全 文 ：第27卷第5期
2008年10月
生态科学
EcologicalS ience
27(5)：384-388
Oct．2008
PhosphorusspeciationinsedimentprofileofMeiliang
Bay,TaihuLakebysequentialfr ctionationand
solutionphosphorus一31 nuclearmagneticresonance
spectroscopy
ZHANGRun．yu1’，WUFeng．chang
2
ChenJing．an1，
J．StateK yLaboratoryofEnvironmentalGeochemistry,InstituteofGeochemistry,ChineseAcademyofSciences,Guiyang550002,China
2．StateEnvironmentalProtectionKeyLaboratoryfo 上出PoHutionControl,ResearchCenterofLakeEco-Environment,Chinese
ResearchA ademyofEnvironmentalScie ces，Beijing10001ZChina
Keywords：sedimentprofile；phosphoms；sequentialfraetionation；solution’‘Pnuclearmagneticresonance
spectroscopy；MeiliangBay
连续提取和液体磷核磁共振表征太湖梅梁湾沉积物中磷的剖面分布
张润宇p，昊事昌2，陈敬安1
1中国科学院地球化学研究所环境地球化学国家重点实验室，贵阳550002
2中国环境科学研究院湖泊生态环境创新基地国家环境保护湖泊污染控制重点实验室，北京100012
【摘要】应用连续提取法(SMT)和液体磷核磁共振(3lpNMR)技术研究了太湖北部梅梁湾沉积物中磷形态和组
成的剖面变化。结果表明，铁／铝磷是沉积物中磷的主要形态，约占总磷含量的44．o_54．6％。总磷、无机磷、有机
磷和铁／铝磷含量均随沉积深度增加呈降低趋势，至18cm以下略有增加，而钙磷却在柱样下部随沉积深度增加呈累
积趋势。31PNMR显示，沉积物磷主要由正磷酸i堂(72．0—99．2呦和磷酸单酯(0．8--25．9％)构成，磷酸二酯、膦酸盐
和焦磷酸盐的相对含量非常低，分别为1．O％、0．4-1．0％和0．1％。正磷酸盐含量在沉积物表层9gill内减少了65％，
9cm以下波动变化，但总体呈降低趋势。这些特征表明沉积物中磷对梅梁湾上覆水体具有强烈的释放潜力，是太湖
富营养化发生的重要因素。
关键词；沉积物剖面；磷；连续提取；液体磷核磁共振：梅梁湾；太湖
中图分类号：x524变球标识码：A 文章编号：1008·8873(2008)05．384-05
收稿日期I2t瑚-097lo收稿，2008-10-10接受
基金项目I国家杰出青年基金项目(40525011)；国家自然科学基金重点项目(40632011)
作者简介s张润宇(t979-,-)，男，博士，研究方向为环境地球化学．
’通讯作者，E-mail：runyuzhaag国126．eom
万方数据
三坦一 张润字，等：连续提取和液体磷核磁共振表征太湖梅梁湾沉积物中磷的剖面分布 385
1 Introduction
Lakesedimentsareconside：redasink懿weIlasasource
fornutrientsa d，therefore，playadecisiverolinthe
phosphorus(P)metabolisminlakes．Theamountof
mobilePinthesedimentsisanimportantp rameterfor
predictinginternalloadingwhichwilloftendetermine
thetrophicstatusofthelakeandthetimelagfor
recoveryafterthereductionin externalloading．
Therefore，thePbe aviorinlakesedimentsCallbe
e伍cientlyevaluatedbasedontheP fractionsor
speciation。insteadofthetot lPcontent．
Fractionationschemesasamethodt characterizeP
bindingtoavarietyoforganicandinorganicsediment
componentshavebeenwidelyused．Accordingtothe
SMTprotocolL“．Pinlakesedimentscarlbedivided
intodifferentfractionssuchasinorganicP(IP)，Pbound
t0Al，Fe，andM oxidesandhydroxides(Fe／A1-P)，
calcium-associatedP(Ca--P)，organicP(OP)，andtotal
P(TP)．Rubancta1．(2001)reportedthatmobileP
comprisesFe／Al-．PandOP．andmobilizationsofthe
twofractionsarethemostimportantmechanismofP
releaseunderhigllpHvaluesandaerobicconditionsⅢ．
OPismainlycomposedofmonocsterandiesterP
compoundsinlakesediments．Reitzeleta1．(2007)
analyzedP speciationinasedimentcorefromthe
SwedishErkenLakebysolution’1Pnuclearm gnetic
resonance(NMR)spectroscopy，andfoundthatestersP
maypersistin hesedimentforlongperiodswhile
polyphosphateandpyrophosphatearedegradedto
orthophosphateathigh rrates【jJ．Itisnecessaryto
definitudeP istributionwithindifferentsediment
environments．Inthi tudy,TaihuL ke，theird
largestfreshwaterlakeinchina，waschosento
investigatetheverticaldistributionofvariousPforms，
andtoevaluateth irpotentialcontributionstothe
overlyingwater．
2 MaterialsandMethods
2．1 Sedimentsampling
TaihuLake(119054"120。36’N，30。56"31033
7
E)is
locatedinthehighlydevelopedandenselypopulated
YangtzeDelta．Itswaterdepthrangesfrom1 to2．5m
(average1．89m)withatotalwatersurfacer aof
about2338．11 km2．SomeareasofTaihuLakesuch勰
MeiliangBayhavebeensufferingserious
eutrophicationproblemswithfrequentoccurrenceof
algabloom．Threeundisturbedsedimentcoreswere
collectedfromMeiliangBay(120012’N，31。30’E)bya
self-madese imentsampleronApril2006．Thecores
wereimmediatelyslicedinto3 cmsegmentsafter
sampling．Segmentsfromthesamedepthofthesecores
werepooledandhomogenizedinordertoobtaina
representatives mpleofsn佑cientsizeforextraction．
Sampleswerethenfreeze．driedandgroundfor
chemicalan yses．
2．2 Pfractions
PfractiousweredeterminedusingtheSMTprotocol，
andtheprocedurewasd scribednapreviousstudytq．
Theoperationallydefinedschemewascomposedofive
steps：Fe|心{，CaP，OP，IPandTP．ForeachP
fraction，threeind pendentreplicateswereanalyzed,
andallthedatawerexpresseda theaverage．P
concentrationswereanalyzedusingthemolybdenum
bluem thod【4】．
2．3 NaOHextractionand儿PNMRSpectroscopy
7．5gsedimentsamplesw reextractedin50mL0．5
reel【■1NaOHsohtionfor24hatroomtemperature【51．
Aftercentrifugationofthextractsat4000xgfor10
min，thesupernatantswerefilteredthrough0．2删m
polysulfonemembranes．Subsamplesworeobtainedfor
analyzingtheconcentrationsofTPa dIPpriorto5
timespre-concentmtionbyro aryevaporationat30。C．
IPwasdeterminedndilutedexUacts(1：100)by
molybdatecolorimetry．TPwasmeasuredbyasimilar
procedurefollowingacid-persulphatedigestionofthe
samples．OPwascalculated弱thediffer ncebetween
TPandIP．
5％(v／v)ofbicarbonatebuff reddithionitesolution
(o．1l molL_‘№lHC03+O．1lreelL-1Na2S204)was
addedtotheconcentratedextractsinordertorenlove
interferencefromparamagneticionssuchasFeandMn
in31PNMRmeasurement【6】．，n坞extractswere
lyopllilizedoverseveraldays．Freeze-driedxtracts
万方数据
i!! 生查型堂坠竺!竺墨生型墨!i竺望 !!堂
(approximately300mg】worerc·dissolvedin0．5mLof
D20(forsignallock)and0．2mLof10melL-‘NaOH，
andthenequilibratedfor5rain．Thesupematantsafter
centrifugationfor10rainat4000xgwereWallsferredto
5 113133NMRtubes．Solution“PNMRspectrawere
obtainedusingaJEOLECX500MHzspectrometer
(Japan)operatingat202．47MHzat25oC．、Veuseda
90。observepulse。atotaIacquisitiontimef5．6S
(acquisitiontime1．6S，pulsed lay4S)andbroadband
protondecoupling．SpectrawereollectedWith
30000scans．Chemicalshiftswererecordedreiativeto
anexternal85％H3P04standard(6=0ppm)．The
spectrawereprocessedu ingvisualinspectionand
automatedpeal【analysistoolsforpeak-pickingand
spectraintegration．Spectrawerplonedwithaline
broadeningof10Hz．
3 ResultsandDiscussiOn
catchmentareaintensifie．dinrecentyears．Thedecrease
inTPconcentrationsintheseaimentprofilemainlywas
attributedto heIPfractionj刀掂contentsof强皿OP
andFe／AI-Pdecreasedwiththeincreaseofd pth，but
alsoincreasedlialebelowthedepthofl8锄．while
Ca_-PatlOWerpartendedtoaccumulatewi hthe
increaseofd pth．RelativecontributionofFe／Al—PWas
44．O一54．6％．ThisfractionWasreportedasanimportant
SOUrOgofbioavailablePineutrophicsedimentsLq．
Therew reintercorrelationsamongvariousPfractions．
TPwasignificantlyorrelatedwithIP．Fe／Al冲and
OP．TherelationshipsbetweenIPcontenta dle}§d．P。
0Pcontentswerealsosignificant．
3．1 VerticaIdistributionsofPfractions
TP，IP，OP，Fe／AI-PandCa inthesedimentprofile
rangedfrom300．2to533．1mgkg-1，from273．7to
409．9mgkg-1，from14．1to123．2mgkg-1，from132tO
263．5mgkg一，andfrom105．8to147．9mgkg-1，
respectively(Fig．n．TPconce trationsin surface
sedimentswerehighparticularly,whichsuggestedthP Fig．1verti明IdistributionsofdifferentPfractionsIn
loadaggravatedwithtimeandhumanctivitiesinthe thesedimentprofileofMeiliangB y．
Table1PcompoundsintheNaOHextractsofMeiliangBaysedimentprofiledeterminedbysolution31PNMR
spectroscopy
’mgkg"1ofdrymatter．ValuesinparenthesesarethepercentagesofNaOH-extractedPforeaehcompound．
“NDreferstonotdetected．
万方数据
5期 张润宇，等：连续提取和液体磷核磁共振表征太湖梅梁湾沉积物审磷的剖面分布 387
0 100 200 300 400 500 600
TotalPinthelakesediments(mgkg‘1)
O 5 10 15 20 25 30
PercentageofOPinNaOHextracts(％)
Fig．2RelationshipsbetweentotalPandNaOHextractedP0 ft)，andthepercentageofOPinthesedimentsa dhe
NaOHextracts(right)．
一⋯． j。．． !竺!!!
广广丌_丁可．111_1T广广r『丌T-T工丁丁T_丌T■T丌丌丌1r—丌_n
20．0 10．0 0 —100 —20．0
Chemicalshift(ppm)
Fig-3Solution31PNMRspectraoftheNaoHextracts
ofMeiliangBaysedimentprofile
Numbersdenotepositionofchemicalshifts：1)phosphonatc，2)
orthophosphate，3)monoesterE4 diesterE5)py ophosphate
3．2 NaOHextractionand儿PNMRanalysis
TotalPintheNaOHextractsrangedfrom69．6to238．4
mgkg-1，withthecorrespondingrecoveryrangingfiom
22％to45％，althoughrelativelyconsistentproportions
ofP werextractedfromostsediments(mean
recovery33％；Fig．2)．OfextractedEbetween37and
178mgkg-1PWaSokrepresentingrecoveriesof11％
t036％(mean21％1oftotal0P．TheyieldofOPWaS
comparabletothresult(27_44％)ofCarmaneta1．
(2000)■andw slOWerthan63％withthextraction
ofNaOH—EDTAbyZhangeta1．(2008)‘“，which
furtherstatedthecombinationofNaOHandEDTACan
recovermo es dimentPthanNaOHalone．Moreover,a
significantcorrelation(∥=O．91，P<0．01)betweenthe
percentageofOPinthesedimentsa dNaOHextractsiS
alsoillustratedinFig．2．111elowerpercentageofOP
determinedintheNaOHextractsthanthatinsediments
maybeduetosomer calcitrantlargerOPmolecules
notbeingextractedbyNaOH．
111eNMRspectraforthesedimentprofilearshownin
Fig．3．Five’1PNMRpeakswereobservedintheNaOH
extracts．Inthesepectra，signalswereinterpretedas
orthophosphateat 6=6_8ppm,pyrophosphateat
6=_-2．5+5)ppmandpolyphosphateat6=---20ppm；as
monoesterPat6=3-6ppm,diesterPat6=2．5十1)ppm
andphosphonateatfi=17．孓-2lppm．Concentrationsand
relativedistributionsofvariousPcompoundsinthe
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万方数据
388 生态科学EcologicalScience 27卷
sedimentprofilearepresentedinTable1．Inall freshwatersediments—Asynthesisofrecentworks．叨．
sedimentextracts，orthophosphatewasthedominantP FreseniusJournalofAnalyticalChemistry，370：224-228．
form,followedbym noesterP，diesterP，phosphonate【31 ReitzelKAhlgrenJ’DeBrabandererI,et以2007．
andpyrophosphate．Similartrendswerealsoreportedin Degradationratesoforganicphosphorusin lake
mostlacustrinesedimentstsJ，withtheexceptionofhe sediment[J]．Biogeochemistry，82：15-28．
absenceofpolyphosphateinthisstudy． 【4】MurphyJRileyJP．1962．Amodifiedsinglesolution
OrthophosphatewasthemostprevailingPcompoundmethodforthedeterminationofphosphateinllatu坞
group．withtherelativecontributionof72．0_-99．2％to watt[J]．AnalyticaChimiAct ,27：31-36．
totalextractedP．Theorthophosphateconcentrationsin 【5】 Carman＆EdlondG，DambergC．2000．Distributionof
the—sedimentsw reveryhighandecreasedrapidly organicandinorganicphosphoruscompoundsinmarine
withdepthinthetop9cmlayers．Thisfurtheruggestedandlacustrinesediments：aMPNMRstudy[J]．ChernicM
thathePreleasepotentialinthesurfacesediments Geology。163：101-114．
fromMeiliangBaywasverylarge．Intensivesignalsat 161AhlgrenJDeBrabandereH，ReitzclKet a1．2007·
年-5．5ppmintheregionofmonoesterPindicatedlarge Sedimentphosphorusextractantsforphosphorus-31n clear
concentrationofphytica id【oJ．Phyticacids magneticresonancealysis：aquantitativeevaluation[J]．
consideredtob amajorcomponentinmanysedimentsJournalofEnvironmentalQuality,36：892-898．
andpossiblyamainconstituentofthehumicmatrix．171ZhangIt,WuF’HeZ，eta1．2008．Phosphoruscomposition
ThisfindingalsosupportedthresultofZhangeta1． inlakesedimentsfromthemidgeandlowerreachesof
(2008)．whosmtedthatresidualOP(mainlycomprisesYangtzeRiverregiona dSouthwesternchi越Plateau,
phyticacidslwasamajorOPfractionandaccountingChina：AMPNMRStudy叨．JournalofE vironmental
for35．7％oftotalOPinthesurface(0-10cm) Quality，inpress．
sedimentsofMeiliangBayusinganimproved【8l HupferM，RObeB，SclmaeiderP．2004．Originand
fractionationscheme吵OtherPcompoundswereonly diagenesisofpolyphosphateinlakesediments：A31PNMR
foundintheuppercentimetersofthes dimentprofile． study[J]．Linmologya dOceanography，49(1)：1·10．
，
f919 ZhangRWhFLiuC，eta1．2008．Characteristicsof
ReIerenc鹤
organicphosphorusfractionsndifferenttrophicsediments
Il】1 RubanV，Lopez-SanchezJ F，PardoP，eta1．1999． oflakesfromthemiddleandlowerreachesofYangtze
Selectionandevaluationof sequentialextraction RiverregionandSouthwesternPlateau．China[J]．
proceduresforthedeterminationofphosphorusformsin EnvironmentalPollution，152：366-372．
1akesediment[j]．JournalofEnvironmentalmo itoring，
1：51-56．
【2l RubanV，L6pez-S缸chezJF，PardoP，eta1．2001．
Harmonizedprotocolandcertifiedreferencemat rialfor
thedeterminationofextractablecont ntsofphosphorusin
万方数据
连续提取和液体磷核磁共振表征太湖梅梁湾沉积物中磷的剖
面分布
作者： 张润宇， 吴丰昌， 陈敬安， ZHANG Run-yu， WU Feng-chang， Chen Jing-an
作者单位： 张润宇,陈敬安,ZHANG Run-yu,Chen Jing-an(中国科学院地球化学研究所,环境地球化学国
家重点实验室,贵阳,550002)， 吴丰昌,WU Feng-chang(中国环境科学研究院湖泊生态环境
创新基地,国家环境保护湖泊污染控制重点实验室,北京,100012)
刊名： 生态科学
英文刊名： ECOLOGICAL SCIENCE
年，卷(期)： 2008,27(5)

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