利用磷进行铅污染土壤原位修复中需考虑的几个问题

20101181ChineseJournalofEco-Agriculture,Jan.2010,18(1):203−209*(863)(2008AA10Z4042006AA06Z360)(1971~),,,,E-mail:[e-mail]:2009-10-20:2009-10-28DOI:10.3724/SP.J.1011.2010.00203*陈世宝1李娜1,2王萌1韦东普1(1./100081;2.071001)由于土壤中磷与铅形成难溶性的磷酸铅类化合物[Pb5(PO4)3X,X=Cl−,OH−,F−等],利用不同廉价含磷物质进行铅污染土壤原位修复被认为是目前最好的铅污染土壤管理措施,受到国内外广泛关注。本文对目前国内外利用磷进行铅污染修复研究的现状进行了综述,对该研究领域中的关键问题,如磷酸铅类化合物形成的反应动力学过程控制、最佳pH、土壤中磷/铅摩尔比等进行了较深入的探讨,并展望了今后的研究方向,以期为铅污染土壤的修复及其效果评价提供参考。铅磷污染土壤原位修复磷酸铅类化合物:X131.3;X53:A:1671-3990(2010)01-0203-07Factorsneededtobere-consideredduringin-situremediationpracticesofPb-pollutedsoilswithPCHENShi-Bao1,LINa1,2,WANGMeng1,WEIDong-Pu1(1.KeyLaboratoryofPlantNutritionandNutrientCyclingofMinistryofAgriculture,InstituteofAgriculturalResourcesandRegionalPlanning,ChineseAcademyofAgriculturalSciences,Beijing100081,China;2.HebeiAgriculturalUniversity,Baoding071001,China)AbstractThepresenceofphosphorus(P)andlead(Pb)insoilcanleadtotheformationofhighlyinsolublemineralsofPb5(PO4)3X(whereXcanbeCl−,OH−,F−,etc.).Hencelow-costphosphate-containingmaterialsutilizationwasproposedasthebestmanagementpractice(BMP)forremediationofPb-pollutedsoils.Currentstudiesinvolvingin-situremediationofPb-pollutedsoilsviaphosphorus-compoundsarereviewedinthispaper.Keyfactorscontrollingpyromorphiteformationkinetic,solutionoptimalpHandP/Pbmolarityratio,etc.arediscussedindetail.Meanwhile,prospectivestudiesarealsodiscussedwiththeviewtoprovidingfurtherinformationonremediationpracticesandtheirefficienciesindealingwithPb-pollutedsoils.KeywordsLead,Phosphorus,PollutedSoil,In-situremediation,Pb5(PO4)3X(ReceivedOct.20,2009;acceptedOct.28,2009),(Pb),,,(USEPA)(Bestmanagementpractice,BMP)[1],,[2−10]/2070,Nriagu[11]Pb2+,,,/(),,204201018(),,(P/Pb),/,/,X-(EXAFS)1磷修复铅污染土壤的机理:,;[12−13]1.1,Ca2+[14−15],(M):Ca10(PO4)6(OH)2+xM2+MxCa10-x(PO4)6(OH)2+xCa2+(1),(H2PO4−),,Naidu[16],,H2PO4−,,1.2/Nriagu[11][Pb5(PO4)3X,X=Cl−OH−F−],,(Fluoropyromophite,FP)(Hydroxypyromorphite,HP)(Chloropyromorphite,CP)[17−18],3[19][11],,pH3~11;pH11~13(Cerussite,PbCO3)pH3~11(Galena,PbS);,−270mV-():Ca10(PO4)6(OH)2(s)+14H+(aq)10Ca2+(aq)+6H2PO4−(aq)+2H2O(2)M2+(aq)+6H2PO4−(aq)+2H2OM10(PO4)6(OH)2(s)(3)Ca10(PO4)6(OH)2(s)+xM2+(Ca10-xMx)(PO4)6(OH)2(s)+xCa2+(4)pH,PbAl3(PO4)2(OH)5H2OLogKsp−99.3,PbFe3PO4(OH)6SO4−112.6,CuFe6(PO4)4(OH)8·4H2O−205.7Santillan-Medrano[20]McGowen[21]Cotter-Howells[22](Analyticaltransmissionelectronmicroscopy,ATEM)X(X-rayabsorptionspectroscopy,XAS),/0.6,(CP)Ruby[23],120(Galena)(Anglesite),(CP)Ma[2],Pb2+,,(Apatite)Lower[5](Atomicforcemi-croscopy,AFM),pH6.0,(HA),2:(Pb1mgL−1),(Heterogeneousnuclea-tion);(Pb100mgL−1),(Homogeneousnucleation)ZhangRyan[24],pH,pH2.0~5.0,(CP),pH6.0~7.0,,,pH[25][22,26−29],,Ca2+,Ca-Pb,Ca2+,1:2051.3,,,,[30−31]2利用磷进行铅污染土壤修复中需要考虑的几个关键因素(Liablefractions),,,()pH//2.1,:(1)(,PA)[(MCP)(DCP)(TSP)][(AP)(PR)(BM)(HA)]3,(BM)(HA)PR(1)表1铅污染土壤常用磷修复剂的溶解性Tab.1SolubilitypropertiesofcommonphosphatesourcesforremediationofPb-pollutedsoilPhosphorustypeAbbreviate/Molecularformula/compositionLogKsp[19,32−33]PhosphoricacidPAH3PO4/CalciumdihydrogenphosphateMCPCa(H2PO4)22H2O−1.14AmmoniumdihydrogenphosphateDAPNH4H2PO4n.a.CalciumhydrogenphosphateDCPCaHPO4−6.66ApatiteAP-IICa5-xNa(PO4)3-x(CO3)x(OH)2−20.00CalciumphosphateTCPCa3(PO4)2−24.00TriplesuperphosphateTSPCa(H2PO4)22H2On.a./Hydroxyapatite/bonecharHA/BMCa5(PO4)3(OH)−55.90GroundphosphaterockPRCa5(PO4)3(OH−,Cl−,F−,CO32−)n.a.n.a.:Nodata.,,,70%;,,[24,34],,[4,8,35],/pHPb2.2pHpH,pH;,pH,pH(6.0),H2PO4−,pHHPO42−,pH/Pb2+,Pb2+Pb2+,pH6.0,[26,36−38],,Chen[39]Ma[27]Stanforth[40],pH7.5,,,pH,pH5~8,pH1,2(2),ZhangRyan[24,34]pHpH2.0~7.0,(HA),pH6.0,206201018表2溶液pH变化对羟基磷灰石(HA)溶解度的影响[19,41]Tab.2SolubilityofHAundervariouspHofequilibriumsolutionpHSolubility(molL−1)56.3010−263.1610−471.5810−685.0110−8,HA,;pH=2.0,HA,,(CP);pH=4.0~5.0,,;pH6.0,HA[10],HApH(2),(),()H+,pH,H+(),H+pH,-,pH[2],,/(0.6),,pH,,pH,Xu[25],,pH(1h)5.84.8,,pH6.3Lin[28],pH6.27.2;Hodson[42](),pH1.0,Ma[27]Hettiarachchi[6,43]Tang[44],pH,,(MCP)(DCP)(TSP),pH,Hettiarachchi[43],2500mgkg15000mgkg1(/1.3~28.0),pH7.05.2Cao[26]7000mgkg−1(/≈4.0),pH7.04.5/28.0,10000mgkg−1[37−38,45],,(pH6.0),2.3,,,,,,[13,46],,pH[PbCO3,Pb3(CO3)2(OH)2](PbSO4)(PbO)(PbS)pHpHEh,[47],,[48−50][6,22,51],,,/2.4///,/,-,/,[40,42],/1:207,,/,//1000/,,pH,/,,//,//2.5/,(),=35,,,(Stoichiometry)()[52],(3),0.6[51,53]3[28−29,35]()表3利用磷进行铅污染原位修复中的磷/铅摩尔分子比例Tab.3OverviewofP/Pbmolarityratiosemployedinin-situremediationofPbpollutionbyPLaboratory/P/PbmolarityratioTreatability/P/PbmolarityratioFieldtest/P/PbmolarityratioMa[2]1.5~100.0Rabinowitz[54]38~52YangMosby[38]19.0ZhangRyan[24,34,55]0.6~2.4Ma[56]30~172XuSchwartz[25]0.6~7.4Cotter-HowellsCaporn[53]0.5~0.66Cao[26]Melamed[36]Chen[57]4.0Ma[58]1.2~25Laperche[4]0.6~1.8Chen[39]6.7MaRao[29]8.0~526.0Ryan[37]ScheckelRyan[45]28.0[59]1.5~3.6Hettiarachchi[6,43,51]2.8~28.0StanforthQiu[40]0.5~6.0Zhu[60]Tang[44]1.7~3.3[61]7.0~14.03研究展望,,,,,pH5.0pH,(DCPTSP)pH,pH,/,,,[59,62-63],,[63](Physiologicallybasedextractiontest,PBET)[23,44](),,()(),,,,,,,,///,X-(XRD)(AFM)208201018(SEM-EDS)(Non-destructivetechniques),[22,32],,X-(EXAFS),,,,