfiaredAnalyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...2-3
Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...3-13.1 QualitativeObservationsDuringDigestions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..3-13.2 Sample Identifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...3-13.3 Weight Changes Following Digestions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...3-23.4 Total Organic Carbon Content ofDigestion Filtrates . . . . . . . . . . . . . . . . . . . . . . . ...3-23.5 Ion Exchange Capacity ofDigested Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...3-33.6 Thermal Analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...3-43.7 .InfiaredAnalysis ofNitric Acid Treated Sulfonated(Cation) and Quatemary
Ammonium(Anion) Polystyrene Copolymer IonExchangeResins . . . . . . . . . . . . ...3-63.7.1 Cation Exchanger-NitricAcidTreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-63.7.2 Anion Exchanger-NitiicAcidTreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-7
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...4-1
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...5-1
AppendixA Thermal Gravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC)Traces forNitric Acid DigestedPurolite Ion Exchange Resin Samples
v
TABLES
3.1 Sample Identifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...3-2
3.2 TOCFound inDigestionFiltrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...3-3
3.3 Ion Exchange Capacity ofDigested Resin Samples and Starting Materials . . . . . . . . . . . . ...3-4
3.4 Thermal Behavior ofIonExchange Resin Samplesin the TemperatureRange, 150 t0400°C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...3-5
3.5 Treatment Conditions forCationExchange Resin Samples . . . . . . . . . . . . . . . . . . . . . . . . ...3-6
3.6 TreatmentConditions forAnionExchange ResinSamples . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-7
4.1 Results Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...4-1
vi
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3.1
3.2
3.3
3.4
A. 1
A.2
A.3
A.4
A.5
A.6
A.7
A.8
A.9
A.1O
All
A.12
FIGURES
Infrared Spectra of Sulfonated Polystyrene Copolymer, Cation Exchange Resin;4000 – 400 cm-’ Region. Resin was treated as follows (a) ffesh resin, no acidtreatment (b) 10M HNOq, 60 “C, 8h, (c) cone HNOt, 60”C, 7h, (d) cone HNOq,95 °C,24h . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Infrared Spectra of Sulfonated Polystyrene Copolymer, Cation Exchange Resin;2000 – 400 cm-’ Region. Resin was treated as follows (a) fresh resin, no acidtreatment (b) 10M HNO~,60°C, 8h, (c) cone HNO~,60°C, 7h, (d) cone HNO~,95 °C,24h . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Infrared Spectra of Quaternary Ammonium Polystyrene Copolymer, AnionExchange Resin; 4000 – 400 cm-’ Region. Resin was treated as follows(a) fresh resin, no acid treatment (b) 10M HNO,, 60°C, 8h, (c) cone HNO,,roomtemp, lh(d)conc HNO~,95°C, 24h . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . 3-9
. . 3-1o
. . 3-11
Infrared Spectra of Quaternary Ammonium Polystyrene Copolymer, AnionExchange Resin; 2000 – 400 cm-l Region. Resin was treated as follows(a) fresh resin, no acid treatment (b) 10M HNO,, 60”C, 8h, (c) cone HNO,,room temp, lh(d)conc HNO~,95°C, 24h . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...3-12
TGAand DSCTraces for Sample CO.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. A-I
TGAand DSCTraces for Sample C1. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. A-2
TGAand DSCTraces for Sample C2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. A-3
TGAand DSCTraces for Sample C3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. A-4
TGAand DSCTraces for Sample C60-1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. A-5
TGAand DSCTraces for Sample C60-2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ., . . . .. A-6
TGAand DSCTraces for Sample C60-3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. A-7
TGAand DSCTraces for Sample CIOO-1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. A-8
TGAand DSCTraces for Sample CIOO-2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. A-9
TGAand DSCTraces for Sample CIOO-3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. A-10
TGAand DSCTraces for Sample AO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. A-11
TGAand DSCTraces for Sample Al . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. A-12
vii
A.13
A.
A.
4
5
A.16
A.
A.
7
8
A.19
A.20
FIGURES (Continued)
TGAand DSCTraces for Sample A2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. A-13
TGAand DSCTracesforSampleA3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..A-14
TGAandDSCTracesfor SampleA60-1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..A-15
TGAandDSCTracesforSampleA60-2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..A-16
TGAandDSCTracesforSampleA60-3 . . . . . . . . .
TGAand DSCTraces for SampleAIOO-1 . . . . . . . .
TGAandDSCTraces forSampleA100-2. . . . . . . . .
. . . . . . .
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. . . . . . . .
. . . . . . . . . . . . . .
. . . . . . . . . . . . . .
. . . . . . . . . . . . . .
. . . . . . . A-17
. . . . . . . A-18
. . . . . . . . A-19
TGAandDSCTracesforSampleAIOO-3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..A-20
...Vm
1.0 INTRODUCTION
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Approximately 73 m’ of heterogeneous solid material, “sludge,” (upper bound estimate, Packer 1997)have accumulated at the bottom of the K Basins in the 100 K Area of the Hanford Site. This sludge is amixture of spent fiel element corrosion products, ion exchange materials (organic and inorganic),graphite-based gasket materials, iron and aluminum metal corrosion products, sand, and debris (Makenaset al. 1996, 1997). In addition, small amounts of polychlorinated biphenyls (PCBS) have been found.Ultimately, it is planned to transfer the K Basins sludge to the Hanford double shell tanks (DSTS). TheHanford Spent Nuclear Fuel (HSNF) project has conducted a number of evaluations to examinetechnology and processing alternatives to pretreat K Basin sludge to meet storage and disposalrequirements. From these evaluations, chemical pretreatment has been selected to address criticalityissues, reactivity, and the destruction or removal of PCBS before the K Basin sludge can be transferred tothe DSTS. Chemical pretreatment, referred to as the K Basin sludge conditioning process, includes nitricacid dissolution of the sludge (with removal of acid insoluble solids), neutrons absorber addition,neutralization, and reprecipitation. Laboratory testing is being conducted by the Pacific NorthwestNational Laboratory (PNNL) to provide data necessa~ to develop the sludge conditioning process.
The proposed K Basin sludge conditioning process for removal, processing, and ultimate disposal of KBasin sludges includes a nitic acid digestion/dissolution step intended primarily to dissolve uraniummetal and/or oxides known to be major sludge components. During this nitric acid treatment step, ionexchange materials (specifically polystyrene-divinylbenzene based resins) consequently would bedisposed of as a part of the acid insoluble solid waste. It is planned to dispose the acid insoluble fractiongenerated from the sludge conditioning process to the Environmental Restoration Disposal Facility(ERDF) (Hatch 1997).
Purolite NRW37, a mixed bed ion exchange resin which consists of 40’%by volume Purolite NRW-1OO(strong acid cation exchange resin) and 60% by volume Purolite NRW-400 (strong based anion exchangeresin) has been used to treat K Basin waters for 5 to 12 years. The anion resin is initially amber in color,and is a hydroxyl form trirnethylamine functionalized polystyrene-divinyl benzene copolymer. Thecation resin is initially nearly black in color and is the hydrogen form sulfonic acid fictionalizedpolystyrene-divinyl benzene copolymer. Accidental discharge of this resin is known to have occurredduring this time. These resin beads have been tentatively identified as components of sludge samplesretrieved from K East basin floor and Weasel Pit. The tests and results discussed in this report describethe fate of Purolite NRW37 during the nitric acid based sludge dissolution process.
The work described in this report was performed in accordance with the “Fiscal Year 1998 Cold TestingWork Plan in Support of K-Basin Sludge Conditioning System Process Development” (Silvers 1997) andthe associated test instruction. In accordance with the work plan, the following items were evaluated:
● change in chemical functionality of the resin e.g., loss of ion exchange fmctional groups andaddition of nitro or nitroso moieties to the resin matrix,
● thermal stability of the rinsed product resins and their propensity to undergo rapid exothermicevents when heated, and
● organic carbon concentration of the digestion solution.
1-1
2.0 EXPERIMENTAL
2.1 Preparation of Ion Exchange Resins
Cation ion-exchange resin, Purolite NRW- 100 in H+form, and anion ion-exchange resin, PuroliteNRW-400 in OH- form, were washed repeatedly with deionized water (DIW) until the specificconductivity of the washings were less than 2 @cm following overnight exposure. The thoroughlywashed resins were then dried overnight at 50“C and subsequently stored in a desiccator (Drierite) untilprepared for the nitric acid digestion tests described below. A portion of each resin type was fin-therdried at 110”C for 4.75 hours to determine moisture content remaining after 50”C drying. Weight losseswere 12.2°/0and 8.3°/0for cation and anion resins respectively.
2.2 Nitric Acid Digestion of Ion Exchange Resin Beads
Digestions were carried out using concentrated HNO~(-15.7 ~) at three temperatures: room temperature(-22°C), 60”C, and 95 “C. All digestions were carried out unstirred except that room temperaturedigestions of anion resin samples were gently stirred by means of a small magnetic stir bar. For cationresin samples, 17 mL of concentrated HNO~/g resin was used and for anion resin samples the ratio was22 mL concentrated HNO~/g resin. These acid/resin ratios were chosen based on the followingassumptions:
● dry resin copolymer matrix is composed of six styrene moieties for each divinylbenzene,
● there are four ion exchange groups per six styrenes,
● the reaction products are COZ,HZO,and NOZ,and
● the resins are completely reacted to these products.
Digestions of each resin type were performed for nominally 1 hour, 7 hours, and 24 hours at each testtemperature. Following the digestions, resin beads from each test were filtered (Millipore HA type,0.45~m pore size), and rinsed five times with DIW. The combined filtrate and rinsings were diluted to aknown volume and set aside for total organic carbon (TOC) analyses.
The rinsed resin beads from each test were dried overnight at 50”C and stored in a desiccator untilprepared for tests to determine 1) residual ion-exchange capacity, 2) thermal behavior (DSC/TGA), and3) presence or absence of nitro/nitroso compounds (FTIR).
2.3 Total Organic Carbon Analyses of Digestion Supernates
Initial attempts to determine TOC of these samples were fraught with difficulties. Results were widelyscattered and not reproducible. It is believed that the high nitrate content and/or high acidity of thesamples introduced an uncontrollable interference in the actual analyses. To circumvent the problem, asample pretreatment procedure was designed and used. This pretreatment procedure consisted of addingwell washed aliquots of anion exchange resin (OH- form) to the digestion supernates, in quantitiessufficient to neutralize the H+and bind nitrate, agitating the resin and supernate on a laboratory shaker to
2-1
achieve ion exchange equilibrium, and analyzing the treated supernate by the usual acidi& Wd spargeTOC procedure. Blanks, i.e., fresh nitric acid diluted to same concentration as that of samples, weresimilarly treated with hydroxide form anion exchange resins and included in the TOC analysis campaign.The TOC content of the blanks could not be neglected relative to those of digestion supemates. Eachsample and blank were analyzed 3 to 5 times and the mean and standard deviations for the replicateswere calculated. Net TOC content of digestion supemates as given in the results section of this reportwere blank corrected and experimental uncertainty values (standard deviations) were calculated from theusual “propagation of errors” algorithm.
2.4 Ion Exchange Capacity Tests/Cation Resin Samples
Approximately 0.2 g aliquots of each digested cation exchange resin sample and an untreated resinsample were placed in glass scintillation vials and contacted with a known volume of knownconcentration of NaOH solution. These vials and contents were agitated on a laboratory shaker table forapproximately 60 hours. The supernates, along with an aliquot of the sodium hydroxide solution used,were analyzed for sodium content by ICP-AES (Procedure PNL-ALO-21 1.2, Rev. O). (Section 7.2.6 ofreferenced procedure was not implemented because it is not applicable to the instrument used.) From theknown total quantity of Na+ introduced to each sample and the residual quantity of sodium ion found insupemates afier ion exchange equilibration, the amount of sodium bound by the resin was calculated bydifference.
2.5 Anion Resin Samples
Approximately 0.5 g aliquots of each digested anion exchange resin sample and an untreated resinsample were placed in glass scintillation vials and contacted with a known quantity of knownconcentration sodium sulfate solution. These vials and contents were agitated on a laboratory shakertable for approximately 60 hours. The supemate and an aliquot of Na$O1 contacting solution wereanalyzed by ICP-AES for sulfur content according to the procedure cited above. The ion exchangecapacity for each sample was then calculated as described in the previous section of this report. Resultswere confising and deemed unreliable mainly because the calculations were based on the assumptionthat the sulfate introduced to each sample would behave as a divalent ion for ion exchange purposes.Tests of the equilibrated supemates revealed that the pH for digested samples was acidic (pH -2 by pHindicator paper) and the pH of supernate over undigested anion resin was definitely basic. At pHs of 2 orless, sulfate ion is known to exist primarily in the monovalent, bisulfate, form. Therefore, the basicassumption of divalent behavior of the sulfate in ion exchange capacity calculations is suspect at best,invalid at worst.
The supemates for all samples were discarded and replaced with 1.0 ~ NaOH, equilibrated as usual bymeans of the shaker platform agitation. The supemate was discarded, replaced with DIW, agitated again,supernate discarded, replaced with DIW, etc. untii the DIW washing pH <9. A fresh aliquot of 1.0 MNaOH was then added to each vial, and the equilibration, washing procedure used until pH of supernateswas less than 9. This procedure was intended to ensure that virtually all of the anion exchange sites ofthe resin samples were occupied by hydroxide ion. These samples were then contacted with a knownquantity of known concentration HC1. After equilibration by shaker platform agitation, the supematesalong with an aliquot of HC1 contacting solution were analyzed for chloride content by ionchromatography (procedure PNL-ALO-2 12). Ion exchange capacity of these anion resin samples wascalculated based on chloride balance as described above for cation resin samples.
2-2
.
.
2.6 Differential Scanning Calorimetry (DSC) and Thermal Gravimetric Analysis (TGA)
%rnplesof dried digested resins and undigested resins were pulverized to powder by standard methods.Thermal behavior tests (DSC and TGA) were conducted under a nitrogen gas blanket atmosphere, usinga 10OC/min temperature ramp rate from ambient temperature (200C) to a maximum temperature of750 “C. Weight change as a function of temperature (time) and heat absorption or liberation as a functionof temperature (time) were recorded.
2.7 Fourier Transform Infrared Analyses
Portions of powdered resin beads were mixed with KBr, pressed into pellets, and analyzed by FTIR forthe presence of significant fi.mctional groups such as nitro or nitroso moieties.
2-3
3.0
3.1
1.
2.
3.
4.
5.
6.
3.2
RESULTS
Qualitative Observations During Digestions
Anion resin floats, cation resin sinks when exposed to 15.7 ~ HNO~.
Immediate and sustained evolution of brown gas (NOX) from anion samples when exposed tocone. HNOSat all temperatures.
Room temperature digestion:. Cation resin - no obvious gas evolution. Digestion supematesyellow in COIOCcation resin digestates darker than those from anion resin.
60”C Digestions: Anion resin samples: immediate white vapor evolved followed quickly bybrown gas (NOX). Cation resin samples: immediate white vapor; brown gas observed as samplesheat up to near 60”C.
95 “C Digestions: anion resin samples same observations as above. Also it should be noted thata fine white precipitate appears to form a film on digestion vial walls which slowly settles tobottom during digestion. No attempt was made to isolate and analyze this white precipitate.This was also observed for room temperature and 60°C digestions. More brown gas evolutionobserved at 95 “C than 60°C.
Cation resin samples after digestion, filtering, and washing were progressively lighter in color asdigestion conditions increased in severity. Supernates were progressively darker yellow in coloras digestion conditions increased in vigor. Anion resin color differences not as apparent butshowed same trend.
Sample Identifications
Samples of resins and filtrates derived from digestions were given the identifications as summarized inTable 3.1 for reference.
3-1
Table 3.1 Sample Identifications
Cation I AnionSample ID Sample ID
co I AO
c1 I Al
C2 I A2
*
C60-2 A60-2
C60-3 I A60-3
Cloo-1 IA1OO-1
c 100-2 I A1OO-2
C1OO-3 I A1OO-3
Digestion I Digestion Temperature CommentsTime (hr) ~c)
o Starting materials
1 22 room temperature digestions
6.5 22 room temperature digestions
24 22 room temperature digestions
1 60 60°C digestions
7 60 60°C digestions
24 60 60”C digestions
1 95 95°C digestions
7.25 95 95°C digestions
24 I 95 I 95°C digestions
3.3 Weight Changes Following Digestions
Weight changes of resin samples following digestions and drying at 50”C varied widely. The range ofobserved weight changes was +5 .6°/0to -8.4°/0for cation resin samples and +0.65°/0to -5.5°/0for anionresin sample. The largest weight losses for both cation and anion resin samples were seen in the 95 ‘C,24 hr digested cases. There was no discernible trend in weight changes for resin samples involved in theother digestion conditions.
3.4 Total Organic Carbon Content of Digestion Filtrates
The TOC content of digestion filtrates of cation resin and anion resin samples was determined and resultscalculated as described in the experimental section of this report. Results are summarized in Table 3.2.
3-2
Table 3.2 TOC Found in Digestion Filtrates
.
.
Cation Cation Resin Sample Anion Resin Anion Resin SampleResin Net TOC & Std Dev. Sample ID Net TOC & Std Dev.Sample ID (mg C/g resin) (mg C/g resin)
cl 1.09 + 0.27 Al 1.83 + 0.83
C2 0.78 * 0.38 A2 1.30 * 0.78
C3 1.23 =!=0.37 A3 2.68 + 0.86
C60-1 1.44 + 0.31 A60- 1 2.18 + 0.95
C60-2 2.18 + 0.26 A60-2 2.23 + 0.84
C60-3 0.72 =t0.23 A60-3 2.92 + 0.82
Cloo-1 1.85 + 0.43 AIOO-1 3.41 * 0.87
cl 00-2 2.06 + 0.27 A1OO-2 12.7* 1.0
c 100-3 6.74 =!=0.34 A1OO-3 40.1 +3.6
Based on the assumed composition (see Section 2.2) and residual moisture content of dried (50 “C) resinbeads, the carbon content of beads was estimated to be approximately 70%. The overall mass lossobserved for anion resin digested for 24 hr at 95‘C was 5.5Y0. Of this overall mass loss, 3.85’%(0.7x5.5) is attributable to carbon. The TOC content of the digestate derived from sample A1OO-3,as given inTable 3.2, was found to be 4.0%. Correlation of bead mass loss and TOC of digestates for other sampleswas poor compared to the good correlation found for A1OO-3sample.
3.5 Ion Exchange Capacity of Digested Resins
The ion exchange capacity of nitric acid digested resin samples and untreated starting materials wasdetermined as described in the experimental section. Results are summarized in Table 3.3. Accuracy ofthese values is estimated from “continuing calibration verification standard” (CCV) results to be ~3’Yo.Precision is conservatively estimated to be tl .5% based on agreement of analytical duplicates.
3-3
Table 3.3 Ion Exchange Capacity of Digested Resin Samples and Starting Materials
●
Cation ResinSample ID
Vendor Spec.
Cation Resin SampleIon Exchange Capacity
(meqlgm)
4.9(dry weight basis)
Anon ResinSample ID
Vendor Spec.
Anion Resin SampleIon Exchange Capacity
(meqlgm)
3.7(dry weight basis)
co 4.62 AO 2.37
cl 4.31 Al 2.07
C2 4.47 A2 2.10
C3 4.47 A3 2.09
C60-1 4.42 A60-1 2.10
C60-2 4.46 A60-2 2.21
C60-3 4.25 A60-3 2.22
Cloo-1 3.82 A1OO-1 2.29
c 100-2 3.52 A 100-2 2.30
C1OO-3 3.04 A1OO-3 2.31
Note: All ion exchange capacity measurements (other than vendor specs) were made onresin material dried overnight at 50”C.
3.6 Thermal Analyses
DSC and TGA analyses of predigestion and post nitric acid digested resin samples were pefiormed byTodd Hart of PNNL under conditions described in the experimental section. The DSC and TGA tracesare appended to this report (Appendix A). Table 3.4 below summarizes the thermal behavior features ofthe samples observed in the temperature range of 150°C and 400”C. Weight losses and heat flows attemperatures below -1 50”C are believed to be associated with loss of residual moisture. Above -400”C,weight losses and heat flows are believed to be due to charring of the basic hydrocarbon bead matrix.Between 150°C and 400”C, weight losses and heat flows are believed to be associated with loss of ion-exchange fictional groups and possibly decomposition of nitro or nitroso organic moieties.
3-4
.
Table 3.4 Thermal Behavior of Ion Exchange Resin Samples in the Temperature Range, 150 to400”C
SampleID
coc1C2
C3
C60-1
C60-2
C60-3
Cloo-1
Cl00-2(a)
Cl00-2(b)
CIOO-3(a)
C1OO-3(b)
AO
Al
A2
A3(a)
A3(b)
A60-1(a)
A60-I(b)
A60-2(a)
A60-2(b)
‘A60-3(a)
A60-3(b)
A1OO-1(a)
A1OO-1(b)
A1OO-2(a)
A1OO-2(b)
A1OO-3(a)
A1OO-3(b)
ReactionHeat HeatFlow EstimatedWeightLossFlowOnsetTemperaturef’C) (J/g) AccompanyingThermal
Event(Y’.)
250 +111 20
258 +127 22
262 I +89 I 24 II
236 -348 25
234 -280 20
237 -668 30
167 -28$
239 -797* 26
164 +219 22
244 -534 29
245 -398 31
170 -9.2—
243 -508 29
180 -11 —
246 -388 26
179 -7.7
242 -463 29
186 -1.7 —
243 -352 30
185** -45
242** -404 28
177*** -62
241*** I -368 I 35 II
* Integrationof heat flow exothermsfrombeginningof first eventto end of secondeventyields an overallexothermof1015 J/grn.
** Integrationof heat flow exothermsfrombeginningof fwsteventto end of secondeventyields an overallexothenn of 559 J/g.
*** Integrationof heat flow exothermsfrombeginningof first eventto end of secondeventyields an overallexothermof 648 J/g.
3-5
.
,
.
.
3.7 Infrared Analysis of Nitric Acid Treated Sulfonated (Cation) and Quaternary Ammonium(Anion) Polystyrene Copolymer Ion Exchange Resins
Two ion exchange resins were treated with varying concentrations of nitric acid at various times andtemperatures followed by analysis by FTIR spectroscopy.
The treatment of the cation exchange resin (sulfonated polystyrene copolymer) with concentrated HNO~at 60 and 95 ‘C showed evidence of nitro-aromatic (Ar-NOz) formation. The anion exchange resin (alkylquaternary ammonium polystyrene copolymer) treated with concentrated HNOq at 95 ‘C showedevidence of nitro-aromatic (Ar-N02) formation. The treatment with less concentrated nitric acid ( 10MHNO~) showed no evidence of nitro-aromatic or nitro-alkyl formation. Treatment of anion exchangerwith concentrated HNO~at room temperature for lhr also showed no evidence of nitro-aromatic or nitro-alkyl formation. The cation exchange resin (sulfonated polystyrene copolymer) is discussed in the firstsection and the anion exchange resin (alkyl quaternary ammonium polystyrene copolymer) is discussedin the second section.
3.7.1 Cation Exchanger - Nitric Acid Treatment
Table 3.5 contains the temperatures and times for acid treatments of the cation exchange resin. Theinfrared spectra were performed on finely ground and dry resins using the KBr pellet method of samplepreparation (Silverstein et al. 1991).
Table 3.5 Treatment Conditions for Cation Exchange Resin Samples
Treatment lD Condltlons Sample ID(a) fresh resin, no acid co
treatment(b) 10M HNOq, 60”C, 8h *
(c) cone HNO~,60”C, 7h C60-2(d) cone HNOS,95“C, C1OO-3
24h* Sample from scoping test
(a) Fresh Resin, No Acid Treatment: The infrared spectra of the untreated cation exchange resins andthe nitric acid treated resin were measured and are shown in Figures 3.1 and 3.2. The spectrum of theuntreated fresh resin (spectrum (a) in Figures 3.1 and 3.2), contains the general features expected for ahydrated, sulfonated polystyrene polymer. The observed broad and intense absorbance in the 3600-2800cm-l region is typical of acid hydrates (Silverstein et al. 1991); absorbance at 3000 – 2900 cm-l areassigned to C-H streching mode (Silverstein et al. 1991; Lin-Vien et al. 1991); absorbance found at1650-1450 cm-l are due to substituted aromatics (Silverstein et al. 1991; Lin-Vien et al. 1991); intensebands located at 1210-1150 and 1035 cm-l are assigned to the asymmetric and symmetric sulfonate S=0stretching frequencies respectively (Silverstein et al. 1991; Lin-Vien et al. 1991). The higher energy
3-6
asymmetric S=0 band found at 1210-1150 cm-l is broad due to the fact that for all sulfonates this band isexpected to appear as a doublet.
(b) 10M HNO,, 60°C, 8hr Treatment: The infrared spectrum of the 10M nitric acid, 60°C washedcation resin (spectrum (b) in Figures 3.1 and 3.2) shows the same general features as found for theuntreated resin discussed above. Specifically, this spectrum is consistent for an aromatic sulfonated ion-exchange resin and shows no additional features. No evidence was seen by infrared spectroscopy tosuggest that either nitroalkanes or nitroaromatic complexes were produced from the resin under the 10MHNO~treatment at 60”C for 8 h.
(c) and (d) CONC HNO~, 60 °C-7hr and 90”C, 24hr Treatment: The infrared spectra for cationresin treatment with concentrated HNO~under 60”C and 7hr, and 95 ‘C and 24hr (spectra (c) and (d)respectively, Figures 3.1 and 3.2) show varying degrees of evidence for aromatic nitration of thecopolymer of the resin in addition to the general features of the untreated resin. Absorption bands fromaromatic nitrate (Ar-NOz) formation are observed in these spectra at 1530 cm-] (asymmetric N02 v) and1350 cm-l (symmetric N02 v) consistent with literature values (Silverstein et al. 1991; Lin-Vien et al.1991). There is evidence of a trace of “free” nitrate in the 95 ‘C, 24h, concentrated nitric acid treatment,in spectrum (d). The 1385 cm-i absorption band is indicative of a non-covalently bound nitrateassociated within the sample matrix. The “free” nitrate was undoubtedly left horn the treatment withconcentrated nitric acid.
3.7.2 Anion Exchanger - Nitric Acid Treatment
Table 3.6 contains the temperatures and times for acid treatments of the anion exchange resin: Theinfrared spectra of these resin samples were performed on finely ground and dry resins using the KBrpellet method of sample preparation (Silverstein et al. 1991).
Table 3.6 Treatment Conditions for Anion Exchange Resin Samples.
Treatment lD Condltlons Sample lD(a) fresh resin, no acid AO
treatment(b) 10M HNO~,60”C, 8h *
(c) cone HNOq, Alroom temp, 1hr
(d) cone HNOq,95 “C, A1OO-3
II I 24h I*Samplefrom scoping test
(a) Fresh Resin, No Acid Treatment: The infrared spectra of the untreated anion exchange resins andthe nitric acid treated resin were measured and are shown in Figures 3.3 and 3.4. The spectrum of theuntreated fresh resin (spectrum (a) in Figure 3.3 and 3.4), contain the general features expected for ahydrated, quaternary ammonium polystyrene polymer. The observed broad and intense absorbance in the3600-2800 cm-l region is typical of acid hydrates (Silverstein et al. 1991); absorbance at 3000 – 2900
3-7
cm-~are assigned to C-H stretching mode (Silverstein et al. 1991; Lin-Vien et al. 1991); absorbancefound at 1650-1450 cm-’ are due to substituted aromatics (Silverstein et al. 1991; Lin-Vien et al. 1991).
(b) 10M HNO,, 60”C, 8hr, and (c) CONC HNO,, room temp, lhr Treatment: The infraredspectrum of the 10M nitric acid, 60”C, 8hr treatment and concentrated HNO~,room temperature-1 hrtreatments (spectra (b) and (c) respectively, Figures 3.3 and 3.4) shows the same general features asfound for the untreated resin discussed above in addition to an intense band at 1385 cm-’ due to unboundnitrate. Specifically, these spectra are consistent for an aromatic quaternary substituted anion-exchangeresin loaded with “free” nitrate. The “free” nitrate denotes that the nitrate ion associated with the resin isfrom the anion exchange of nitrate for hydroxide after nitric acid treatment and not due to covalentlybound nitrate from nitration reactions. No evidence was seen by infrared spectroscopy to suggest thateither nitroalkanes or nitroaromatic complexes were produced from the resin under the 10M HNO~treatment at 60”C for 8 hr or concentrated HNO~,room temperature-1 hr treatment.
(d) CONC HNO,, 95°C, 24 hr Treatment: The infrared spectra for anion resin treatment withconcentrated HNO~under 95 “C and 24 hr (spectrum (d) Figures 3.3 and 3.4) shows evidence foraromatic nitration of the copolymer of the resin in addition to the general features of the untreated resinand associated “free” nitrate. The “free” nitrate denotes that the nitrate ion associated with the resin isfrom the anion exchange of nitrate for hydroxide after nitric acid treatment and not due to covalentlybound nitrate from nitration reactions. Absorption bands from aromatic nitrate (Ar-NOz) formation areobserved in these spectra at 1530 cm-] (asymmetric NOZv) and -1370 cm-l (symmetric NOZv) consistentwith literature values (Silverstein et al. 1991; Lin-Vien et al. 1991). The 1370 cm-] symmetric NOZvband is a shoulder on the more intense “free” nitrate absorption band (1385 cm-’).
3-8
.
.
0
sulfonated polystyrene copolymer,cation exchange resin
(a) fresh resin, no acid treatment
I acid wash, 60°C, 8 hY
1 I.
Ail
J (c) resin, cone HN03 “free” NO:60°C, 7 h
aromatic
hitL/ W-’w ‘wI (d) resin, cone HN03
95°C, 24 h
JI
4000 3000 2000 1000
Wavenumber, cm-qt
Figure 3.1 Infrared Spectra of Sulfonated Polystyrene Copolymer, Cation Exchange Resin;4000 – 400 cm-i Region. Resin was treated as follows (a) fresh resin, no acidtreatment (b) 10M HNOS,60”C, 811.(c) cone HNO~,60”C, 711,(d) cone HNO:,95 ‘C, 24h
3-9
.
,
sulfonated polystyrene copolymer,cation exchange resin
1 1 Isulfonate S=0 u
/“7’assymsym
no acid treatment
.
A (b) resin, IOM I-IN03
acid wash, 60”C, 8 k
A
aromatic-N02
~
(c) resin, cone HN03assym u sym v
treatment, 60”C, 7 h
(d) resin, cone HN03
treatment, 95”C, 24 h
,2000 1500 1000 500
Wavenumber, cm-q
Figure 3.2 Infrared Spectra of Sulfonated Polystyrene Copolymer, Cation Exchange Resin;2000 – 400 cm-’ Region. Resin was treated as follows (a) fresh resin, no acidtreatment (b) 10M HN03, 60°C, 811,(c) cone HN03, 60°C, 711,(d) cone HN03,95”C, 24h
3-1o
quaternary ammonium polystyrene copolymer,anion exchange resin
a
substitutedaromatic II
A
(a) fresh resin, no acid treatment
T
“free” NO
(b) resin, IOM FIN03 acid wash, 6tYC, 8 h )( /
(c) resin, cone HN03
room temperature, 1 hr /[
aromatic-N02assym u\
(d) resin, cone HN03
95°C, 24 hr \
sym u (sh
/ aromaticN02
4000 3000 2000 1000
Wavenumber, cm-f
Figure 3.3 Infrared Spectra of Quaternary Ammonium Polystyrene Copol ymer, AnionExchange Resin; 4000-400 cm-’ Region. Resin was treated as follows(a) fresh resin, no acid treatment (b) 10M HN03, 60”C, 811,(c) cone HN03,room temp, 1h (d) cone HN03, 95 “C, 24h
3-11
quaternary ammonium polystyrene copolymer,anion exchange resin
substitutedaromatic u
(a) fresh resin,no acid treatment
(b) resin, 10M HN03
acid wash, 60°C, 8 h
(c) resin, cone HN03
J~ room temperature, 1 h
aromatic-N02assym u
\. k’aromatic-N02sym v (sh)
(d) resin, cone HN03
95”C, 24 h
2000 1500 1000 500
VVavenumber, cm-q
Figure 3.4 Infrared Spectra of Quaternary Ammonium Polystyrene Copolymer, AnionExchange Resin; 2000-400 cm-’ Region. Resin was treated as follows(a) fresh resin, no acid treatment (b) 10M HNO,, 60°C, 811,(c) cone HNO,,room temp, 1h (d) cone HNO:, 95 “C, 241~
3-12
4.0 SUMMARY
Results for tests performed in the course of this work are summarized in Table 4.1 below.
Table 4.1 Results Summary
OtherObservations-Ion Exchange DigestateTOC DSCResults(a) Presenceof”) Comments
Sample Capacity(maq/g) (mgC/gresin) (J/g) NitroaromaticsID
co 4.62 NIA +111 no startingmaterial
c1 4.31 1.1 +127 na no obviousgas evolutiSupernatesyellow;dar
C2 4.47 0.8 +9.0 na with largerexposure
C3 4.47 1.2 +89 na
C60-1 4.42 1.4 +102 na SomeNO, evolvedasreactionmixtureheats
C60-2 4.46 2.2 -154 na
C60-3 4.25 0.7 -348 na
Cloo-1 3.82 1.9 -280 na
C1OO-2 3.52 2.1 -674 na
CIOO-3 3.04 6.7 -1015 yes
AO 2.37 NIA +219 no startingmaterial
Al 2.07 1.8 -534 no Resin floats in coneHlBrowngas (NO~ evol
A2 2.10 1.3 -398 na upon contactwith coneHNOq.MoreNO, at hi,
A3 2.09 2.7 -517 na T. Digestatesnot as ye.
A60-1 2.10 2.2 -399 na as correspondingcatio]resin digestates
A60-2 2.21 2.2 -471 na
A60-3 2.22 2.9 -354 na
A1OO-1 2.29 3.4 -354 na
A1OO-2 2.30 13 -490 na
A1OO-3 2.31 40 -648 yes
(a) Heat absorbed(+) or liberated(-) in the 150°Cto 400”Crange(b) From FTIR measurementN/A = not applicable;na = not analyzed.
4-1
5.0 CONCLUSIONS
Significant changes in measured properties of resin beads were obsetied only at the most extremedigestion conditions (95 °C;7and24hr). Atlessrigorous conditions, onlyvery small losses of ionexchange functionality were seen. The extent of resin bead matrix disruption, as measured by TOC ofdigestion filtrates, was only significant at the most extreme processing conditions.
Radionuclides sorbed or associated with the organic ion exchange resins (OIER) can restrict disposal ofthis solid to the Environmental Restoration Disposal Facility (ERDF). Solids to be delivered to theERDF must meet Waste Acceptance Criteria (WAC) for radionuclide concentrations (ERDF WasteAcceptance Criteria, BHI-00139, Rev. 2, Table 4-l). The radionuclides most likely controlling theERDF acceptance of K Basins’ solid residues are *37CS(32 Ci/m3 or 32 pCi/mL) and the transuranics(TRU; 100 nCi/g). The transuranic isotopes have individual limits; 24’Amis 0.05 ”Ctim3(50 nCi/mL),238F%is 1.5 Ci/m3 (1,500 nCi/mL), and 239Puand 240Puare each 0.029 Ci/m3 (29 nCi/mL). The effectiveuranium limit for disposal to ERDF, 0.0026 g U/mL 2,may also foreclose ERDF disposal of certain KBasins residues. The radionuclide activities of OIER retrieved from the K Basins must bedecontaminated to these levels to allow ERDF disposal. The TRU content of rinsed OIER retrieved fromthe K East Basin (Sample KES-H-08) has been found to range from about 650 to 850 nCi/g dried resin.
“*37CSand 0.003 g U per gram of dried resin (Schmidt et al.The unrinsed OIER also contains 144 pCI1999).
Based on the above radionuclide concentrations in the actual OIER in KE Basin sludge and the levels ofdefunctionalization achieved during the cold OIER testing (i.e., 3% to 34% defunctionization for thecation and 3°/0to 13°/0for the anion resin material), acid digestion in 15.7 ~ HN03 is predicted to beinsufficient to decontaminate the OIER to the levels necessary to meet the ERDF WAC. However,recent results from digestion of actual OIER from KE Basin sludge in 10 ~ HN03 indicate that higherlevels of decontamination were achieved than predicted from the cold OIER digestion (Schmidt et al.1999). For sieved and rinsed OIER from sample KES-H-08, at ratios of about 1 g resin per 20 mL acid,about 80°/0of the uranium, .25°/0of the plutonium, and 70°/0or more of the americium activity wereremoved. Cesium distributions were not measured but high removals would be expected. Residualactivities in the acid-treated OIER were 160 to 340 nCi/gTRU(110-190 nCi 239’240Ptdg,20-120
“137Cs/g(uranium concentrations were not detectable but likely were nearnCixlAm/g), and 1.5-34 pCl0.0003 g U/g based on ~ tests at higher loadings).
The differences in results obtained from the digestions performed on the cold OIER and the digestionsperformed on the hot OIER collected from KE Basin sludge can be partially attributed to the followingfactors: 1) the cold testing examined defunctionalization, whereas the decontamination achieved duringthe hot testing included the effects ofboth defimctionalization and displacement, 2) the initialradionuclide concentrations associated with the hot OIER may have included particulate mater that waseasily digested (i.e., possibly inflating the initial concentrations of the OIER), and 3) the ion exchange
2 The ERDF WAClimit for 23*Uand its daughters is 0.012 Ci/m3. With 8 alphaand 6 beta decays in the 23*Udecaychainand a specificactivityof 3.36x10-7Ci 23*U/g, the specificactivityof the 23*Uchain is 4.7x10-6Ci/g. TheERDF limit for 23*Uthus is 0.00256g 23sU/mL.The ERDFlimit for 235U(daughtersnot included)is 0.0027 Ci/m3and the specificactivity of 235Uis 2.16x10*Ci/g. Ilus the ERDFlimit for ‘5U is 0.0013g 235U/mL.The relativeIirnitsof the two uranium isotopes,and the nominal0.7%enrichmentof the K Basinssludge,mean that 23*Uconcentrationlimits ERDF disposal. Therefore,the effectiveuraniumlimit for disposalto ERDF is 0.0026g U/mL.
5-1
capacity in the cold work was determined with Na+ (cation resin) and Cl- (anion resin). The bindingafllnity of OIER for 137CS,239’240Pu,and 241Amdiffer from that of Na+and Cl-.
Based on the results obtained for the digestions of the hot OIER, it may be possible to remove cesium,uranium, and americium to meet ERDF criteria by performing multiple washing contacts of retrievedOIER with strong HN03. However, such an approach would be less successful for plutonium wherestrong anion exchange sorption occurs at high HN03 concentrations and strong cation exchange sorptionoccurs at low HNO~concentrations, especial considering that very little defimctionalization occurs toeither the anion or cation resin. Consequently, a more sophisticated leaching approach will likely berequired to decontaminate the OIER to the levels necessary to meet the ERDF WAC.
FTIR spectra of digested resins show evidence for formation of small amounts of nitroaromaticcompounds (nitrated resin matrix). Thermal analyses suggest that nitric acid treated resin beads canundergo exotherrnic decomposition reactions in the 160“C to 4000C temperature range. The largestexothermic event(1015 J/g) was observed for sample C100-3. These results indicate that some level ofsafety evaluation will likely be required if the OIER will be digested or leached with nitric acid. Afternitric acid leaching or digestion, it maybe necessary to contact the OIER with base to hydrolyzenitroaromatics and neutralize and remove residual acid.
Acknowledgments
Contributors to this report include SA Bryan, TR Hart, RL Sell, SO Slate, LMP Thomas, andGK Ruebsamen.
5-2
6.0 REFERENCES
*
&
*
ERDF 1997. ERDF Waste Acceptance Criteria, BHI-00139, Rev. 2, Table 4-1.
Hatch, H. J. 1997. “K Basin Sludge Storage and Disposal Recommendation.” Letter to J. D. Wagoner,FDH-9755700. Fluor Daniel Hanford, Inc., Richkmd, Washington.
Lin-Vien, D., N. B. Colthup, W. G. Fateley, J. G. Grasselli. 1991. “Infrared and Raman CharacteristicFrequencies of Organic Molecules” Academic Press, Inc. New York.
Makenas, B. J., T. L. Welsh, R. B. Baker, E. W. Hoppe, A. J. Schmidt, J. Abref~, J. M. Tingey, P. R.Bred%and G. R. Golcar. 1997. “Analysis of Sludge from Hanford K East Basin Canisters.” HNF-SP-1201, DE&S Hanford, Inc., Richland, Washington.
Makenas, B. J., T. L. Welsh, R. B. Baker, D. R. Hansen, and G. R. Golcar. 1996. “Analysis of Sludgefrom Hanford K East Basi Floor and Weasel Pit.” WHC-SP- 1182, Westinghouse Hanford Company,Richland, Washington, April 1996.
Packer, M. J. 1998. “K Basins Sludge Inventory Composition.” HNF-SD-T1-053, Rev. O,DE&SHanford, Inc., Richland, Washington.
Schmidt, A. J., K. L. Silvers, P. R. Bredt, C. H. Delegard, E. W. Hoppe, J. M. Tingey, A. H. Zacher, T. L.Welsh, and R. B. Baker. 1999. “Supplementary Information on K-Basin Sludges.” HNF-2367, Rev. O.Fluor Daniel Hanford, Inc., Richland, Washington.
Silvers, K. L. 1997. “Transmittal of Fiscal Year 1998 Cold Testing Work Plan in Support of K BasinSludge Condition System Process Development.” Letter Number 28510-03, to R. P. Omberg (DE&S)from K. L. Silvers, November 6, 1997, Pacific Northwest National Laboratory, Rlchkmd, Washington.
Silverstein, R. M., G. C. Bassler, T. C. Morril. 1991. “ Spectrometric Identification of OrganicCompounds” 5* Edition. John Wiley and Sons, Inc., New York.
6-1
Appendix A
Thermal Gravimetric Analysis (TGA) and Differential Scanning Calorimetry(DSC) Traces for Nitric Acid Digested Purolite Ion Exchange Resin Samples
NETZSCH-Ger!tlebauGmbHThermalAnalysis—.——..—.———— ——.. —.-— .——.—..-..—.. _—_. ———_ ..——.-. .-. .-. ———— . —.—— ...-. ..______
DSClmWlmg TG1%
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
100 200 300 400 500 600 700
TemWrature/eC——. - ... . ..———. ..— _ . _.__ .—_- . _______._-_,INSTRUMENT STA 409C SAMPLE
.———C-ORESIN
—. —.. —-—...-. . ________11,200 mg MODWTYPE OF MEAS.:
FILE: co REFERENCE: empty.S~P+corr.
0.000 mg SEGM:PROJECT RESIN MATERIALIDENTITW C-ORESIN
C-ORESIN CRUC:CORR / TEMP.CAL.-/SENS-FILE:
DSC/TG pan A1203BLANK.BSSI1.96.TSSII -96.ESS ATMOS,: N2115%
DATE/TIME: 19.02.9614:12 RANGE 20 *C/10.O(Kfmin)/750 *C TG-CORR/M.RANGE:LABORATORY: flattelle SAMPLE CARJTC:
020/50DSC(/TG) HIGH RG 2/S DSC-CORRIM.RANGE:
OPERATOR; _.-.-. .IRI!.. . . . RWWK-..-. . ... .... ... .. . . . .. .. .. . ... ..... . ... . .. . . .._._ .,_ ,..,_. . . .020/500
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STAhamp.+corr.empty 0.000 mg
MATERIAL C2 resinSEGM: 1/1CRUC:
CORR /TEMP. CAL.-/SENFlL12l2 BLANK.BSS11-98.TSSII-98 .ESSDSC/TG pan AJ203
ATMOS.: N2/15%RANG12 20 “C/10 .O(Klmln)/750 “C TG-CORRIM.RANGE:SAMPLE CARJTC:
020/50DSC(fTG) HIGH RG 2/S DSC.CORWM.RANGE 02W500
.... EEM&. . ... .. ....... ... ... .... ... ... ... . . . ,._-,... . .. . . . . . . ... .. . . . . . . . . . ----- . . . . . . . . ..
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Figure A.3 TGA and DSC Traces for Sample C2
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STA 409CC3ResinC3 resin24.02,9808:35BattelleTR!+. . ... .
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REMARK-.. . .. . ..... . . .... . ... . . . ..:.,.. :.... . . . . . ..- .,
Figure A.4 TGA and DSC Traces for Sample C3
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20 “Clt 0.O(K/mln)/750 “CDSC(/TG) MIDDLE RG 2/K
--—l--~- ‘--
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.. . ..- ..12,200 mg0.000 mg
90
80
70
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40
30
.-—-.———-—- ..----- ., _____._ .._- . .MODE/TYPE OF MEAS.: STAkIamD.
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Figure A.8 TGA and DSC .Traces for Sample. C 100-1
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..- ——. . . . ........_——__— Temperature l~C.._-.._... . . . . .. . . . . .+ —--------------- . . ._--_ .-.. --_ . ...-INSTRUMENT
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FILE C1OO-2 REFERENCE 0.000 mg~;~amp.
PROJECT RselnSEGM:
MATERIAL CIOO-2 Resin CRUCIDENTITY CIOO-2 Resin CORR I TEMP.CAL.-ISENS-FILE
DSC/TG pan A1203---/97091 9.TSS1970919.ESS ATMOS.: n2125
DATWTIME 06.03.9815:35 RANGG 20 ●CHO.O(K/min)1750*C TG-CORRIM.RANGELABORATORY BaUelle SAMPLE CARJTC:
000/500DSC(/TG) MIDDLE RG 21K DSC-CORWM.RANGE 000/5000
OPERATOR:_. ... . _ . trt! . . . . REIAR~ .._ .-.. _._. --- .. .. .. . . . . . .. . . . . . . . .. . . .. .. .. . .. . . .-_-.,. . . . ..
Figure A.9 TGA and DSC Traces for Sample C1OO-2
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INSTRUMENT STA 409C SAMPLE ‘—-—--”--” ‘---” “C1OO-3RESIN 7.300 mgREFERENCE emply 0.000 mgMATERIAL C1OO-3RESIN I
FILE C1OO-3PROJECT RESIN1DENWI% CIOO-3 RESINDATEfTIME: 19.02.9811:32LABORATORY BatlelleOPERATOR: T5H-.. . ... . . . . .
CORR; TEMP.CAL.-ISENS-FILE BLANK.BSSII-98.TSSI1-98.ESSRANGE 20 “Cl10.O(K/mln)1750 “CSAMPLE CAR.~C: DSCUTG) HIGH RG 2/S
Km
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Figure A.1O TGA and DSC Traces for Sample C1OO-3
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..-.. ..—.————.—.-—. .— —— .... ————._____________ ________ ....-. ——..—_.
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INSTRUMENT STA 409C SAMPLE AOresin
FILE AO REFERENCE7.000 mg MODEM’PE OF MEAS.:
emplySTAJsamp.+corr.
PROJECT Resin MATERIAL0.000 mg SEGM: 1/1
AOresin CRUC DSCITG pan At203IDENTITY: AOresinDATWTIME:
CORR I TEMP.CAL.-ISENS-FILE BLANK.BSSI1-98.TSSI1 -96.ESS ATMOS.: N2115%18.02.9809:22 RANGE
LABORATORY20 *CMO.O(tVmin)/750“C TG-CORRIM.RANGEt
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Figure A.11 TGA and DSC Traces for Sample AO
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12.100mgempty 0.000 mg
MATERIAL A60-1 resin~jtl~ TEMP.CAL.-ISENS-FILE BIANKS3SS11-98.TSSII -96.ESS
20 “Cl10.O(K/min)/750 ‘CSAMPL~ CAR./lC: DSC(fTG) HIGH RG 21S
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Figure A.15 TGA and DSC Traces for Sample A60-1
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20 *Cl10.0(l@in)f750 ●CSAMPLE CARJTC: DSCUTG) HIGH RG 2/S
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