陶瓷固化体的浸出行为及其机理
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摘要
高放废物(HLW)在深地质处置后,其中的放射性核素有可能浸出并伴随地下水循环进入人类环境。这是固化体中放射性核素进入生物圈最可能的途径,因此HLW固化体的化学稳定性是固化基材筛选的主要依据。陶瓷固化体作为第二代HLW固化体,具有长程有序的特点,相比玻璃固化体,更容易定量表征,这对于固化体浸出机理的研究有着重要的意义。然而陶瓷固化体的浸出机理与评价方法研究都处于起步阶段,也缺乏被处置库接收的标准。为规范/建全陶瓷固化体化学稳定性评价方法,认识放射性核素的浸出机制,本文概述了核废物固化体化学稳定性研究方法、研究重点;总结了相关陶瓷的水热蚀变研究现状,分析了其中核素的浸出率;探讨了影响因素及其影响方式;最后归纳了目前提出的浸出机制以及存在的问题。
The radionuclides in high-level radioactive waste(HLW) forms may be leached out over geological time and enter the human environment with groundwater circulation after deep geological disposal. This is likely the potential way for radionuclides to enter the biosphere. Therefore, the long-term chemical durability of HLW waste forms is the key issue for selecting suitable waste forms. Ceramic waste forms, regarded as the second generation of HLW forms, are of long-range ordered structures, whose physical properties can be easily characterized quantitatively. It is of great importance and significance to study the leaching mechanism of ceramic waste forms. However, not only the studies of leach mechanisms, but also the evaluation methods of ceramic waste forms are in their infancy. There is also lack of the standards of ceramic waste forms received by the repository. The present paper summarizes the research methods and key points of chemical durability, reviews the research status of hydrothermal alteration of related ceramics, and analyzes the leaching rate of radionuclides. In addition, the paper also discusses the influencing factors and their influencing modes, and finally concludes the leaching mechanisms and existing problems.
The radionuclides in high-level radioactive waste(HLW) forms may be leached out over geological time and enter the human environment with groundwater circulation after deep geological disposal. This is likely the potential way for radionuclides to enter the biosphere. Therefore, the long-term chemical durability of HLW waste forms is the key issue for selecting suitable waste forms. Ceramic waste forms, regarded as the second generation of HLW forms, are of long-range ordered structures, whose physical properties can be easily characterized quantitatively. It is of great importance and significance to study the leaching mechanism of ceramic waste forms. However, not only the studies of leach mechanisms, but also the evaluation methods of ceramic waste forms are in their infancy. There is also lack of the standards of ceramic waste forms received by the repository. The present paper summarizes the research methods and key points of chemical durability, reviews the research status of hydrothermal alteration of related ceramics, and analyzes the leaching rate of radionuclides. In addition, the paper also discusses the influencing factors and their influencing modes, and finally concludes the leaching mechanisms and existing problems.
引文
[1]WANGJ,SUR,CHENWM,etal.Deepgeologicaldisposalof high-levelradioactivewastesinChina.ChineseJournalofRock Mechanics&Engineering, 2006, 25(4):649–658.
[2]EWING R C. Long-term storage of spent nuclear fuel. Nature Materials, 2015, 14(3):252–257.
[3]谭宏斌,李玉香.放射性废物固化方法综述.云南环境科学,2004, 23(4):1–3.
[4]CHEN F Y, JIE W Q, DELBERT E D. Corrosion property of iron phosphatesimulatedHLWmelts.JournalofInorganicMaterials,2000, 15(4):653–659.
[5]EWING R C. Nuclear waste forms for actinides. Proc. Nat. Acad.Sci., 1999, 96(7):3432–3439.
[6]WANG L L, XIE H, CHEN Q Y, et al. Synthesis and charaterizationofthorium-dopedNd2Zr2O7pyrochlore.JournalofInorganic Materials, 2015, 30(1):81–86.
[7]DONALD I W, METCALFE B L, TAYLOR R N J. The immobilization of high level radioactive wastes using ceramics and glasses.Journal of Materials Science, 1997, 32(22):5851–5887.
[8]何涌.高放废液玻璃固化体和矿物固化体性质的比较.辐射防护, 2001, 21(1):43–47.
[9]HAYWARDPJ,CECCHETTOEV.Developmentof sphene-basedglassceramicstailoredforcanadianwastedisposal conditions. Mater. Res. Soc. Symp. Proc., 1981, 6:91–97.
[10]盛嘉伟,罗上庚,汤宝龙.高放废液的玻璃固化及固化体的浸出行为与发展情况.硅酸盐学报, 1997, 25(1):83–88.
[11]张华.高放固化体处置条件下的浸出和模型研究.北京:中国原子能科学研究院博士学位论文, 2004.
[12]MENDELJE.NuclearWasteMaterialsCharacterizationCenter.Topp S V, Semiannual progress report, PNL-5683 America, 1985:1–54.
[13]C1285-02,Standardtestmethodsfordeterminingchemicaldurabilityofnuclear,hazardous,andmixedwasteglassesandmultiphase glass ceramics:The product consistency test(PCT).
[14]吴萍萍,张骋,徐海芳,等.玻璃固化体抗浸蚀性能实验研究进展.现代技术陶瓷, 2010, 31(3):28–34.
[15]EJ/1186-2005,放射性废物体和废物包的特性鉴定.
[16]K?HLERSJ,HAROUIYAN,CHA?RATC,etal.Experimental studiesofREEfractionationduringwater–mineralinteractions:REEreleaseratesduringapatitedissolutionfrompH2.8to9.2.Chem. Geol., 2005, 222(3/4):168–182.
[17]ICENHOWERJP,STRACHANDM,LINDBERGMJ,etal.Dissolution Kinetics of Titanate-based Ceramic Waste Forms:ResultsfromSingle-passFlowTestsonRadiationDamagedSpecimens. United States:N. p., DOI:10.2172/15003935.
[18]HAYWARD P J, WATSON D G, MCILWAIN A K, et al. Leaching studiesofspheneceramicscontainingsubstitutedradionuclides.Nuclear and Chemical Waste Management, 1986, 6(1):71–80.
[19]GEISLERT,PIDGEONRT,KURTZR,etal.Experimentalhydrothermalalterationofpartiallymetamictzircon.Am.Mineral.,2003, 88(10):1496–1513.
[20]TOULHOATN,TOULHOATN,MONCOFFREN,etal.Enhancement of zirconolite dissolution due to water radiolysis. MRS Proceedings, 2006, 985:0985–NN09–04.
[21]BERGER A, GNOS E, JANOTS E, et al. Formation and composition of rhabdophane, bastn?site and hydrated thorium minerals during alteration:implicationsforgeochronologyandlow-temperature processes. Chem. Geol., 2008, 254(3):238–248.
[22]张华,杨建文,李宝军,等.富烧绿石在模拟处置条件下的浸出行为研究.核化学与放射化学, 2004, 26(2):65–70.
[23]FRUGIER P, MARTIN C, RIBET I, et al. The effect of compositionontheleachingofthreenuclearwasteglasses:R7T7,AVM and VRZ. J. Nucl. Mater., 2005, 346(2/3):194–207.
[24]PIRLETV.Influenceofthenear-fieldconditionsonthemobile concentrationsofNpandTcleachedfromvitrifiedHLW.MRS Proceedings, 2004, 824:CC7.5.
[25]李鹏,丁新更,杨辉,等.钙钛锆石玻璃陶瓷体的晶化和抗浸出性能.硅酸盐学报, 2012, 40(2):324–328.
[26]盛嘉伟,罗上庚,汤宝龙,等.90-19/U模拟高放玻璃固化体的浸出特性评价.核化学与放射化学, 1995, 17(1):1–6.
[27]SHINHY,PARKH,YOOK.Theeffectoftemperatureonthe leaching of monazite obtained from heavy mineral sands. Geosystem Engineering, 2012, 15(2):118–122.
[28]HAWTHORNEFC,GROATLA,RAUDSEPPM,etal.Alphadecay damage in titanite. Am. Mineral., 1991, 76(3/4):370–396.
[29]滕元成,曾冲盛,任雪潭,等.合成榍石的化学稳定性.原子能科学技术, 2010, 44(1):14–19.
[30]GEISLERT,ZHANGM,SALJEEKH.Recrystallizationofalmostfullyamorphouszirconunderhydrothermalconditions:an infraredspectroscopicstudy.J.Nucl.Mater.,2003,320(3):280–291.
[31]RIZVANOVA N G, GAIDAMAKO I M, LEVCHENKOV O A, et al. Interaction of metamict zircon with fluids of various composition. Geochemistry International, 2007, 45(5):465–477.
[32]TRIBET M, TOULHOAT N, MONCOFFRE N, et al. Leaching of a zirconolite ceramic waste-form under proton and He2+irradiation.Radiochimica Acta, 2008, 96(9/10/11):619–624.
[33]P?ML P, GEISLER T, COBOS-SABATéJ, et al. The mechanism ofthehydrothermalalterationofcerium-andplutonium-doped zirconolite. J. Nucl. Mater., 2011, 410(1):10–23.
[34]P?ML P, MENNEKEN M, STEPHAN T, et al. Mechanism of hydrothermalalterationofnaturalself-irradiatedandsyntheticcrystallinetitanate-basedpyrochlore.Geochim.Cosmochim.Acta,2007, 71(13):3311–3322.
[35]MITAMURAH,MATSUMOTOS,STEWARTMWA,etal.?-Decaydamageeffectsincurium-dopedtitanateceramiccontaining sodium-free high-level nuclear waste. J. Am. Ceram. Soc.,1994, 77(9):2255–2264.
[36]EWING R C, HAAKER R F, LUTZE W. Leachability of zircon as afunctionofalphadose.MRSOnlineProceedingLibrary,1980,11(1):389–397.
[37]BEGG B D, HESS N J, WEBER W J, et al. Heavy-ion irradiation effectsonstructuresandaciddissolutionofpyrochlores.J.Nucl.Mater., 2001, 288(2):208–216.
[38]GEISLERT,TRACHENKOK,RíOSS,etal.Impactof self-irradiationdamageontheaqueousdurabilityofzircon(Zr SiO4):implicationsforitssuitabilityasanuclearwasteform.Journal of Physics Condensed Matter, 2003, 15(37):1597–1605.
[39]SALJEEKH,CHROSCHJ,EWINGRC.Is“metamictization”ofzirconaphasetransition?Am.Mineral.,1999,84(7/8):1107–1116.
[40]TRACHENKO K, DOVE M T, SALJE E K H. Reply to comment on'largeswelling andpercolationinirradiatedzircon'. Journal of Physics Condensed Matter, 2003, 15(15):6457–6471.
[41]TROCELLIERP,DELMASR.Chemicaldurabilityofzircon.NuclearInstandMethodsinPhysicsResearchB,2001,181(1):408–412.
[42]GEISLER T, PIDGEON R T, BRONSWIJK W V, et al. Transport ofuranium,thorium,andleadinmetamictzirconunderlowtemperaturehydrothermalconditions.Chem.Geol.,2002,191(1):141–154.
[43]GEISLERT,RASHWANT,RAHNAA,etal.Low-temperature hydrothermal alteration of natural metamict zircons from the eastern desert, Egypt. Mineralogical Magazine, 2003, 67(3):485–508.
[44]GEISLER T, SCHALTEGGER U, TOMASCHEK F. Re-equilibration of zircon in aqueous fluids and melts. Elements, 2007, 3(1):43–50.
[45]ZHANGM,MADDRELLER,ABRAITISPK,etal.Impactof leachonleadvanado-iodoapatite[Pb5(VO4)3I]:aninfraredand Ramanspectroscopicstudy.MaterialsScience&EngineeringB,2007, 137(1):149–155.
[46]GEISLER T, P?ML P, STEPHAN T, et al. Experimental observation of an interface-controlled pseudomorphic replacement reaction inanaturalcrystallinepyrochlore.Am.Mineral.,2005,90(10):1683–1687.
[47]GEISLERT,ULONSKAM,SCHLEICHERH,etal.Leaching anddifferentialrecrystallizationofmetamictzirconunderexperimentalhydrothermalconditions.Contrib.Mineral.Petrol.,2001,141(1):53–65.
[48]LIANJ,ZUXT,KUTTYKVG,etal.Ion-irradiation-induced amorphization of La2Zr2O7 pyrochlore. Phys. Rev. B, 2002, 66(66):054108–1–5.
[2]EWING R C. Long-term storage of spent nuclear fuel. Nature Materials, 2015, 14(3):252–257.
[3]谭宏斌,李玉香.放射性废物固化方法综述.云南环境科学,2004, 23(4):1–3.
[4]CHEN F Y, JIE W Q, DELBERT E D. Corrosion property of iron phosphatesimulatedHLWmelts.JournalofInorganicMaterials,2000, 15(4):653–659.
[5]EWING R C. Nuclear waste forms for actinides. Proc. Nat. Acad.Sci., 1999, 96(7):3432–3439.
[6]WANG L L, XIE H, CHEN Q Y, et al. Synthesis and charaterizationofthorium-dopedNd2Zr2O7pyrochlore.JournalofInorganic Materials, 2015, 30(1):81–86.
[7]DONALD I W, METCALFE B L, TAYLOR R N J. The immobilization of high level radioactive wastes using ceramics and glasses.Journal of Materials Science, 1997, 32(22):5851–5887.
[8]何涌.高放废液玻璃固化体和矿物固化体性质的比较.辐射防护, 2001, 21(1):43–47.
[9]HAYWARDPJ,CECCHETTOEV.Developmentof sphene-basedglassceramicstailoredforcanadianwastedisposal conditions. Mater. Res. Soc. Symp. Proc., 1981, 6:91–97.
[10]盛嘉伟,罗上庚,汤宝龙.高放废液的玻璃固化及固化体的浸出行为与发展情况.硅酸盐学报, 1997, 25(1):83–88.
[11]张华.高放固化体处置条件下的浸出和模型研究.北京:中国原子能科学研究院博士学位论文, 2004.
[12]MENDELJE.NuclearWasteMaterialsCharacterizationCenter.Topp S V, Semiannual progress report, PNL-5683 America, 1985:1–54.
[13]C1285-02,Standardtestmethodsfordeterminingchemicaldurabilityofnuclear,hazardous,andmixedwasteglassesandmultiphase glass ceramics:The product consistency test(PCT).
[14]吴萍萍,张骋,徐海芳,等.玻璃固化体抗浸蚀性能实验研究进展.现代技术陶瓷, 2010, 31(3):28–34.
[15]EJ/1186-2005,放射性废物体和废物包的特性鉴定.
[16]K?HLERSJ,HAROUIYAN,CHA?RATC,etal.Experimental studiesofREEfractionationduringwater–mineralinteractions:REEreleaseratesduringapatitedissolutionfrompH2.8to9.2.Chem. Geol., 2005, 222(3/4):168–182.
[17]ICENHOWERJP,STRACHANDM,LINDBERGMJ,etal.Dissolution Kinetics of Titanate-based Ceramic Waste Forms:ResultsfromSingle-passFlowTestsonRadiationDamagedSpecimens. United States:N. p., DOI:10.2172/15003935.
[18]HAYWARD P J, WATSON D G, MCILWAIN A K, et al. Leaching studiesofspheneceramicscontainingsubstitutedradionuclides.Nuclear and Chemical Waste Management, 1986, 6(1):71–80.
[19]GEISLERT,PIDGEONRT,KURTZR,etal.Experimentalhydrothermalalterationofpartiallymetamictzircon.Am.Mineral.,2003, 88(10):1496–1513.
[20]TOULHOATN,TOULHOATN,MONCOFFREN,etal.Enhancement of zirconolite dissolution due to water radiolysis. MRS Proceedings, 2006, 985:0985–NN09–04.
[21]BERGER A, GNOS E, JANOTS E, et al. Formation and composition of rhabdophane, bastn?site and hydrated thorium minerals during alteration:implicationsforgeochronologyandlow-temperature processes. Chem. Geol., 2008, 254(3):238–248.
[22]张华,杨建文,李宝军,等.富烧绿石在模拟处置条件下的浸出行为研究.核化学与放射化学, 2004, 26(2):65–70.
[23]FRUGIER P, MARTIN C, RIBET I, et al. The effect of compositionontheleachingofthreenuclearwasteglasses:R7T7,AVM and VRZ. J. Nucl. Mater., 2005, 346(2/3):194–207.
[24]PIRLETV.Influenceofthenear-fieldconditionsonthemobile concentrationsofNpandTcleachedfromvitrifiedHLW.MRS Proceedings, 2004, 824:CC7.5.
[25]李鹏,丁新更,杨辉,等.钙钛锆石玻璃陶瓷体的晶化和抗浸出性能.硅酸盐学报, 2012, 40(2):324–328.
[26]盛嘉伟,罗上庚,汤宝龙,等.90-19/U模拟高放玻璃固化体的浸出特性评价.核化学与放射化学, 1995, 17(1):1–6.
[27]SHINHY,PARKH,YOOK.Theeffectoftemperatureonthe leaching of monazite obtained from heavy mineral sands. Geosystem Engineering, 2012, 15(2):118–122.
[28]HAWTHORNEFC,GROATLA,RAUDSEPPM,etal.Alphadecay damage in titanite. Am. Mineral., 1991, 76(3/4):370–396.
[29]滕元成,曾冲盛,任雪潭,等.合成榍石的化学稳定性.原子能科学技术, 2010, 44(1):14–19.
[30]GEISLERT,ZHANGM,SALJEEKH.Recrystallizationofalmostfullyamorphouszirconunderhydrothermalconditions:an infraredspectroscopicstudy.J.Nucl.Mater.,2003,320(3):280–291.
[31]RIZVANOVA N G, GAIDAMAKO I M, LEVCHENKOV O A, et al. Interaction of metamict zircon with fluids of various composition. Geochemistry International, 2007, 45(5):465–477.
[32]TRIBET M, TOULHOAT N, MONCOFFRE N, et al. Leaching of a zirconolite ceramic waste-form under proton and He2+irradiation.Radiochimica Acta, 2008, 96(9/10/11):619–624.
[33]P?ML P, GEISLER T, COBOS-SABATéJ, et al. The mechanism ofthehydrothermalalterationofcerium-andplutonium-doped zirconolite. J. Nucl. Mater., 2011, 410(1):10–23.
[34]P?ML P, MENNEKEN M, STEPHAN T, et al. Mechanism of hydrothermalalterationofnaturalself-irradiatedandsyntheticcrystallinetitanate-basedpyrochlore.Geochim.Cosmochim.Acta,2007, 71(13):3311–3322.
[35]MITAMURAH,MATSUMOTOS,STEWARTMWA,etal.?-Decaydamageeffectsincurium-dopedtitanateceramiccontaining sodium-free high-level nuclear waste. J. Am. Ceram. Soc.,1994, 77(9):2255–2264.
[36]EWING R C, HAAKER R F, LUTZE W. Leachability of zircon as afunctionofalphadose.MRSOnlineProceedingLibrary,1980,11(1):389–397.
[37]BEGG B D, HESS N J, WEBER W J, et al. Heavy-ion irradiation effectsonstructuresandaciddissolutionofpyrochlores.J.Nucl.Mater., 2001, 288(2):208–216.
[38]GEISLERT,TRACHENKOK,RíOSS,etal.Impactof self-irradiationdamageontheaqueousdurabilityofzircon(Zr SiO4):implicationsforitssuitabilityasanuclearwasteform.Journal of Physics Condensed Matter, 2003, 15(37):1597–1605.
[39]SALJEEKH,CHROSCHJ,EWINGRC.Is“metamictization”ofzirconaphasetransition?Am.Mineral.,1999,84(7/8):1107–1116.
[40]TRACHENKO K, DOVE M T, SALJE E K H. Reply to comment on'largeswelling andpercolationinirradiatedzircon'. Journal of Physics Condensed Matter, 2003, 15(15):6457–6471.
[41]TROCELLIERP,DELMASR.Chemicaldurabilityofzircon.NuclearInstandMethodsinPhysicsResearchB,2001,181(1):408–412.
[42]GEISLER T, PIDGEON R T, BRONSWIJK W V, et al. Transport ofuranium,thorium,andleadinmetamictzirconunderlowtemperaturehydrothermalconditions.Chem.Geol.,2002,191(1):141–154.
[43]GEISLERT,RASHWANT,RAHNAA,etal.Low-temperature hydrothermal alteration of natural metamict zircons from the eastern desert, Egypt. Mineralogical Magazine, 2003, 67(3):485–508.
[44]GEISLER T, SCHALTEGGER U, TOMASCHEK F. Re-equilibration of zircon in aqueous fluids and melts. Elements, 2007, 3(1):43–50.
[45]ZHANGM,MADDRELLER,ABRAITISPK,etal.Impactof leachonleadvanado-iodoapatite[Pb5(VO4)3I]:aninfraredand Ramanspectroscopicstudy.MaterialsScience&EngineeringB,2007, 137(1):149–155.
[46]GEISLER T, P?ML P, STEPHAN T, et al. Experimental observation of an interface-controlled pseudomorphic replacement reaction inanaturalcrystallinepyrochlore.Am.Mineral.,2005,90(10):1683–1687.
[47]GEISLERT,ULONSKAM,SCHLEICHERH,etal.Leaching anddifferentialrecrystallizationofmetamictzirconunderexperimentalhydrothermalconditions.Contrib.Mineral.Petrol.,2001,141(1):53–65.
[48]LIANJ,ZUXT,KUTTYKVG,etal.Ion-irradiation-induced amorphization of La2Zr2O7 pyrochlore. Phys. Rev. B, 2002, 66(66):054108–1–5.
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