UNIVERSIDADE DE BRASLIA - UNB

INSTITUTO DE GEOCINCIAS - IGD

ISTOPOSDEENXOFREDECOMPLEXOSALCALINOCARBONATTICOSNA
MARGEMDABACIADOPARANGOIS,MINASGERAISESOPAULO

DISSERTAODEMESTRADO
No275

CAROLINESIQUEIRAGOMIDE

Orientador:JOSAFFONSOBROD
CoOrientador:BERNHARDMANFREDBHN

BRASLIA,2011

UNIVERSIDADE DE BRASLIA - UNB

INSTITUTO DE GEOCINCIAS - IGD

ISTOPOSDEENXOFREDECOMPLEXOSALCALINOCARBONATTICOSNA
MARGEMDABACIADOPARANGOIS,MINASGERAISESOPAULO

DISSERTAODEMESTRADONo275

CAROLINESIQUEIRAGOMIDE

readeConcentrao:MineralogiaePetrologia
Orientador:JOSAFFONSOBROD
CoOrientador:BERNHARDMANFREDBHN

Membros da Banca Examinadora:

Jos Affonso Brod- UFG/UnB
Lucieth Cruz Vieira - UnB
Srgio de Castro Valente UFRRJ

15/03/2011
BRASLIA/DF

AGRADECIMENTOS

Agradeoameusfilhotes,GaeleIuri,elessominhaforanosmomentosmaisdifceis,minhaalegriade
vivererazopelaqualenfrentotodososmomentoscomagarraeenergianecessria.Aoamordaminhavida,
responsvel por dar dois solzinhos em minha vida, Luiz Zarref, meu companheiro, marido, amado, amante,
namorado,paixo...quesempremedeuforaeapoioemtodosossentidos.

Agradeoaomeupai,Afonso,peloesforo,dedicaoeensinamentos,eaosmeusirmos,Guilhermee
Ramon, pela cumplicidade e amizade. minha av, pedagoga da famlia, que sempre me apoiou em minhas
decisesacadmicaseseorgulhadanetinhaquegostadessavida.minhaMezinha,Natalcia,eaoseuJos
Carlos,quesempremeacolheram,apoiaramecompreenderammesmosementenderporquetantacorreria.
tiaNeusinhaeJaquelinequecuidaramcomtantocarinhodomeupequenoIurienquantoestiveescrevendoem
Catalo.

Agradeoafamliabuscap,Paulinho,Gustavo,Luci,IsabelaeDindinha,peloapoio,ajudaeportornar
possvelamoradaemcomunidade.

A todos os amigos e amigas, pelos momentos de alegria, estudos, farras e reflexes. Em especial,
agradeoKatita,Bela,Raquel,Bibi,Jean,Cupim,Juaetantosquecolaborarameforamfundamentaisnesta
etapa de minha vida, e que mesmo sem entender porque diabos essa menina estuda tanto, sempre me
apoiaramecompreenderammeussumios.

Aosamigosdageologia,peloapoioepartilhadachoradeiradonuncaacaba,peloslanchinhosnahora
do desespero para uma energia a mais, pela ajuda com o trabalho, pelos papos nos intervalos para um
cafezinho...EmespecialDiana,LuizPaulo,MariBegeeAnaCatarina.

AosmultiresgeocrongicosparaajudaraCarol,emespecialBrbara(debabamedonetuno)e
Jaqueline(debabapessoaqueresolvetodasascoisas).TambmagradeoaoManciniquemeaturoudemais
com as perguntas e amostras a serem analisadas, rico com a ajuda e pacincia, Lucieda pela companhia e
atenoeJ(sempredisponvel,incrvelcomoelaconsegue!).

Agradeo o professor Elton, pelo apoio e ajuda sempre que solicitado. Ao professor Bernhard pela co
orientaoeensinamentosparaqueessetrabalhofossepossvel.

Agradeo especialmente aos meus orientadores Affonso e Tereza Brod, meus pais geolgicos que
foramfundamentaisemminhaformaoequecomtantocarinho,dedicao,firmezaesabedoriaauxiliaram,
participaramecompartilharamtantosmomentosdesuperaoeaprendizado.

Capes,pelabolsa,quesitofundamentalparaarealizaodestetrabalho.

Porfim,agradeoatodosetodasquenoforamlembradosnesteagradecimento,masqueforameso
importantesnomeuprocessodeformao.

ABSTRACT

Thisthesispresentspetrographic,chemical,andsulphurisotopedata,inordertocontributeto

elucidate the origin, evolution and differentiation mechanisms (e.g. fractional crystallization, liquid
immiscibility, magma mixing and degassing) in alkalinecarbonatite complexes of the Alto Paranaiba
IgneousProvince(APIP)andintheJacupirangacomplex,fromthePontaGrossaProvince.
TheAPIPisoneofthelargestultrapotassicultramaficprovincesworldwide,andoneofthefew
known kamafugitecarbonatite associations. It includes six carbonatite complexes (Catalo I, II, Serra
Negra, Salitre, Arax, Tapira), which are multiphase intrusions formed by rocks belonging to the
bebedourite,phoscoriteandcarbonatiteseries.ThePontaGrossaProvince,unlikeAPIP,isdominated
bysodicalkalinerocks.Jacupirangawasthesolecomplexstudiedfromthisprovince,andiscomposed
ofrocksofthecarbonatiteandijoliteseries.

Therocksfromcarbonatitecomplexes,especiallythoseofthecarbonatiteseries,oftencontain

sulphides(pyrite,pyrrhotite,chalcopyrite,galena,bornite,pentlandite)andsulphates(mainlybarite).
Therefore,sulphurisanimportantelementforresearchinthepetrogenesisoftheserocks.Thiswork
presentsthefirstsulphurisotopedatafromAPIPandPontaGrossacomplexes.Themaintoolsusedin
thisstudyincludepetrography,mineralchemistryandisotopicanalysisofsulphidesandsulphatesin
carbonatites, phoscorites and bebedourites, in APIP, and carbonatites and jacupiranguites, in
Jacupiranga.

The studied samples show mesoscopic and microscopic quench textures, such as bladed

carbonate and sulphide crystals, with interstitial microgranular aggregates of carbonate, barite and
sulphides.Theseareinterpretedastheresultofrapidcrystallizationduringdegassingofasupercooled
carbonatitemagma.

TheCO2degassingatAPIPcomplexeswasstudiedinpreviousworksbytheResearchGroupin

AlkalineRocksandAssociatedMineralizationsandthisworkaddsdegassingofsulphurgaseousphases
(H2Sand/orSO2)tothatpicture.
Thesulphurisotoperesultsinsulphidesfromsamplesshowingevidenceofdegassingvaryfrom
core to rim, with the latter showing higher (less negative) 34S, compared with the former, which
indicatesthatdegassingtookplaceinanoxidizingenvironment.

Isotopic data indicates that as magma differentiation progresses it consumes particullarly

heavier isotopes into the solid phases, leaving a residual magma/fluid enriched in 32S. On the other
hand, sulphur loss by degassing under oxidizing conditions lead the residue to evolve toward higher
34S.

The sulphur isotope composition of the studied complexes is consistent with the expected

valuesforigneousrocksandcarbonatitecomplexes.Dataforworldwidecarbonatitesofvariousages
suggestthatthesulphurisotopeglobalcompositioninthemantlemighthaveprogressivelychanged
towardsmorenegative34Svalueswithtime.

RESUMO

Esta dissertao apresenta dados petrogrficos, de qumica mineralede istopos estveisde

enxofre,comointuitodecontribuirparaelucidaragnese,evoluoemecanismosdediferenciao
(processos como cristalizao fracionada, imiscibilidade de lquidos, mistura de magmas e
desgaseificao) em complexos alcalinocarbonatticos da Provncia gnea do Alto Paranaba (APIP) e
emJacupiranga,umcomplexoCarbonatticodaProvnciaPontaGrossa.
A Provncia gnea do Alto Paranaba (APIP) uma das maiores provncias ultramaficas
ultrapotssicasmundiaiseumadaspoucasassociaeskamafugticascarbonatticasconhecidas.Inclui
6 complexos carbonatticos (Catalo I, II, Serra Negra, Salitre, Arax, Tapira) que so intruses
multifsicasformadasporrochasdassries bebedourtica,carbonatticae foscortica.AProvnciade
Ponta Grossa, diferente da APIP, dominada por rochas alcalinas sdicas. Jacupiranga, o nico
complexo desta provncia estudado no presente trabalho, composto de rochas das sries
carbonatticaeijoltica.
As rochas dos complexos carbonatticos, principalmente as da srie carbonattica,
frequentemente contm sulfetos (pirita, pirrotita, calcopirita, galena, bornita, pentlandita) e sulfatos
(principalmente barita). Portanto, o enxofre um elemento importante no estudo de processos de
formaodessasrochas.EsteoprimeirotrabalhoaapresentardadosisotpicosdeSnoscomplexos
daAPIPePontaGrossa.

As principais ferramentas utilizadas para o estudo incluem petrografia, qumica mineral e

anliseisotpicadesulfetosesulfatosemrochasdassriescarbonattica,foscorticaebebedourtica,
naAPIP,edecarbonatitosejacupiranguitos,emJacupiranga.

A petrografia das amostras permitiu o reconhecimento de texturas interpretadas como de

resfriamentorpido,comocristaisalongados(laminares)principalmentedecarbonatoesulfeto,cujos
insterstcios esto preenchidos por agregados microgranulares de carbonato, barita e sulfetos. Estas
texturassointerpretadascomoresultadodecongelamento(quench)duranteadesgaseificaodeum
magmasuperresfriado.
A desgaseificao de CO2 nos complexos da APIP foi estudada em trabalhos anteriores do
Grupo de Pesquisa em Rochas Alcalinas e Mineralizaes Associadas e este trabalho agrega a
desgaseificaodegasessulfetados(H2Se/ouSO2).
As anlises de istopos de S em amostras com evidncias petrogrficas de desgaseificao
apresentam uma diferena ncleo e borda do gro de sulfeto, onde a borda possui maiores valores
(menos negativos) de 34S em relao ao ncleo, o que leva concluso de que o processo de
desgaseificaoocorreuemambienteoxidante.
Os dados isotpicos indicam que a medida que os processos de diferenciao progridem, os
istoposmaispesadossoconsumidosdeixandoomagmaresidualenriquecidoem 32S,aopassoque
queduranteadesgaseificaodevolteiscomS,emcondiesoxidantes,omagmaresidualenriquece
em34Snoscomplexosestudados.
A composio isotpica de enxofre dos complexos estudados coincide com os valores
esperadospararochasgneaseparacomplexoscarbonatticos.Osdadosdecarbonatitosmundiais,de
vrias idades, sugerem que a composio isotpica de enxofre no manto pode ter mudado
progressivamenteaolongodotempogeolgico,emdireoavaloresmaisnegativosde34S.

ndice
CAPTULO1.................................................................................................................................................1
Introduo...............................................................................................................................................1
CAPTULO2.................................................................................................................................................5
Mtodos..................................................................................................................................................5
AnlisesemMicrossondaEletrnica......................................................................................................5
Preparaodeamostras.....................................................................................................................5
Procedimentosanalticos....................................................................................................................6
IstoposdeEnxofre................................................................................................................................7
Revisobibliogrfica...........................................................................................................................7
Preparaodeamostras.....................................................................................................................9
Laserablationmultiplecollectorinductivelycoupledplasmamassspectrometry(LAMCICPMS)9
Procedimentosanalticos..................................................................................................................11
Tratamentodosdados......................................................................................................................12
CAPTULO3...............................................................................................................................................13
SulfurisotopesfromalkalinecarbonatitecomplexesalongthebordersoftheParanBasinGois,
MinasGeraisandSoPauloStates,Brazil............................................................................................13
Abstract.............................................................................................................................................13
1.
Introduction............................................................................................................................13
2.
Geologicalsetting...................................................................................................................15
3.
Sampledescription.................................................................................................................19
4.
Analyticalmethods.................................................................................................................34
5.
Results.....................................................................................................................................35
5.1.MineralChemistry......................................................................................................................38
5.2.SulfurisotopevariationsintheAPIPcomplexesandJacupiranga............................................40
5.3.Sulfurisotopevariationsbyrocktype.......................................................................................42
5.4.Sulfurisotopevariationsfromrimtocore................................................................................44
5.5.Sulphidesulphideisotopicvariation.........................................................................................46
5.6.Sulphidesulphateisotopicvariationandfractionation............................................................47
5.7.Comparisonwithothercarbonatites.........................................................................................49
6.
Conclusions.............................................................................................................................51
7.
References..............................................................................................................................55
CAPTULO4...............................................................................................................................................62
Concluses............................................................................................................................................62
REFERNCIASBIBLIOGRFICAS................................................................................................................66
ANEXOS........................................................................................................................................................i
AnlisesdeIstoposdeEnxofre..........................................................................................................i
DadosdeQumicaMineraldeBarita...................................................................................................v
DadosdeQumicaMineraldeSulfeto..............................................................................................viii

ndicedeFiguras
Figura2.01DesenhoesquemticodosistemaMCICPMS(ManualThermoFinnigan2003)................................................10
Figure 3.01 Carbonatite occurrences surrounding the Paran Basin. The carbonatite complexes studied in this work are
shownasstars.ModifiedfromOliveiraetal.(2004)andWooley&Kjarsgaard(2008)..16
Figure3.02CarbonatitefromtheCataloIIcomplex.A:phlogopite(phl),magnetite(mgt)andrecristalyzedpyrite(py).
cbt=carbonate Field width: 5mm. Plane polarized light; B: Same as A in reflected light. C: Backscattered image of a
carbonate(cbt)+barite(brt)massincarbonatitefromtheCataloIIcomplex.D:Highermagnificationviewoftheback
scatteredimageinA..20
Figure3.03TexturalfeaturesofnelsonitesfromtheCataloIIcomplex.A:Apatite(Ap)andpyrochlore(Pcl)innelsonite,
planepolarizedlight.Fieldwidth:5mm.B:SameasA,inreflectedlight,showingchalcopyrite(Cpy)andsubordinatepyrite
(Py).Fieldwidth:5mm.C:Phlogopite(Phl),apatite(Ap),pyrochlore(Pcl),carbonate(Cbt)andmagnetite(Mgt)innelsonite,
planepolarizedlight.Fieldwidth:5mm.D:Pyrite(Py)andrarechalcopyrite(Cpy)replacingmagnetite;notethattheearlier
magnetite contained ilmenite (Ilm) exsolution lamellae that remained preserved upon dissolution and substitution of the
magnetitegrain,formingatrellistexture,reflectedlight.Fieldwidth:1,5mm.21
Figure 3.04 Textural features of sulphides and barites in carbonatites from the Catalo I complex. A: Apatite (Ap),
carbonate(Cbt)andphlogopite(Phl)incrosspolarizedlight.Fieldwidth:5mm.B:SameasAinreflectedlight,showinga
smoothsurfaceforpyrite(Py).Fieldwidth:5mm.C:Phlogopite(Phl),carbonate(Cbt),barite(Brt);notetheintergrowthof
pyriteandbarite.Crosspolarizedlight.Fieldwidth:5mm.D:SameasCinreflectedlight,pyrite(Py)andmagnetite(Mgt);
note the intergrowth of pyrite and barite. Field width: 5mm. E: Pyrite (Py) with pitted surface, probably resulting from
recrystallizationasmicrogranularaggregates.Reflectedlight.Fieldwidth:5mm.F:Pyrite(Py)withskeletalappearanceand
irregular surfaces, probably resulting from recrystallization as microgranular aggregates. Reflected light. Field width:
5mm.22
Figure3.05TexturalfeaturesofsulphidephoscoritesfromtheCataloIcomplexA:Apatite(Ap)andphlogopite(Phl)from
phoscorites in cross polarizedlight.Fieldwidth: 5mm. B:Same as A in reflectedlight,showinga pitted surface in various
pyrite (Py) individual grains and very fine grained chalcopyrite (Cpy) aggregates with a dusty appearance. Field width:
5mm.C:Apatite(Ap)andphlogopite(Phl).Planepolarizedlight.Fieldwidth:5mm.D:SameasC,inreflectedlightshowing
pyrite (Py); note the amoeboid geometry of the interstitial pyrite aggregates, suggesting that they formed from an
immisciblesulphideliquid.Fieldwidth:5mm.23
Figure3.06TexturalfeaturesofnelsonitesfromtheCataloIcomplex.A:Apatite(Ap),carbonate(Cbt),pyrochlore(Pcl)
and phlogopite (Phl) in nelsonite, plane polarized light showing flow orientation of phlogopite and apatite crystals. Field
width: 5mm. B: Pyrite (Py) grains with pitted surface and finegrained chalcopyrite (Cpy) aggregates. Field width:
5mm....24
Figure 3.07 Serra Negra carbonatites. A: Coarsegrained carbonate (Cbt) in cross polarized light; Field width: 5mm. B:
SameasA,inreflectedlight,showingasmallpyritegrain(Py).Fieldwidth:5mm.25

ii

Figure3.08TexturalfeaturesofcarbonatitesfromtheSalitrecomplex.A:Apatite(Ap),carbonate(Cbt),phlogopite(Phl)
andpyrochlore(Pcl)inplanepolarizedlight.Fieldwidth:5mm.B:Elongatedsulphidegrain,pyrrhotite(Po)isthegrainwith
a skooth surface, pyrite (Py) is the irregular surface grain, and chalcopyrite (Cpy) is present in small amounts, bordering
pyrrhotiteandpyrite.Reflectedlight.Fieldwidth:5mm.C:Carbonate(Cbt),barite(Brt)andpyrite(Py)showingzonationin
carbonate crystals. Plane polarized light. Field width: 5mm. D: Carbonate (Cbt) and complexly zoned barite (Brt). Cross
polarizedlight.Fieldwidth:5mm26
Figure3.09TexturalfeaturesofsulphidephoscoritesfromtheSalitrecomplex.A:Coarsegrainedphoscorite,composedof
olivine(Ol),phlogopite(Phl)inplanepolarizedlight.Fieldwidth:5mm.B:SameasAinreflectedlight,showingpyrite(Py)
replacingmagnetite;ilmenite(Ilm),chalcopyrite(Cpy)andpyrrhotite(Po).Fieldwidth:5mm.27
Figure 3.10 Bebedourite from the Salitre complex. A: Coarse grained bebedourite, composed of clinopyroxene (Cpx),
phlogopite (Phl), magnetite, ilmenite, pyrite. Field width: 5mm. B: Same as A in reflected light, showing magnetite (Mgt)
replacementbypyrite(Py).Fieldwidth:5mm27
Figure3.11Texturalfeaturesoffinegrainedaggregatesofsulphide,bariteandcarbonateincarbonatitefromtheArax
complex.A:Criptocrystalinecarbonatemass,withintergrownofbariteaggregatesandsulphide,crosspolarizedlight.Field
width:5mm.B:Sameas"A",inreflectedlight.Fieldwidth:5mm..28
Figure 3.12 Textural features of sulphide and carbonate in carbonatite from the Arax complex A: Typical texture of
carbonatite pyrite (Py), with very irregular grain surfaces, probably resulting from recrystallization of microgranular
aggregates and very finegrained aggregates of chalcopyrite (Cpy), and subordinate pyrite, with a dusty appearance.
Reflectedlight.Fieldwidth:5mm.B:Sulphideswithablobaspect,showingroundcontoursthatmayindicateseggregation
ofasulphideimmiscibleliquid,withpyrrhotite(Po),pyrite(Py)andchalcopyrite(Cpy).Reflectedlight.Fieldwidth:5mm.C:
Carbonateaggregatesmarkedbysubparallelcurvedlines.Planepolarizedlight.Fieldwidth:5mm.D:Sameas"C"incross
polarizedlight.E:Crosssectionofcarbonateaggregatesshowingconcentricgrowthlines.Planepolarizedlight.Fieldwidth:
5mm. F: Same as "E", in cross polarized light, showing a circling maltese cross similar to the spherulitic
extinction..29
Figure 3.13 Phoscorite. A: Phoscorite with magnetite (Mgt), phlogopite (Phl), apatite (Ap) and carbonate (Cbt). Plane
polarized light. Field width: 5mm. B: Pyrite (Py) with pitted surface and magnetite (Mgt). Reflected light. Field width:
5mm.30
Figure3.14TexturalfeaturesofcarbonatitesfromTapiracomplex.A:Carbonatitewithcarbonate(Cbt),olivine(Ol)and
apatite(Ap).Crosspolarizedlight.Fieldwidth:5mm.B:Carbonatitewithsomemicrogranularcarbonatesofcolloidalaspect
(arrow).Planepolarizedlight.Fieldwidth:5mm.31
Figure3.15A:BSEimageofafinegrainedmasscontainingdolomite(Cbt)andskeletalbarite(Brt).B:BSEimageofafine
grained mass containing different carbonate types and barite, 001: Barite; 002: Barite; 003: Srcarbonate; 004: Sr
carbonate;005:Dolomite;006:Calcite;007:Calcite.31
Figure 3.16 Textural features of phoscorites from Tapira complex. A: Phoscorite showing carbonate (Cbt), olivine (Ol),
apatite (Ap), granular chalcopyrite and pyrite with pitted surface. Cross polarized light. Field width: 5mm. B: Same as A,

iii

showing granular chalcopyrite (Cpy) and pyrite (Py) with pitted surface under reflected light. Field width:
5mm......32
Figure 3.17 Textural features of carbonatites from Jacupiranga complex. A: Carbonatite with apatite (Ap) and
disseminated pyrrhotite (Po) in plane polarized light. Field width: 5mm. B: Texture suggestive of carbonatesulphide
immiscibilityshowingpyrrhotite(Po)andchalcopyrite(Cpy),notethebloblikeaspectofthepyrrhotitenearthelowerright
corner.Reflectedlight.Fieldwidth:5mm.C:Carbonatite withmicrogranularaggregatesof pyrite(Py),formingconcentric
circularoramoeboidallines.Ilm=ilmenite.Reflectedlight.Fieldwidth:3.5mm33
Figure3.18TexturalfeaturesofjacupirangitesfromJacupirangacomplex.A:Jacupirangiteshowingclinopyroxene(Cpx)
withmagnetite(Mgt)andinterstitialchalcopyrite(Cpy).Crosspolarizedlight.Fieldwidth:5mm.B:Sameas"A",inreflected
light. C: Jacupirangite showing nepheline (Ne) with sympletitic texture, titanite (Ttn) and clinopyroxene (Cpx). Plane
polarizedlight.Fieldwidth:5mm.D:Sameas"C",incrosspolarizedlight.Fieldwidth:5mm...34
Figure3.19ClassificationofsulphidesaccordingtoCuSFeinatomicproportions.39
Figure3.20Comparedmajorelementvariationsinthestudiedsulphidesforeachcomplex..,.39
Figure 3.21. Sulphur isotope data for alkaline carbonatite complexes from APIP and Ponta Grossa Province. Red bars
representsulphidedataandbluebarsrepresentsulphatedata..41
Figure 3.22. Sulphur isotope data for sulphides and sulphates from the APIP and Jacupiranga alkaline carbonatite
complexes,byhostrocktypeandcomplex..43
Figure3.23.Sulphurisotopedataforsampleswithevidenceofdegassing,showingdifferentvaluesfromcoretorim.Note
thatboththevariationinsinglegrainsandthecomparisonbetweendifferentrocktypesindicateincreasingvaluesof34S
withprogressivedegassing.45
Figure3.24.Sulphurisotopedataforsulphidesfromthestudiedalkalinecarbonatiticcomplexes.Blacksolidhorizontalbar:
magmaticsulphide;Unfilledhorizontalbar:sulphidefromfenites.47
Figure3.25.Sulphurisotopecompositionforsulphideandsulphateinthesamesample....47
Figure3.26.Modellingofsulphidesulphatefractionation(Miyoshietal.,1984)forthestudiedsamples...48
Figure3.27.SulphurisotopedatafromalkalinecarbonatitecomplexesintheWorld.APIPresults(thiswork)areshownas
verticalbarsinthetopsectionofthefigureblueandredbarsrepresentbariteandsulphides,respectively.Thehorizontal
bars(solidcolors=sulphides,unfilledbars=barite)inthebottomsectionrepresentotherworldwidecomplexes,inorderof
increasing age from top to bottom: Bearpaw Mountain (Mitchell & Krouse 1975; ~48Ma Duke, 2009), Magnet Cove
(Mitchell & Krouse, 1975; 99Ma Wooley & Kjarsgaard, 2008), Oka (Mitchell & Krouse 1975; 117Ma Wooley &
Kjarsgaard,2008),Tuva(118Ma,Nikiforovetal.2006),Jacupiranga(thiswork;131MaWooley&Kjarsgaard,2008#),Kola
Province(Mitchell&Krouse1975,Shin&Lee2007;~250340MaDownesetal2005),Swartbooisdrif(Druppel2006;750Ma
Wooley & Kjarsgaard, 2008), Mountain Pass (barite data only) (Mitchell & Krouse 1975; 1.4Ga Wooley & Kjarsgaard,
2008),SuperiorProvince(Farreletal.2010;1,897Mato1,093MaFarreletal.2010),Phalaborwa(Mitchell&Krouse1975;
2.02GaWooley&Kjarsgaard,2008).50

iv

Figure 3.28. Correlation of sulphur isotope composition of worldwide carbonatites with the respective ages. Note the log
scaleoftheageaxis.Datasourcesasinfigure3.27.51

ndicedeTabelas

Tabela2.01Limitesdedetecoparacadaelemento,nasanlisesdesulfeto..................................................................6
Tabela2.02Limitesdedetecoparacadaelemento,nasanlisesdesulfato..................................................................6
Tabela2.03Parmetrosdeconfiguraodoespectrmetroparaanlisesinsitu...........................................................12
Table3.01Representative34Sresults.......................................................................................................................36
Table3.02Representativeandaveragechemicalcompositionsofthestudiedssulphides.37
Table3.03Representativecompositionsofthestudiedsulphates.38
Table3.04Sulphurisotopedataforthesamplesthatpresentdifferencesbetweenrimandcore..46

CAPTULO1
Introduo
Processos como cristalizao fracionada, imiscibilidade de lquidos, mistura de magmas e
desgaseificao vem sendo estudados pelo Grupo de Pesquisa em Rochas Alcalinas e Mineralizaes
Associadas, da Universidade de Braslia e Universidade Federal de Gois. Esta dissertao se insere
nessecontextotrazendodadosdeistoposestveisquecolaboramnaelucidaodagnese,evoluo
emecanismosdediferenciaoemComplexosAlcalinosdaProvnciagneadoAltoParanaba(APIP)e
doComplexodeJacupiranga,naProvnciaPontaGrossa.
Diversos estudos geoqumicos, mineralgicos, de istopos estveis (principalmente C, O) e
radiognicos (Sr, Nd, Pb, alm dos sistemas ReOs e LuHf) tem sido realizados na APIP e outras
provnciasalcalinasdabordadaBaciadoParan(e.g.Gibsonetal.,1995b,Bizzietal.,1995,Comin
ChiaramontieGomes,1996,2005,Carlsonetal.,2007,Cordeiroetal.,2011).Entretanto,emboraas
rochas dos complexos carbonatticos da APIP, em particular as das sries foscortica e carbonattica,
frequentemente contenham sulfetos (pirita, pirrotita, calcopirita, bornita) e sulfatos (principalmente
barita),elasaindanohaviamsidoestudadasdopontodevistadeistoposestveisdeS.
Esta tcnica tem sido aplicada a problemas petrolgicos e metalogenticos em complexos
carbonatticos como, por exemplo, Swartbooisdrif, Namibia (Drppel et al. 2006), e Magnet Cove,
BearpaweMountainPass,EUA(MitchelleKrouse,1975).Dentreasprincipaisaplicaes,destacamse:

Determinaodaorigemmagmticaouhidrotermaldoenxofreresponsvelpelaformaode
sulfetosesulfatosemcarbonatitoserochasassociadas(Nikiforovetal.2006)
Determinao da variao isotpica com temperatura, fugacidade de oxignio e estado de
diferenciaodomagma(Drppeletal.2006).
Monitoramentodeprocessostardioscomofenitizaoemineralizaes(Drppeletal.2006).
DesgaseificaodeespciesvolteiscomoSO2eH2Sapartirdemagmas(Zheng,1990).

Na APIP, esta dissertao constitui o primeiro estudo de istopos de S. O trabalho aborda a

composio isotpica tanto de sulfetos quanto de sulfatos presentes em diversos litotipos dos
complexos alcalinocarbonatticos da provncia e incluiu, alm das anlises isotpicas, a obteno de
dadospetrogrficos,imagensdemicroscopiaeletrnica,anlisedequmicamineralegeoqumicade
rochatotal.Osresultadospermitiramestabelecerdiferenasentrecomplexosedentrodeummesmo
sistema,asquaispodemestarrelacionadasaprocessosdediferenciao,comocristalizaofracionada
e desgaseificao. Resultados analticos representativos so apresentados no captulo 3 e as tabelas
comosresultadoscompletossoapresentadasaofinaldotrabalho,comoanexos.
AProvnciagneadoAltoParanaba,oestedeMinasGeraisesuldeGois,resultadeintenso
magmatismo alcalino que gerou corpos intrusivos (diques, condutos, diatremas e complexos
plutnicos) e extrusivos (lavas e piroclsticas) de afinidade kamafugtica (Leonardos et al., 1991,
Almeida e Svisero, 1991, Gibson et al., 1995b, Carlson et al., 1996, 2007, Brod et al., 2000, 2004,
CominChiaramonti e Gomes, 2005). uma das maiores provncias ultramaficasultrapotssicas
mundiais (Gibson et al. 1995a,b), e uma das poucas associaes kamafugticascarbonatticas
conhecidas (Brod et al., 2000). Sonoki & Garda (1988) e Gibson et al. (1995b) fornecem idades
radiomtricas entre 80 e 90 Ma para a Provncia. Os complexos carbonatticos da APIP (Catalo I, II,
Serra Negra, Salitre I, II, III, Arax, Tapira) so intruses multifsicas formadas por rochas das sries
bebedourtica,carbonatticaefoscortica.

CataloI,situado20kmaNEdacidadedeCatalo,aproximadamentecircular,com6kmna

direo NS e 5,5 km EW, encaixado em rochas metassedimentares do Grupo Arax. Consiste de

dunitos, bebedouritos, carbonatitos, foscoritos e nelsonitos, alm de flogopititos metassomticos, e
abrigaimportantesdepsitosdeP,Nb,terrasraras,Tievermiculita(Carvalho&Bressan,1997,Brodet
al2004,RIbeiro,2008).
CataloII,cercade10kmaNNWdeCataloI,intruderochasdoGrupoArax,formandoum
pequenoaltotopogrficoirregular,alongadonadireoNESWecommargenssinuosas,sugerindoa
existncia de intruses mltiplas. Machado Junior (1992) descreve os tipos litolgicos como
piroxenitos, quartzo sienitos, feldspato alcalino sienitos, calcita carbonatitos, silicocarbonatitos,
dolomita carbonatitos e lamprfiros, alm de flogopititos metassomticos. Alm destes litotipos,

Palmieri et al. (2009) e Jcomo et al (2010) reportam a ocorrncia de nelsonitos na poro sul do
Complexo.
SerraNegra,alestedacidadedePatrocnio,omaiorcomplexocarbonatticodaAPIP,com65
km2. Intrude quartzitos do Grupo Canastra, formando uma estrutura dmica muito pronunciada.
composto por calcita carbonatito, dolomita carbonatito, foscorito, bebedourito, dunito e peridotito
(Brodetal.2004,Grassoetal.,2009).
Salitre,imediatamenteasuldocomplexoSerraNegra,formacomesteumsistemadeintruses
coalescentes(Mariano&Marchetto,1991),econsistede3intrusesdistintas.SalitreI,com35km2,
composto por bebedourito, tinguaito, traquito, fenito, apatita carbonatito, calcita carbonatito,
dolomita carbonatito e foscorito (Barbosa et al. 2004, 2008, 2009) . Salitre II, com 2,5 km2, situado
entre Serra Negra e Salitre I, contm principalmente rochas ultramficas (dunito, perovskitito,
bebdourito,localmentecortadospordiqueseveioscarbonatticos).SalitreIIIumpequenocorpoa
sul de Salitre I, essencialmente formado por piroxenitos, com foscoritos subordinados (Brod et al
2004).

Arax(Barreiro)umcomplexorelativamentepequeno(15km2),circular,localizadoacercade

6 km a sul da cidade de Arax, composto por carbonatitos, foscoritos, bebedouritos, dunitos,

lamprfiros (flogopitapicritos) e um grande volume de flogopititos derivados do metassomatismo
sobre as rochas ultramficas (Issa Filho et al., 1984, Traversa et al., 2001). A intruso gerou uma
estruturadmicanosxistosequartzitosdoGrupoIbi(Seer,1999).
Tapira, 30 km a SE da cidade de Arax, aproximadamente elptico, com 35km2, composto
principalmenteporbebedourito,comcarbonatitoesienitosubordinadoserarosmelilitolitoedunito,
todoscortadospordiquesultramficosdeafinidadekamafugtica(Brodetal,2000,2003).
AProvnciadePontaGrossa,bordalestedabaciadoParan,dominadaporrochasalcalinas
sdicasNesienito,malignito,melteigito,ijolito,fonolito,carbonatito,lamprfiro,pulaskito,dunito,
piroxenito, urtito, ankaratrito, gabro alcalino, sienogabro, sienodiorito, sienito, fonolito peralcalino,
olivinagabroalcalino,sienodiorito,essexito,basanito,fonotefrito,shonkinitoetraquito(Morbidelliet
al. 1995). A provncia composta por estruturas plutnicas denominadas Banhado, Itapirapu,
Jacupiranga, Juqui e Tunas, pipes and plugs Barra doPonta Grossa, Barra doTeixeira, Cerro Azul,
MatoPreto,MorrodoChapueSeteQuedas(Rubertietal.2005).

Jacupiranga, o nico complexo da Provncia de Ponta Grossa estudado neste trabalho, est
localizado cerca de 10km a oeste da cidade de Jacupiranga e imediatamente a norte da cidade de
Cajati noestado deSo Paulo. O complexo intrudiu ogrupo Aungui(Ruberti etal. 2005)etem um
formatooval(aproximadamente65km2)comumpequenoncleoalongadodecarbonatito(Morroda
Mina) que intrudiu jacupiranguitos. As rochas que compem o complexo so piroxenitos
jacupiranguitos, peridotitos serpentinizados, ijolitos, nefelinasienitos, carbonatitos, essexitos,
monchiquitosetinguatos(Gomesetal.1990).

CAPTULO2
Mtodos

As principais ferramentas aplicadas no projeto incluem petrografia, qumica mineral e anlise

isotpicadesulfetosesulfatosemrochasdassriescarbonattica,foscorticaebebedourtica,naAPIP,
ecarbonatitosejacupiranguitos,emJacupiranga.
As amostras foram selecionadas a partir de critrios texturais e mineralgicos conhecidos de
estudosanterioresdoGrupo.Partedasamostrasjvinhasendoestudadaporoutrosmtodoseoutra
partefoicoletadaespecficamenteparaesteprojeto.Semprequepossvelprocurouseobteramostras
que contivessem ao mesmo tempo sulfetos e sulfatos. Devido ao processo de intemperismo que
facilmente atinge essas rochas, todas as amostras so testemunhos de sondagem ou amostras de
afloramentos frescosnointeriordasminasdefosfato,cedidaspelaempresasdemineraoFosfrtil
(CataloI,SerraNegra,Salitre),AngloAmerican(CataloII),eBunge(TapiraeArax).
Foram confeccionadas lminas delgadas polidas, parte no laboratrio de laminao da
Universidade de Braslia UnB e parte em laboratrio externo universidade. As amostras para as
outrastcnicasanalticasforamselecionadasapartirdadescriopetrogrficadessaslminas.
A composio isotpica de enxofre foi determinada em LAMCICPMS (Laser AblationMulti
CollectorInductivelyCoupledPlasmaMassSpectrometer)noLaboratriodeGeocronologiadoIG/UnB,
emgroindividuaisdesulfetosesulfatos.
AcomposioqumicadefasesmineraisfoideterminadapormicrossondaeletrnicaJEOLJXA
8230,emmodoWDS,noLaboratriodeMicrossondaEletrnicadoIG/UnB.

AnlisesemMicrossondaEletrnica
Preparaodeamostras
Os sulfetos e sulfatos foram separados manualmente com o auxlio de alicate e/ou micro
retficacomdiscodiamantado(raiodeaproximadamente1cm)emontadosemresinacomapenasum
groemcadaseo.Vriasmontagensforamacopladasemumaseopolidaquefoiposteriormente
limpaemultrassomemetalizadacomcarbonoparaanliseemmicrossondaeletrnicaJEOLJXA8230.

Algumasanlisesforamrealizadasemlminasdelgadaspolidastambmmetalizadascomcarbono.O
bompolimentoextremamenteimportantenaanlise,paraevitarvariaesdosefeitosdeabsoro.
Procedimentosanalticos
Os sulfatos foram primeiramente investigados em modo de disperso por energia (EDS
energydispersive spectroscopy) e observados em imagens de eltrons retroespalhados (BSE back
scattered electrons). Posteriormente, a anlise quantitativa dos sulfetos e sulfatos foi realizada em
mododedispersoporcomprimentodeonda(WDSwavelengthdispersivespectroscmetry).
O componentechave do EDS um detector semicondutor que um contador proporcional.
Este sistema normalmente utilizado para anlises qualitativas, e tambm permite a execuo de
anlisessemiquantitativasrpidas(fraodesegundo)eoperade0eVa10keV(informaesinternas
dolaboratrio).
NosistemadeDispersoporComprimentodeOnda(WDS)aamostra,ocristaldedifraoeo
detector tipo contador proporcional esto contidos em uma mesma circunferncia. O princpio de
funcionamentodosistemaseguealeidedifraodeBragg(n=2d.sen).,onde.osistemaWDSmais
lento,comresoluoemtornode5eVeconseguediferenciarasobreposiodepicoscomdiferena
deenergiamenordoque150eV,oquenopossvelnosistemaEDS.
Asamostrasdesulfetoforamanalisadasa20kV,oslimitesdedetecosoapresentadosna
tabela2.01.

Tabela2.01Limitesdedetecoparacadaelemento,nasanlisesdesulfeto.

As

Pb

Fe

Co

Ag

Se

Cu

Ni

Pt

Pd

Zn

38

96

40

45

43

18

138

50

40

52

21

42

As amostras de sulfato tambm foram analisadas a 20kV e os limites de deteco so

apresentadosnatabela2.02.

Tabela2.02Limitesdedetecoparacadaelemento,nasanlisesdesulfato.

Mg

Si

Al

Ba

Ca

Cr

Fe

Se

Sr

Pb

Mn

29

92

59

563

149

93

204

104

232

1933

137

168

94

IstoposdeEnxofre
Revisobibliogrfica
O estudo de istopos de S pode auxiliar na identificao da gnese e evoluo das rochas
estudadas. O fracionamento de enxofre pode ser causado por diversos processos e varia de acordo
com a temperatura, O2, balano de massa, condies dexidoreduo do ambiente, diferenciao
magmtica, alm de processos superficiais e interaes com bactrias redutoras. Alguns estudos
anteriores (Nikiforov et al. 2006, Drppel et al. 2006, Farrel et al. 2010) abordam os controles da
variao isotpica de S em funo da temperatura, comparando diferentes carbonatitos em um
mesmocomplexoalcalino,oudistintoscomplexosentresi,bemcomoosefeitosdadesgaseificaode
SO2 e H2S e da fenitizao sobre a composio isotpica original. Esses estudos demonstram a
importnciadosistoposestveisdeSnoestudodecomplexoscarbonatticos,masatcnicanohavia
ainda sido aplicada aos complexos da Provncia gnea do Alto Paranaba, o que motivou o presente
trabalho.
As variaes na composio isotpica de sulfetos, sulfatos ou espcies de S aquoso resultam do
fracionamento entre as fases minerais envolvidas, o qual controlado fundamentalmente pela
temperaturaouporreaesdeoxidaoereduo(Seal,2006):

em alta temperatura (sistemas gneos) as distintas fases minerais tendem a estar em

equilbrioisotpico,

emtemperaturaintermediria(sistemashidrotermais),

em baixa temperatura (diagnese sedimentar) o fracionamento isotpico tende a

prevalecer.

Alm disso, processos superficiais (intempricos) tambm geram fracionamento isotpico, que
aparecelocalmenteemregistrosgeolgicos(Seal,2006).
Seal (2006) detalha o ciclo geoqumico do Enxofre e indica duas pocas onde a variabilidade
isotpicadeSdegrandeimportncianosprocessosuperficiais.
Antesde2,4Ga,oregistrosedimentarrevelavariaolimitadade34Sentresulfetosesulfatose
ampla variao de 33S, indicando que antes de 2,4 Ga o principal fracionamento de S era
independentedamassa.Apartirde2,4Ga.comoaparecimentodeumaatmosferaricaemoxignioe

o consequente diminuio das reaes fotoqumicas que geram o fracionamento independente da

massa,avariaoseinverteecomeaahavervariaoamplade34Selimitadade33S.
H cerca de 0,7 Ga, outra grande mudana na variabilidade de 34S de sulfetos e sulfatos
sedimentaresocorre,indicadaporumamaiorgamadecomposies,quenovamentefoiinterpretada
emtermosdeaumentodeconcentraesatmosfricasdeoxignio.
Oregistroisotpicodasbactriasredutorasdesulfatopodeserencontradoemmuitospontosdo
ciclo do enxofre, desde sulfetos e sulfatos sedimentares, at camadas de carvo, depsitos
hidrotermais de assoalhoocenico,depsitos continentaisdo tipo Mississipi Valey formadosa partir
de bacias de salmoura, e dos magmas de todas as composies que tiveram interao com rochas
crustais(Seal,2006).
Os estudosdeistoposestveisdeSpodemelucidaraspectosda gneseeevoluodemagmas
alcalinosecarbonatitos,conformeosexemplosabaixo:
Zheng definiu que 34S de uma rocha gnea pode se afastar do magma original simplesmente
devidodestilaoRayleighduranteadesgaseificaodeSO2e/ouH2S,oudevidoaofluxoseletivode
enxofre atravs do fracionamento de equilbrio por troca isotpica entre o sulfato e sulfeto na
temperatura de solidificao do magma. A intensidade da mudana na composio isotpica de S
dependedaO2,dobalanodemassaedamedidaemqueosistemaseabre.
O processo de desgaseificao Rayleigh pode ser identificado pela correlao de 34S e a
concentrao total de enxofre. O fracionamento isotpico e solubilidade de enxofre no magma est
relacionadocomaO2quecontrolaasrazessulfato/sulfetoeFe3+/Fe2+(Zheng,1990).
Nikiforov et al. (2006) determinaram 34S em: fenocristais de pirita, de siderita e ankeritacalcita
carbonatitoprimrios;baritaprimriadosideritacarbonatito;pseudomorfosdesulfatosepigenticos
hidrotermais (baritocelestina e celestina) sobre barita primria; e metacristais de pirita em rochas
encaixantes do complexo carbonattico de Tuva Central e detectaram desvios de 34S em relao a
composioprimriaquepodemserexplicadospelaremooisotpicadeenxofrelevesobaformade
SO2, como resultado de uma intensa desgaseificao sob alta fugacidade de oxignio. Os sulfatos
hidrotermaisapresentaramvaloreselevadosde34S.
Mitchell e Krouse (1975) estudaram distintos complexos carbonatticos e obtiveram resultados
diferentes para cada um deles, relacionando a variao com os parmetros T, O2 e pH durante a

formao.OsresultadosindicaramquecomadiminuiodaTeaumentodeO2,amdiade34Sfica
maisnegativaemrelaomdiadomagmaoriginal.
Drppeletal.(2006)determinaramavariaoisotpicacomtemperatura,fugacidadedeoxignio
e estado de diferenciao do magma e monitoraram processos tardios como fenitizao e
mineralizaesemferrocarbonatitosdeSwartbooisdrif,Nambia.

Preparaodeamostras
Neste trabalho, as determinaes da composio isotpica foram realizadas sobre as mesmas
amostras analisadas em microssonda eletrnica, isto , gros separados manualmente, resinados e
polidos.OequipamentoutilizadofoiumMCICPMSNeptune(ThermoFinnigan)comlaserNewWave
UP213Nd:YAGacoplado.Ospadresderefernciaparaanliseinsitudesulfetosjestavamprontos
nolaboratriodegeocronologia,enquantoqueospadresdesulfatoforamcolocadossobpressode
10tonpor5minutosusandoumaprensahidrulicaPerkinElmerparaconfeccionarcomprimidos.

Laserablationmultiplecollectorinductivelycoupledplasmamassspectrometry(LAMCICPMS)
OMCICPMSumespectrmetrodemassacapazdemedirdiversasmassasaomesmotempo.
compostopor3mdulos:ummduloICP(inductivelycoupledplasma),ummduloESA(eletrostatic
analyser)eummdulomulticoletor(Figura2.01).Asespecificaesedescriodofuncionamentodo
equipamento,apresentadasabaixo,foramretiradasdoManualThermoFinniganNeptune.


Figura2.01DesenhoesquemticodosistemaMCICPMS(ManualThermoFinnigan2003)

MduloICP

Estemduloestrelacionadogeraodeplasma.Eleincluicontroladoresdefluxoparao

fornecimentodeargnio(gscarreadordaamostra),ogeradorRFqueligaoplasma,oestgioXYZ
daposiodatocha,e,finalmente,acmaradesprayeatochaemsi.
A amostra (gs ou lquido) alimentada continuamente na nebulizao (sistema de
admisso),ondeumaerosolcontendoargnioeaamostragerado.Esteaerossolguiadoparaa
cmara de pulverizao, que remove as gotas maiores. A mistura ento refinada em aerosol,
direcionada para o injetor da tocha do plasma, injetada no centro do plasma e instantaneamente
dissolvidaeionizada.

MduloESA
Este mdulo responsvel por relanar e acelerar ons. Ele inclui a interface de plasma,
sistemadelentesdetransfernciaeoanalisadoreletrosttico(ESA).
Os ons (assim como eltrons, prtons e todos os tipos de molculas de gs) entram no
espectrmetro de massa atravs dos orifcios na ponta do cone de amostragem. O fluxo de gs
principal vai para a bomba de interface, enquanto os ons vo para o cone skimmer. Os ons so

10

extrados do fluxo de gs atravs da lente de extrao e seguem no sistema pela lente de

transferncia.
Apartirdosistemadelentesdetransferncia,ofeixedeonsentranoanalisadoreletrosttico
(ESA), que focaliza os ons. ons com energias diferentes esto focalizados em pontos ligeiramente
diferentesaolongodaimagem.Poucoantesdaimagemintermediria,osonssoaceleradosparao
finaldeenergiadofeixedeonsa10keV.

MduloMulticoletor
A seo final do instrumento abrange o m, o zoom ptico, o multicoletor e o sistema
amplificadordecorrente.Aseparaodemassaeadetecodeonsocorremnestemdulo.
O Netuno equipado com um conjunto de lentes de zoom. Usando as duas lentes de
quadrupoloposicionadasantesedepoisdom,adispersodemassapodeseralteradaemcercade
5%.Ozoompticodinmicopodeserutilizadoparacompensardispersesdemassaligeiramente
diferentesparaosdiferenteselementos.
O Multicoletor equipado com nove copos de medida Faraday (contagem em V) mais oito
contadoresdeons(contagememcps).Osdetectoressomovidosamotorepodemserposicionados
precisamenteaolongodoplanofocaldaslentesdeons.
Aextraodaamostraparaanlisefoirealizadacomlaseracoplado.OlaserutilizaHecomogs
carreadordaspartculasliberadasinsitupelolaseresemisturacomoArantesdeentrarnomdulo
ICP,substituindoonebulizadorquesomenteusadoparaanlisedesolues.

Procedimentosanalticos
O equipamento foi calibrado, primeiramente, com solues padro medindo a massa 32S no
faraday L2, a massa 33S no copo central e a massa 34S no faraday H1 levando em considerao as
interferncias possveis (16O,

17

O,

18

O,

15

N, 1H). Com a extrao da amostra por laser essas

interfernciasdiminuem,masaindafeitamaisumacalibraonolaserparamelhoraraintensidade
do sinal e garantir a reproduo do padro para anlises in situ. As amostras so lidas em grupo de
quatro leituras, para um branco e um padro. Os padres utilizados para calibrao e correo dos

11

dadosforamNBS123,IAEAS1,IAEAS2,calcopirita(padrointerno)epirita(padrointerno)paraos
sulfetos,eNBS127eIAEAS3paraossulfatos.
Osparmetrosutilizadosparaolaserforam10Hzdefreqncia,100mdetamanhodofeixee
53%daenergiadolaser.Josparmetrosdeoperaodoespectrmetropodemvariaracadadiade
anlise.Osparmetrosaproximadossoapresentadosnatabela2.03.
Asanlisesforamrealizadasemmodoraster(linhadeanlise),quemaisutilizadodoqueomodo
ponto, para obter um material de anlise mais homogneo em relao ao tempo (Craddock et al.
2008).
Tabela2.03Parmetrosdeconfiguraodoespectrmetroparaanlisesinsitu.
CoolGas
15
AuxGas
0,7
SampleGas
0,998
AddGas1
0
AddGas2
0,44
PosioX
0,810
PosioY
0,970
PosioZ
0,320

Tratamentodosdados

Osresultadossoexpressosnanotaocomumdeltapermil(),querepresentauma
comparaocomopadroderefernciaViennaCanyonDiabloTroilite(VCDT)quecalculadoda
seguintemaneira:

R amostra Rpadro
x10
R padro

OndeRarazoisotpica(34S/32S)medidaparaaamostraeparaopadroqueovalordereferncia.
Aprecisoanalticafoiemtornode0,1a0,5.

12

CAPTULO3
SulfurisotopesfromalkalinecarbonatitecomplexesalongthebordersoftheParan
BasinGois,MinasGeraisandSoPauloStates,Brazil

C.S.Gomidea,J.A.Brodb,T.C.JunqueiraBrodb,B.Buhna,E.S.R.Barbosab,P.F.O.Cordeiroa,M.
Palmieric,C.B.Grassod,M.G.Torrese
aInstitutodeGeocincias,CampusUniversitrioDarcyRibeiro,UniversidadedeBraslia(UnB),CEP70910900,Braslia,DFBrazil.

InstitutodeEstudosScioAmbientais,UniversidadeFederaldeGois(UFG),CaixaPostal131,CEP74001970,Goinia,GOBrazil.
AngloAmerican.
dFosfertil.
eUniversidadeCatlicadeBraslia.
b
c

Abstract
This work presents petrographic, chemical, and sulphur isotope data in alkalinecarbonatite
complexes of the Alto Paranaiba Igneous Province (APIP) and in the Jacupiranga complex, from the
Ponta Grossa Province. The rocks from carbonatite complexes, especially those of the carbonatite
series, often contain sulphides (pyrite, pyrrhotite, chalcopyrite, galena, bornite, pentlandite) and
sulphates(mainlybarite).Therefore,sulphurisanimportantelementforresearchinthepetrogenesis
of these rocks. This work presents the first sulphur isotope data from APIP and Ponta Grossa
complexes.
The studied samples show mesoscopic and microscopic quench textures, such as bladed
carbonate and sulphide crystals, with interstitial microgranular aggregates of carbonate, barite and
sulphides.Theseareinterpretedastheresultofrapidcrystallizationduringdegassingofasupercooled
carbonatite magma. The CO2 degassing at APIP complexes was studied in previous works from
Research Group in Alkaline Rocks and Associated Mineralizations and this work adds degassing of
sulphurgaseousphases(H2Sand/orSO2)tothatpicture.Thesulphurisotoperesultsinsulphidesfrom
samples showing evidence of degassing vary from core to rim, with the latter showing higher (less
negative) 34S, compared with the former, indicating that degassing took place in an oxidizing
environment.
Isotopic data indicates that as magma differentiation progresses it consumes particullarly
heavier isotopes into the solid phases, leaving a residual magma/fluid enriched in 32S. On the other
hand, sulphur loss by degassing under oxidizing conditions lead the residue to evolve toward higher
34S.
Keywords:Carbonatite,sulphide,sulphate,APIP,Jacupiranga,sulphurisotope,degassing.

1. Introduction

ThecarbonatitecomplexesandalkalinerocksfromtheAltoParanabaIgneousProvince(APIP)and
from otheralkaline provinces occurring at thebordersof the Paran Basin have been the subjectof
studiescomprisinggeochemistry,mineralogy,andstable(mostlyC,O)andradiogenic(Sr,Nd,Pb,Re

13

Os,LuHf)isotopes(e.g.Gibsonetal.,1995a,CominChiaramonti&Gomes,2005,Carlsonetal.,2007).
Although many of the rocks in these complexes, particulary those belonging to the carbonatite and
phoscoritepetrogeneticseries(e.g.Barbosa,2009),containsulphidesand/orsulphates,theywerenot
yetstudiedforsulphurisotopiccomposition.
This technique has been applied to assess petrological and metallogenetic problems in other
carbonatite complexes, such as Swartbooisdrif, Namibia (Drppel et al. 2006), and Magnet Cove,
BearpawandMountainPass,intheUSA(Mitchell&Krouse,1975).Sulfurisotopesstudieshavebeen
successfulindeterminingthemagmaticorhydrothermaloriginofthesulphur(Nikiforovetal.2006),
assessingthe variationof isotopecompositionwithtemperature,oxygenfugacityanddifferentiation
stageofmagma,aswellasstudyingfenitizationandmineralizationprocesses(Drppeletal.2006)and
degassingofSO2andH2Sfrommagmas(Zheng,1990).
Mitchell & Krouse (1975) stated that each carbonatite appears to have its own mean sulphide or
sulphate isotopic composition. Deines (1989) compiled the 34S composition of sulphides from
carbonatites and found that it varied from20 to +5suggesting that some differences between
carbonatitecomplexesmayreflectSisotopeheterogeneityinthemantle.
InthisstudywereportthefirstSisotopedataforcarbonatitesinBrazil.WediscussSstableisotope
and petrographic data for various rock types and minerals in carbonatite complexes from the Alto
ParanabaIgneousProvince(APIP)andfortheJacupirangacomplex(PontaGrossaAlkalineProvince),
with the aims of understanding the genesis and evolution of these complexes and comparing them
withothercomplexesworldwide.
InvariousAPIPcomplexes,CandOstableisotopedatadefineadegassingtrendforCO2(Junqueira
Brodetal.inpreparation,Gomideetal.,2008,Cordeiroetal.,2011).However,theserocksmayalso
degasssulphur,takingintoaccount that theyusuallycontaincrystallizedsulphidesand/orsulphates,
and that sulphur is an important volatile constituent in alkaline magmas associated with CO2 and
halogens(Bailey&Hampton,1990).Furthermore,Zheng(1990)interpretedthesignificantdifferences
inthesulphurisotopecompositonofsomeigneousrocksrelativelytometeoritesandprimarymantle
as the result of Rayleigh outgassing and selective flux process. In this work we propose that the
degassing process in alkaline carbonatites magmas drives sulphur isotope ratios to positive values,

14

whereas fractionation from less evolved (bebedourites, in the APIP, and jacupiranguites, in the
Jacupirangacomplex)tomoreevolvedrocks(carbonatites)drivestheseratiostonegativevalues.

2. Geologicalsetting

A voluminous Cretaceous alkaline magmatism occurred in central and southern Brazil, and in
eastern Paraguay (CominChiaramonti and Gomes, 1996, 2005). Almeida (1983) argued that alkaline
rocksspreadingoveralargeareaoftheSouthAmericanPlatformsouthofthe15oSlatitudearedivided
in 3 groups: those located at the borders of the Paran basin, those in the east coastal region and
thoseineasternBolivia.ThatauthoradoptedtheconceptofAlkalineProvincetodivideanddescribe
geographic groups showing petrographic relations with each other and belonging to a particular age
range. The Provinces were named as Poos de Caldas, Alto Paranaba, Rio VerdeIpor, Paraguai
Oriental, Mariscala, Piratini, Santa Catarina, Ponta Grossa, Ipanema, Serra do Mar, Velasco and
Candelria. In this work we study carbonatite complexes of the Alto Paranaba and Ponta Grossa
Provinces.
Gibsonetal.(1995a)interpretedtheEarlyCretaceousalkalinemagmatism(approximately130Ma)
and the contemporaneous Paran magmatism as related with the Tristan da Cunha mantle plume,
whereasGibsonetal.(1995b,1997)andBrodetal.(2005)correlatedtheLateCretaceousmagmatism
(about85Ma)atthenorthandnortheastbordersoftheParanBasinwiththeimpactoftheTrindade
mantleplume(Gibsonetal.1995b)atthesubcontinentallithosphereofcentralBrazil.Thompsonet
al.(1998)statethattheshiftedtrajectoryoftheTrindadeplumegeneratedtheSerradoMarprovince,
inSEBrazil.
Ernesto(2005)arguedagainstthemantleplumemodelbasedonpaleomagneticdata,statingthat
theseprovinces(includingtheParanfloodbasalts)wereneverplacedaboveplumes.Thisreinforced
the alternative model proposed by Ernesto et al. (2002) according to which these provinces were
generated by thermal sources unrelated with material transfer from the lower mantle to the
lithosphere.
Some of the alkaline provinces surrounding the Paran Basin contain carbonatite complexes,
occurring as massive cores (plugs, stocks) usually displaying oval to circular outlines in map view

15

(Gomes et al. 1990). Among these, the APIP complexes, and the Jacupiranga complex in the Ponta
GrossaProvincewerethesubjectofthisresearch(figure3.01).
The Alto Paranaba IgneousProvince, locatedin southernGois andwesternMinas GeraisStates,
resultsfromanintense,LateCretaceusalkalinemagmatismthatgeneratedintrusive(dykes,conduits,
diatremes,andcarbonatiticcomplexes)andextrusive(lavasandpyroclasticrocks)bodies(Leonardos
etal.,1991,Gibsonetal.,1995b,Brodetal.,2000,CominChiaramonti&Gomes,2005,Carlsonetal.,
2007). It is one of the largest ultramaficultrapotassic provinces of the world (Gibson et al. 1995b).
Kamafugite is by far the dominant rocktype in the province, forming one of the few known
kamafugitecarbonatiteassociations(Brodetal.,2000).
TheAPIPalkalinecarbonatitecomplexes(CataloI,II,SerraNegra,SalitreI,II,III,AraxandTapira)
arerelativelyshallow(e.g.SantosandClayton,1995;Brodetal.,2001,Ribeiroetal.,2005),multistage
intrusions formed by rocks derived from various (bebedourite, carbonatite, and phoscorite)
petrogeneticseriesrelatedtoeachotherbyfractionalcrystallization,liquidimmiscibilityanddegassing
(Brodetal.,2004,Ribeiro,2008,Cordeiroetal.,2010,Barbosa,2009).

Figure3.01CarbonatiteoccurrencessurroundingtheParanBasin.Thecarbonatitecomplexesstudiedinthisworkare
shownasstars.ModifiedfromOliveiraetal.(2004)andWooley&Kjarsgaard(2008).

16


Catalo I, located 20km to the northeast of Catalo city, is a multiphase intrusion composed of
dunite, clinopyroxenite, bebedourite, carbonatite, phoscorite, nelsonite and metassomatic
phlogopitites,andhostsimportantdepositsofphosphate,niobium,rareearthelements,titaniumand
vermiculite (Carvalho & Bressan, 1997, Brod et al., 2004, Ribeiro, 2008, Cordeiro et al., 2011). The
complex evolved from a phlogopitepicrite magma by several stages of fractional crystallization and
liquidimmiscibility(Ribeiro,2008).Magnesiocarbonatiteisbyfarthedominantcarbonatitetypeinthe
complex.Sulphidesoccurtowardsthemoreevolvedstagesinthecomplex,andaretypicallypresentin
somephoscorites andinmanynelsonites andcarbonatites.Sulphate (barite)occursat aneven later
stage,bothinmagmaticcarbonatiteandinlatestage,postmagmaticveins.
CataloII,nearly10kmNNWfromCataloI,isanelongated(NESW)bodywithsinuousmargins,
suggesting the existence of multiple intrusions. Machado Junior (1992) describes pyroxenites, quartz
syenites, alkalifeldspar syenites, calcite carbonatites, silicocarbonatites, dolomite carbonatites e
lamprophyres,

and

metasomatic

phlogopitites.

Calciocarbonatites

dominate

over

magnesiocarbonatites. Palmieri (2011) recognized at least two separate magmatic systems in the
complex, one in the north, dominated by phoscorite and the other in the south, dominated by
nelsonite. Sulphides and sulphates occur mainly in the southern (nelsonite) domain of the complex.
Sulphides are common accessory phases both in nelsonites and in carbonatites. Sulphates occur in
latestageBarichmagnesiocarbonatites.
SerraNegraislocatedtotheeastofPatrocniocity,inwesternMinasGeraisandisthelargestAPIP
carbonatitecomplex,with65km2.Itisdominantlycomposedofdunite,bebedourite,andcarbonatite,
with rare trachytes. Both calciocarbonatite and magnesiocarbonatite occur (Grasso et al. 2010). The
complex intrudedquartzitesfrom CanastraGroupandgeneratedavery pronounced domestructure
(Brod et al. 2004). Sulphides occur as accessory phases in carbonatites (especially
magnesiocarbonatites).
SalitreconsistsofthreebodieslocatedtothesouthoftheSerraNegraComplex,andcomposewith
the latter a system of coalescing intrusions (Mariano & Marchetto, 1991). Salitre I, with 35 km2, is
composed of bebedourite, tinguaite, trachyte, fenite, apatitecarbonatite, calcite carbonatite and
phoscorite.SalitreII,with2.5km2,islocatedbetweenSerraNegraandSalitreI,andcontainsmainly

17

ultramaficrocks(dunite,perovskitite,bebedourite,localycutbycarbonatiticdikesandveins).SalitreIII
isasmallbodytothesouthofSalitreI,formedbypyroxenites,withsubordinatedphoscorites(Brodet
al 2004, Barbosa, 2009). Both calciocarbonatite and magnesiocarbonatite occur in the complex.
Sulphides are present in bebedourite, phoscorite and carbonatite, and sulphate occurs only in late
stagemagnesiocarbonatite.
Arax(alsoknownasBarreiro)isasmall(15km2)complexlocatedapproximately6kmtothesouth
of Arax city. In many aspects, this complex is similar to Catalo I. It is composed of carbonatites,
phoscorites and a large volume of phlogopitites derived from the metasomatism of ultramafic rocks
suchasbebedouritesanddunites(IssaFilhoetal.,1984,Traversaetal.,2001).Magnesiocarbonatiteis
thedominantcarbonatitetype.Theintrusiongeneratedadomicstructureinschistsandquartzitesof
theNeoproterozoicIbiGroup(Seer,1999).Sulphideoccursaspyrite,chalcopyrite,sphalerite,galena
and cobaltite in carbonatites, especially ferrocarbonatites, which are clearly subordinate to the
previous carbonatite types (Traversa et al. 2001). Sulphate (barite) occurs in carbonatites. Samples
containing both sulphide and sulphate were obtained from carbonatites and one sample from
phoscorite.
Tapira,30kmtotheSEofAraxcity,isanapproximatelyellipticalcomplexwith35km2,composed
mainly bybebedourite,withsubordinatecarbonatiteandsyeniteandraremelilitoliteanddunite,all
cut by ultramafic dikes of kamafugite affinity (Brod, 1999, Brod et al., 2000, Brod et al., 2003).
Calciocarbonatitedominatesovermagnesiocarbonatite
ThePontaGrossaProvinceislocatedattheeasternmarginoftheParanaBasin.UnliketheAPIP,this
province is EarlyCretaceous in age, and dominated by sodic alkaline rocks Nesyenite, malignite,
melteigite,ijolite,phonolite,carbonatite,lamprophyre,pulaskite,dunite,pyroxenite,urtite,ankaratite,
alkaligabbro,syenogabbro,syenodiorite,syenite,peralkalinephonolite,alkaliolgabbro,syenodiorite,
essexite, basanite, phonotephrite, shonkinite and trachyte (Morbidelli et al. 1995). It comprises
plutonicstructuresBanhadao,Itapirapu,Jacupiranga,JuquiandTunas,pipesandplugsBarrado
PontaGrossa,BarradoTeixeira,CerroAzul,MatoPreto,MorrodoChapeuandSeteQuedas(Rubertiet
al.2005).
Jacupiranga(alsoknownasCajati),theonlycomplexfromthePontaGrossaProvincestudiedhere,
islocatedca.10kmtothewestofJacupirangacityandnorthwardsfromtheCajatitown,inSoPaulo

18

State.ItisemplacedintotheAunguigroup(Rubertietal.2005)andhasanovalshape(about65km2)
withasmallelongatedcarbonatitecore(MorrodaMina)thatintrudedintojacupiranguites.Themain
rocktypes in the complex are pyroxenitejacupirangite, serpentinized peridotite, ijolite, nepheline
syenite,carbonatite,essexite,monchiquite,andtinguaite(Gomesetal.1990).Bothcalciocarbonatite
and magnesiocarbonatite are present in the complex. Sulphides are accessory phases in some
carbonatites,andalsooccur,rarely,injacupirangites.

3. Sampledescription

CataloII

Samples from Catalo II include different types of carbonatites and nelsonites. The carbonatites
(figure3.02)varyfromcoarsegrainedtomicrocrystalline,andmaycontainvariousamountsofapatite.
Phlogopite,tetraferriphlogopite,magnetitewithilmeniteexsolutionlamellae,andbaritearecommon,
pyrochloreisanaccessoryphase,andamphibolewasfoundrarely.Pyrite,pyrrhotiteandchalcopyrite
arethesulphidephases.Pyriteisusuallygranularandeuhedral,butoftenshowsveryirregulargrain
surfaces,probablyresultingfromrecrystallizationofmicrogranularaggregates(figure3.02b).Itisalso
found as veins or scattered grains. Chalcopyrite occurs as small anhedral grains. Pyrrhotite occurs
restrictedlyinthestudiedsamples,astabulargrainsorformingnettexture.Bariteistheonlysulphate
present,asfinegrainaggregatesorasacriptocrystalinemasstogetherwithcarbonate.Bariteismore
abundantthansulphidesinthecarbonatites.
Carbonates in the Catalo II carbonatite samples have a cloudy aspect, marked by brownish
irregular patches with a "dusty" aspect. Presumably this results from the quench precipitation of
carbonateduringoscillatorytemperaturebehaviorinheterogeneousregionscreatedbyCO2degassing
in the magma chamber (JunqueiraBrod in preparation). Although carbonate is the dominant phase,
barite, sulphides, and phlogopite may also be present in these criptocrystalline aggregates (figure
3.02c,d).

19

Figure3.02CarbonatitefromtheCataloIIcomplex.A:phlogopite(phl),magnetite(mgt)andrecristalyzedpyrite(py).
cbt=carbonate Field width: 5mm. Plane polarized light; B: Same as A in reflected light. C: Backscattered image of a
carbonate(cbt)+barite(brt)massincarbonatitefromtheCataloIIcomplex.D:Highermagnificationviewoftheback
scatteredimageinA

Nelsonites(figure3.03)arefinetocoarsegrained,composedofmagnetite,apatite,phlogopite,
carbonate,andvariableamountsofpyrochlore.Sulphideisrelativelyabundantintheserocks.Pyrite
occursaseuhedralgrains,asveins,orasscatteredcrystals.Itisoftenassociatedwithmagnetiteand
sometimes replaces this mineral (figure 3.03d), indicating a latestage formation. Chalcopyrite may
form concentrations about 1.5cm wide in some samples (figure 3.03b), and also occurs as very fine
grainaggregateswithadustyappearance,associatedwithpyrite.Borniteisveryrare,includedinor
intergrownwithchalcopyriteBaritewasnotfoundinthisrocktype.

20

Figure 3.03 Textural features of nelsonites from the Catalo II complex. A: Apatite (Ap) and pyrochlore (Pcl) in
nelsonite, plane polarized light. Field width: 5mm. B: Same as A, in reflected light, showing chalcopyrite (Cpy) and
subordinatepyrite(Py).Fieldwidth:5mm.C:Phlogopite(Phl),apatite(Ap),pyrochlore(Pcl),carbonate(Cbt)andmagnetite
(Mgt)innelsonite,planepolarizedlight.Fieldwidth:5mm.D:Pyrite(Py)andrarechalcopyrite(Cpy)replacingmagnetite;
notethattheearliermagnetitecontainedilmenite(Ilm)exsolutionlamellaethatremainedpreservedupondissolutionand
substitutionofthemagnetitegrain,formingatrellistexture,reflectedlight.Fieldwidth:1,5mm.

CataloI

ThestudiedsamplesfromCataloIarecarbonatites,phoscorites,nelsonites,magnetititesandfenites.
The carbonatites (figure 3.04) are fine to coarse grained, and may contain various amounts of apatite,
phlogopite, magnetite and barite, tetraferriphlogopite, perovskite, pyrochlore. Common textural
featuresaremicrogranularbaritepockets,apatitewithfloworientation,andalignedgrainsofmagnetite.
Sometimesmagnetitecontainsilmeniteexsolutionlamellae,andmaydevelopaskeletalaspectifthehost
magnetiteisdisolvedofreplaced.Somecarbonatitesdisplaybladedcarbonateandsulphidecrystals(figure
3.04d,f) typical of rapid crystallization as described by JunqueiraBrod (in preparation). In these samples,

21

carbonatesmayalsoformgranular(recrystallized)aggregatesordiffusemassesliketheonesdescribedfor
CataloII.Apatiteprismsareoftenalongthefacesofbladedcarbonatecrystals.

Figure3.04TexturalfeaturesofsulphidesandbaritesincarbonatitesfromtheCataloIcomplex.A:Apatite(Ap),carbonate
(Cbt)andphlogopite(Phl)incrosspolarizedlight.Fieldwidth:5mm.B:SameasAinreflectedlight,showingasmoothsurfacefor
pyrite(Py).Fieldwidth:5mm.C:Carbonate(Cbt),barite(Brt);notetheintergrowthofpyriteandbarite.Crosspolarizedlight.Field
width:5mm.D:SameasCinreflectedlight,barite,pyrite(Py)andmagnetite(Mgt);notetheintergrowthofpyriteandbarite.Field
width: 5mm. E: Pyrite (Py) with pitted surface, probably resulting from recrystallization as microgranular aggregates. Reflected
light.Fieldwidth:5mm.F:Pyrite(Py)withskeletalappearanceandirregularsurfaces,probablyresultingfromrecrystallizationas
microgranularaggregates.Reflectedlight.Fieldwidth:5mm.

22

Barite is a common phase inCatalo I carbonatites, occurring as radial aggregates, mixed in irregular
carbonate masses and associated with sulphides or filling voids between bladed carbonate crystals,
surroundedby small carbonateneedles. Thedominantsulphide speciesisgranular,euhedraltoanhedral
pyritemostlyshowingasmoothsurface(figure3.04b).Morerarelypyritemayhaveaverypittedsurface
(figure3.04e,f)analogoustothoseofCataloII,orbeinterstitial.Chalcopyriteisrareanditwasfoundonly
assmall,veryfinegrainedaggregatesnearpyrite.
Phoscorites (figure 3.05) are coarse grained to pegmatoid and essentially composed of apatite,
magnetite, carbonate, and phlogopite, with or without olivine and rare sulphide. Phlogopite is often a
pseudomorphoverolivine.Pyriteandchalcopyriteshowthesametexturalvarietiesasinthecarbonatites
(figure3.05b).Inphoscorites,theamoeboidcontoursofsomepyriteaggregatessuggestthatitmayhave
precipitatedfromanimmisciblesulphideliquid(figure3.05d).

Figure3.05TexturalfeaturesofsulphidephoscoritesfromtheCataloIcomplexA:Apatite(Ap)andphlogopite(Phl)
from phoscorites in cross polarized light. Field width: 5mm. B: Same as A in reflected light, showing a pitted surface in
various pyrite (Py) individual grains and very fine grained chalcopyrite (Cpy) aggregates with a dusty appearance. Field
width:5mm.C:Apatite(Ap)andphlogopite(Phl).Planepolarizedlight.Fieldwidth:5mm.D:SameasC,inreflectedlight
showingpyrite(Py);notetheamoeboidgeometryoftheinterstitialpyriteaggregates,suggestingthattheyformedfroman
immisciblesulphideliquid.Fieldwidth:5mm.

23


Nelsonites(figure3.06)arefinetomediumgrained,composedofmagnetite,apatite,phlogopite,
carbonate,andpyrochlore,withsulphidesasaccessoryphase.Sometimesthepercentageofmagnetite
is high enough to allow the rock to be classified as a magnetitite. Sulphide (mostrly pyrite and
chalcopyrite)isrelativelyabundantintheserocks.Pyriteoccursaseuhedralindividualgrains,asveins,
asaninterstitialphase,orasaggregatesofbladedgrains(figure3.06b).Thelatterareinterpretedas
formed by rapid crystallization. Chalcopyrite is less abundant than pyrite and usually occurs as fine
aggregatesorsmallgrains.

Figure 3.06 TexturalfeaturesofnelsonitesfromtheCataloIcomplex.A:Apatite(Ap),carbonate(Cbt),pyrochlore

(Pcl)andphlogopite(Phl)innelsonite,planepolarizedlightshowingfloworientationofphlogopiteandapatitecrystals.Field
width:5mm.B:Pyrite(Py)grainswithpittedsurfaceandfinegrainedchalcopyrite(Cpy)aggregates.Fieldwidth:5mm.

Fenitesoccurbothexternally(fenitizedPrecambriancountryrocks)andinternallyintheCatalo
I complex. In this work we studied only the internal fenites, which result from a strong potassic
metasomatism that converted the original ultramafic rocks (dunites, pyroxenites, and bebedourites)
intomagnetiterichphlogopitites(e.g.Grassoetal.,2006,Palmierietal.,2006,Ribeiro,2008).These
rocks are oftencross cut by numerouscarbonatiteveins, andthephlogopitevarietyistypically fine
grained tetraferriphlogopite. The sulphide present is pyrite. Catalo I fenites were included in this
studytoassessthesulphurisotopecompositionofathemetasomaticfluidsinvolvedinthelatestage
evolutionofthecomplex.

24

SerraNegra

TheonlyrocktypeanalyzedfromSerraNegraiscarbonatite(figure3.07).Inthestudiedsamples
carbonateissubhedral,formingaroughlyequigranularmosaictexture.Smallamountsofapatitemay
be present. Both phlogopite and tetraferriphlogopite varieties are found in euehdral to subhedral
lamellae, and the mica is usually associated with barite, when the second is present. Rare,
disseminated,finegrainedpyriteisthesolesulphidefoundinthesesamples.

Figure3.07SerraNegracarbonatites.A:Coarsegrainedcarbonate(Cbt)incrosspolarizedlight;Fieldwidth:5mm.B:
SameasA,inreflectedlight,showingasmallpyritegrain(Py).Fieldwidth:5mm.

Salitre

Samples from the Salitre complex comprise carbonatites, phoscorites and bebedourites. The
carbonatites (figure 3.08) are fine to coarse grained and contain variable amounts of apatite,
phlogopite, magnetite, and barite. More rarely, was found pyrochlore. Apatite ranges from trace
amountstoamajorcomponent,leadinginextremecasestoagradationtoacarbonaterichapatitite.
Sulphidescomprisepyrite,pyrrhotite,chalcopyrite(figure3.08b)andgalenabutonlytheformertwo
were large enough grains to be analysed for sulphur isotopes. Pyrite usually occurs as granular
aggregates or as grains with irregular surface, disseminated in the rock. Pyrrhotite shows smooth
surface and may form bladed cystals of scattered grains. Chalcopyrite forms discontinuous
microgranularpatches.

25

Figure 3.08 Texturalfeaturesofcarbonatites fromthe Salitre complex.A:Apatite (Ap), carbonate (Cbt),phlogopite

(Phl)andpyrochlore(Pcl)inplanepolarizedlight.Fieldwidth:5mm.B:Elongatedsulphidegrain,pyrrhotite(Po)isthegrain
withaskoothsurface,pyrite(Py)istheirregularsurfacegrain,andchalcopyrite(Cpy)ispresentinsmallamounts,bordering
pyrrhotiteandpyrite.Reflectedlight.Fieldwidth:5mm.C:Carbonate(Cbt)andpyrite(Py)showingzonationincarbonate
crystals.Planepolarizedlight.Fieldwidth:5mm.D:Carbonate(Cbt)andcomplexlyzonedbarite(Brt).Crosspolarizedlight.
Fieldwidth:5mm.

Phoscorites (figure 3.09) are coarse grained, composed of apatite, magnetite, carbonate,
phlogopite, olivine, perovskite. Sulphides comprise pyrite, pyrrhotite and chalcopyrite, usually
occurring together. In some cases the textural relationships indicate latestage substitution of other
minerals (e.g. figure 3.09b) but, in others, they are disseminated grains. Pyrite has irregular surface,
andisdisseminatedintherockorreplacingmagnetite(figure3.09b).Pyrrhotiteistypicallygranular.
Chalcopyriteisrare,occurringasdustyaggregatesnearpyritegrains.

26

Figure 3.09 Textural features of sulphide phoscorites from the Salitre complex. A: Coarse grained phoscorite,
composedofolivine(Ol),phlogopite(Phl)inplanepolarizedlight.Fieldwidth:5mm.B:SameasAinreflectedlight,showing
pyrite(Py)replacingmagnetite;ilmenite(Ilm),chalcopyrite(Cpy)andpyrrhotite(Po).Fieldwidth:5mm.

Bebedourites (figure 3.10) are coarse grained, composed of diopside, phlogopite, apatite,
magnetite, perovskite, melanite, titanite). Sulphide, usually pyrite, is rare, disseminated and
interstitial.

Figure3.10BebedouritefromtheSalitrecomplex.A:Coarsegrainedbebedourite,composedofclinopyroxene(Cpx),
phlogopite (Phl), magnetite, ilmenite, pyrite. Field width: 5mm. B: Same as A in reflected light, showing magnetite (Mgt)
replacementbypyrite(Py).Fieldwidth:5mm.

27

Arax

Most of the Arax samples studied in this work are carbonatites, and one sample is a

phoscorite. The carbonatite (figure 3.11 and 3.12) samples are fine to coarse grained, formed by
carbonate, apatite, phlogopite, magnetite and barite. Sulphide is either disseminated or shows a
bladed texture. Alternatively, it has a blob aspect, with round contours, which may represent
seggregation of a sulphide immiscible liquid (figure 3.12b). Pyrite, pyrrhotite and chalcopyrite are
present.Pyriteandpyrrhotiteshowpittedsurface,occurringasaggregates(figure3.12a).Chalcopyrite
is rare, forming a finegrained cloudy mass (figure 3.12a) next to pyrite and pyrrhotite. Some of the
carbonate,bariteandsulphidetexturesareinterpretedastheresultofrapidcrystallizationresultingin
cryptocrystalineaggregateslikethosedescribedforCataloIIbut,atArax,thisaggregatesseemsto
betheinterfacebetweenthecryptocrystallinemassesandthebladedcrystals(figure3.11).

Figure 3.11 Textural features of finegrained aggregates of sulphide, barite and carbonate in carbonatite from the
Araxcomplex.A:Criptocrystalinecarbonatemass,withintergrownofbariteaggregatesandsulphide,crosspolarizedlight.
Fieldwidth:5mm.B:Sameas"A",inreflectedlight.Fieldwidth:5mm.

Carbonates are sometimes microcrystalline showing a colloidal aspect. These carbonate masses
form elongate aggregates marked by subparallel curved lines (figure 3.12c,d). In cross section, they
have an almost circular profile and may show alternating concentric circular lines (figure 3.12e,f)
markedbydifferentshadesofbrowninplanepolarizedlight.Undercrossedpolarstheyshowacircling
maltesecrosssimilartothespheruliticextinction.

28

Figure3.12TexturalfeaturesofsulphideandcarbonateincarbonatitefromtheAraxcomplexA:Typicaltextureof
carbonatite pyrite (Py), with very irregular grain surfaces, probably resulting from recrystallization of microgranular
aggregates and very finegrained aggregates of chalcopyrite (Cpy), and subordinate pyrite, with a dusty appearance.
Reflectedlight.Fieldwidth:5mm.B:Sulphideswithablobaspect,showingroundcontoursthatmayindicateseggregation
ofasulphideimmiscibleliquid,withpyrrhotite(Po),pyrite(Py)andchalcopyrite(Cpy).Reflectedlight.Fieldwidth:5mm.C:
Carbonateaggregatesmarkedbysubparallelcurvedlines.Planepolarizedlight.Fieldwidth:5mm.D:Sameas"C"incross
polarizedlight.E:Crosssectionofcarbonateaggregatesshowingconcentricgrowthlines.Planepolarizedlight.Fieldwidth:
5mm.F:Sameas"E",incrosspolarizedlight,showingacirclingmaltesecrosssimilartothespheruliticextinction.

29

Barite often fills tabular voids in aggregates of bladed carbonate. This texture is indicative of
degassingcontrolled crystallization, and similar to those described by JunqueiraBrod et al. (in
preparation) for an analogous stage of degassing in the Catalo I Complex. As the degassing
progresses, causing the decrease of temperature in the liquid, it facilitates the precipitation of
carbonatemarkedbygrowthlinesshownbytheelongatedaggregates.
The phoscorite (figure 3.13) sample is coarsegrained, composed of apatite, magnetite,
carbonate, phlogopite, and olivine (figure 3.13a). Pyrite is the sulphide present in this rock. It is
typically associated with magnetite and has an irregular surface like the one described for the other
complexes(figure3.13b).

Figure 3.13 Phoscorite. A: Phoscorite with magnetite (Mgt), phlogopite (Phl), apatite (Ap) and carbonate (Cbt). Plane
polarizedlight.Fieldwidth:5mm.B:Pyrite(Py)withpittedsurfaceandmagnetite(Mgt).Reflectedlight.Fieldwidth:5mm.

Tapira

MostsamplesfromTapiraarecarbonatites,withalessernumberofbebedourites,phoscoritesand
fenites. The carbonatites (carbonate, apatite, phlogopite, magnetite, ilmenite and barite, olivine,
tetraferriphlogopite, perovskite)(figure3.14) are fine to coarsegrained. The modal percentageof
apatitevariesfrom2%to20%aproximately.

30

Figure3.14TexturalfeaturesofcarbonatitesfromTapiracomplex.A:Carbonatitewithcarbonate(Cbt),olivine(Ol)
and apatite (Ap). Cross polarized light. Field width: 5mm. B: Carbonatite with some microgranularcarbonates of colloidal
aspect(arrow).Planepolarizedlight.Fieldwidth:5mm.

Carbonatesaresometimesmicrocrystallineshowingacolloidalaspect(figure3.14b)similartothat
observedinsamplesfromArax,andothercasesformacriptocrystalineaggregatelikethatdescribed
forCataloII(figure3.15).Thesulphidespresentarepyrite,pyrrhotiteandchalcopyrite.Pyriteoccurs
as grains with pitted surface, as skeletal grains and as disseminated limpid grains. Pyrrhotite varies
from wellformed grains to pitsurfaced. Chalcopyrite is rare and associated with the other two
sulphides.

Figure3.15A:BSEimageofafinegrainedmasscontainingdolomite(Cbt)andskeletalbarite(Brt).B:BSEimageofa
finegrained mass containing different carbonate types and barite, 001: Barite; 002: Barite; 003: Srcarbonate; 004: Sr
carbonate;005:Dolomite;006:Calcite;007:Calcite.

31

Bebedouritesarefinetomediumgrained,composedofdiopside,phlogopite,apatite,magnetite,
perovskite, titanite, with disseminated sulphides. The predominant sulphide species is pyrrhotite
withsubordinatechalcopyrite,bothusuallyinterstitialtotheotherphases.
Phoscoriteiscoarsegrained,composedofapatite,magnetite,carbonate,phlogopite,andolivine
(figure3.16a).Sulphideisdisseminatedandbothchalcopyriteandpyritearepresent.Pyriteshowsan
irregularsurfaceliketheonedescribedtotheothercomplexes,whereaschalcopyriteisfoundaswell
formedgrains(figure3.16b).

Figure3.16TexturalfeaturesofphoscoritesfromTapiracomplex.A:Phoscoriteshowingcarbonate(Cbt),olivine(Ol),
apatite (Ap), granular chalcopyrite andpyrite with pitted surface. Cross polarized light. Field width: 5mm. B: Same as A,
showinggranularchalcopyrite(Cpy)andpyrite(Py)withpittedsurfaceunderreflectedlight.Fieldwidth:5mm.

Tapira fenites have similar composition, texture and origin as those described in Catalo. The
sulphidepresentispyriteandisassociatedwithcarbonatiteveins.

Jacupiranga

Jacupirangasamplesaremostlycarbonatites.Nevertheless,jacupirangitewasalsostudiedinorder
to compare its sulphur isotopes with bebedourites and other silicate rocks from the APIP. The
carbonatites (figure 3.17) vary from fine to coarse grained and consist of carbonate, apatite,
phlogopite, magnetite, ilmenite, barite, olivine, tetraferriphlogopite, perovskite. The most
commonsulphideispyrrhotitefollowedbypyrite,chalcopyriteandpentlandite.Pyrrhotitevariesfrom
wellformedtoirregularlysurfacedgrains whereaspyriteandchalcopyritearerareandwellformed.

32

Sulphides may appear as disseminated grains or a large aggregate that seems to be associated with
carbonatesulphide liquid immiscibility processes (figure 3.17b). Alternatively, pyrite occurs as
concentric microgranular aggregates, forming circular lines (figure 3.17c). This may be the sulphide
equivalent of the elongate carbonate aggregates and could be interpreted as the result of gradual
precipitationofsulphideduringsulphurgaseousloss.

Figure 3.17 Textural features of carbonatites from Jacupiranga complex. A: Carbonatite with apatite (Ap) and
disseminated pyrrhotite (Po) in plane polarized light. Field width: 5mm. B: Texture suggestive of carbonatesulphide
immiscibilityshowingpyrrhotite(Po)andchalcopyrite(Cpy),notethebloblikeaspectofthepyrrhotitenearthelowerright
corner.Reflectedlight.Fieldwidth:5mm.C:Carbonatite withmicrogranularaggregatesof pyrite(Py),formingconcentric
circularoramoeboidallines.Ilm=ilmenite.Reflectedlight.Fieldwidth:3.5mm.

Jacupirangites(figure3.18)(clinopyroxene,nepheline,magnetite,apatite,phlogopite,carbonate,
amphibole) are medium grained. The nepheline may show symplectitic texture (figure 3.18c,d).
Sulphides(chalcopyriteandpyrite)areinterstitialandwellformed(smoothsurface)(figure3.18b).

33

Figure 3.18 Textural features of jacupirangites from Jacupiranga complex. A: Jacupirangite showing clinopyroxene
(Cpx) with magnetite (Mgt) andinterstitial chalcopyrite (Cpy).Cross polarized light. Field width: 5mm.B: Same as "A", in
reflectedlight.C:Jacupirangiteshowingnepheline(Ne)withsympletitictexture,titanite(Ttn)andclinopyroxene(Cpx).Plane
polarizedlight.Fieldwidth:5mm.D:Sameas"C",incrosspolarizedlight.Fieldwidth:5mm.

4. Analyticalmethods

SulfurisotopiccompositionsweredeterminedattheGeochronologyLaboratoryoftheInstituteof
Geosciences,UniversityofBrasilia(UnB)byLAMCICPMS(LaserAblationMultiCollectorInductively
Coupled Plasma Mass Spectrometry) on handpicked minerals (sulphide and sulphate). The analyses
were carried out using a Neptune MCICPMS coupled with a NewWave UP213 Nd:YAG as ablation
sourceforinsituanalysisofsolidsamples.
SulfurreferencematerialsIAEAS1,S2,S3,NBS127andNBS123(CoplenandKrouse,1998;Ding
etal.,2001;QiandCoplen,2003)wereusedtocalibratelaboratory(inhouse)standards(pybsband
cpybsb) and to enable interlaboratory comparison against the VCDT scale. The analytical precision

34

(1) was about 0.1 to 0.5. All sulfur isotope compositions are reported in the standard delta
notation relative to VCDT. Three percent HNO3 blank solutions were used to quantify sulfur blanks
throughoutcalibrationsessionsandduringanalysis.Heflowwereusedtoquantifysulfurblanks.
Powders of reference standards were prepared as pellets using a PerkinElmer hydraulic press.
Pelletswerepressedwithoutadditionofabinderundervacuumat10tonsfor5min,sulphideminerals
weremountedindependentlyonglassslidesinepoxyresinandpolishedtogiveaflatsurfacesuitable
forlaserablationsampling.Alinescan(raster)protocolisusedinpreferencetoasinglecratermode,
inordertoobtainahigherandmoreuniformrateofmaterialremovalwithrespecttotime(Craddock
etal.2008).
SulphidesandsulphateschemicalcompositionwereobtainedwithaJEOLJXA8230microprobeat
UniversityofBrasilia.ThesulphateswerefirstlyexploredbyEDS(EnergyDispersiveSpectrometry)and
observed by BSE (BackScatteres Electrons) and then analysed by WDS (WavelengthDispersive
Spectrometry)at20kV.SulphidesweredirectlyanalisedbyWDSat20kV.

5. Results

In sampling for this study we tried to systematically represent all available sulphide and/or
sulphatebearing rocktypes from which it was possible to mechanically extract these minerals for
analysis. The set of analysed rocktypes comprises: phoscorite and carbonatite from Arax;
carbonatite, phoscorite, nelsonite, magnetitite, and metassomatic phlogopitite from Catalo I;
carbonatiteandnelsonitefromCataloII;carbonatitefromSerraNegra;bebedourite,phoscoriteand
carbonatite from Salitre; bebedourite, carbonatite, phoscorite, and metasomatic phlogopitite from
Tapira;andcarbonatiteandjacupirangitefromJacupiranga.
Barite is the only sulphatefound, usually occurring as masses in latestage magnesiocarbonatites
(e.g.CataloI,CataloII,SalitreandTapira)orinpostmagmaticveins(e.g.CataloI).
The sulphides present in the sample set are pyrite, pyrrhotite, chalcopyrite, bornite and galena. Of
these, bornite is rare and galena was found only in samples from Jacupiranga but it was too finely
grained to allow a reliable analysis. Therefore, our discussion will focus on the three remainder
sulphidespecies.Pyriteoccursinallpetrographictypesinavarietyoftextures:bladedphenocrysts
or tabular aggregates associated with carbonate and/or magnetite in nelsonites and

35

magnesiocarbonatites (JunqueiraBrod et al. in preparation); interstitial grains sometimes replacing

magnetite; millimetric pyrite veins and, very rarely, as centimetric massive pyrite intercepts in drill
cores. Pyrrhotite occurs in carbonatites both as fenocrists and interstitial grains, and also as a rare
interstitial phasein bebedourites. Chalcopyriteoccursinall petrographictypesandmay befoundas
intersticial grains or as aggregatesof anhedralgrains, and sometimes replaces pyrite. Borniteis rare
andoccursassociatedwithchalcopyriteinnelsonite.
Table3.01showsrepresentativesulphurisotopedata,alongwiththeanalysedmaterials(Sbearing
phase,hostrock,andcomplex).

Table3.01Representative34Sresults.

N of
2
1
5
1
1
3
2
4
2
6
8
2
2
6
5
1
1
3
1
13
3
1
4
1
3
1
6
4
1
1
1
5
10

34

SVCDT
from7.22to12.16
6.25
from6.68to12.31
6.68
5.28
from5.62to7.08
from4.86to5.98
3.26to12.88
from17.36to24.55
from2.2to10.91
from2.58to9.59
from2.13to0.51
from4.66to5.03
from5.02to8.76
from2.84to12.36
5.72
5.98
from8.12to8.78
8.24
from11.63to4.39
from7.93to11.69
7.59
from1.31to16.75
6.49
from2.59to9.55
2.19
from6.79to13.15
from3.95to9.01
8.61
1.70
0.84
from3.15to6.08
from3.15to5.37

Mineral
barite
chalcopyrite
pyrite
pyrrhotite
bornite
chalcopyrite
pyrite
barite
pyrite
pyrite
pyrite
barite
pyrite
pyrite
pyrrhotite
chalcopyrite
pyrite
pyrite
pyrrhotite
pyrite
pyrrhotite
pyrite
barite
chalcopyrite
pyrite
pyrrhotite
pyrite
pyrrhotite
pyrite
chalcopyrite
pyrite
pyrite
pyrrhotite

Rock
Carbonatite
Carbonatite
Carbonatite
Carbonatite
Nelsonite
Nelsonite
Nelsonite
Carbonatite
Fenite/Carbonatite
Carbonatite
Nelsonite
Carbonatite
Bebedourite
Carbonatite
Carbonatite
Phoscorite
Phoscorite
Carbonatite
Carbonatite
Carbonatite
Carbonatite
Phoscorite
Carbonatite
Bebedourito
Bebedourito
Bebedourito
Carbonatite
Carbonatite
Fenito
Bebedourite
Bebedourite
Carbonatite
Carbonatite

Complex
CatalaoII
CatalaoII
CatalaoII
CatalaoII
CatalaoII
CatalaoII
CatalaoII
CatalaoI
CatalaoI
CatalaoI
CatalaoI
Salitre
Salitre
Salitre
Salitre
Salitre
Salitre
SerraNegra
SerraNegra
Araxa
Araxa
Araxa
Tapira
Tapira
Tapira
Tapira
Tapira
Tapira
Tapira
Jacupiranga
Jacupiranga
Jacupiranga
Jacupiranga

36

Todiscussvaluesitisinitiallynecessarytonotethatthesulphurisotopecompositionofsulphur
rich minerls is strongly related with the redox conditions under which these minerals form. For
example,insystemscontaingbothsulphatesandsulphides,theformerarealwaysheavier(higher34S)
than the latter (e.g. Seal et al. 2006, Nikiforov et al. 2006, Miyoshi et al.1984, Mitchell and Krouse,
1975).Thisisalsotrueofthesulphidesulphatepairsstudiedinthiswork.Similarrelationshipswere
obtained in degassing experiments in systems crystallizing sulphides only. In this case, sulphur
degassingunderoxidizingconditionsdrives34Softheresidualsystemtowardshighervalues,whereas
sulphur degassing under reducing conditions has the oposite effect (Zheng, 1990). In our work we
adopttheseconceptstocomparetheisotopicvariationsbothinsulphatesulphideandinsulphideor
sulphateonlysystems.

Table3.02Representativeandaveragechemicalcompositionsofthestudiedssulphides.

mineral
pyrite

sample
C87G*
average
rocktype
carbonatite #=252

Fe
46.27
46.395
Cu
0.018
0.019
Pb
0.075
0.230
0.185
0.155
Co
Ag
0.021
0.004
Zn
0.005
0.005
Ni
0
0.020
Pt
0.01
0.004
Pd
0
0.002
53.368
53.008
S
As
0.074
0.025
Se
0
0.029
Total
100.03
99.90
a

Fe
0.995
1.001
Cu
0.000
0.000
Pb
0.000
0.001
Co
0.004
0.003
Ag
0.000
0.000
Zn
0.000
0.000
Ni
0.000
0.000
Pt
0.000
0.000
Pd
0.000
0.000
S
1.999
1.992
As
0.001
0.000
Se
0.000
0.000
total
3
3
cations
1.00
1.01
anions
2.00
1.99
*representativesample
a
atomicproportionsfor3ions
b
atomicproportionsfor1S
c
atomicproportionsfor4ions
d
atomicproportionsfor10ions

pyrrhotite
AT49*
carbonatite

60.145
0
0.27
0.079
0
0.024
0
0
0.001
39.414
0.004
0.087
100.02
b

0.875
0.000
0.001
0.001
0.000
0.000
0.000
0.000
0.000
0.999
0.000
0.001
1,88
0.88
1.00

average
#=76

chalcopyrite
165911C*
nelsonite

average
#=24

bornite
165911C1*
nelsonite

59.858
0.020
0.164
0.195
0.003
0.002
0.028
0.006
0.002
39.104
0.002
0.036
99.42

0.879
0.000
0.001
0.003
0.000
0.000
0.000
0.000
0.000
1.000
0.000
0.000
1,88
0.88
1.00

30.673
33.897
0.211
0.036
0.018
0.016
0.009
0
0
34.833
0
0.06
99.75

30.330
33.661
0.135
0.037
0.024
0.023
0.006
0.003
0.002
34.596
0.001
0.034
98.85

1.009
0.984
0.001
0.001
0.000
0.001
0.000
0.000
0.000
2.003
0.000
0.001
4
2.00
2.00

11.383
61.736
0
0.008
0.281
0
0.063
0
0.008
25.293
0
0.095
98.87

1.012
0.982
0.002
0.001
0.000
0.000
0.000
0.000
0.000
2.001
0.000
0.001
4
2.00
2.00

1.035
4.934
0.000
0.001
0.013
0.000
0.005
0.000
0.000
4.006
0.000
0.006
10
5.99
4.01

average
#=2

11.332
61.933
0
0.022
0.259
0
0.039
0
0.004
25.410
0.0045
0.0625
99.07

1.028
4.937
0.000
0.002
0.012
0.000
0.003
0.000
0.000
4.014
0.000
0.004
10
5.98
4.02

37

5.1.MineralChemistry

Data from 388 microprobe analyses are considered for this section. Table 3.02 shows
representative results and averages for each sulphide species found and Table 3.03 shows
representativebariteanalyses.Overall,pyriteisthemostcommonSbearingphase.Bariteistheonly
studiedsulphateandwasfoundinfourofthesevenComplexes(CataloI,II,SalitreandTapira).
Table3.03Representativecompositionsofthestudiedsulphates.
sample 144054
SH1BH2
ASL12B2
rock
carbonatite carbonatite carbonatite
complex CataloII
CataloI
Salitre
BaO 65.17
66.27
64.61
SO3
34.29
33.62
34.27
SeO2 0.50
0.00
0.00
MgO 0.00
0.02
0.01
SiO2
0.00
0.00
0.00
0.04
0.08
Al2O3 0.11
P2O5 0.07
0.00
0.02
CaO 0.00
0.00
0.00
Cr2O3 0.00
0.00
0.00
FeO 0.11
0.02
0.01
SrO
0.00
0.09
1.11
PbO 0.00
0.00
0.00
MnO 0.02
0.00
0.02
Total 100.26
100.05
100.14
atomsperformulaunitbasedon4oxygen
Ba
0.9849
1.0201
0.9799
Pb
0.0000
0.0000
0.0000
Sr
0.0000
0.0019
0.0250
Ca
0.0000
0.0000
0.0000
Si
0.0000
0.0000
0.0000
Al
0.0048
0.0019
0.0037
P
0.0022
0.0000
0.0008
Cr
0.0000
0.0000
0.0000
Fe
0.0034
0.0006
0.0002
Mg
0.0000
0.0013
0.0005
Mn
0.0007
0.0000
0.0007
S
0.9925
0.9910
0.9954
Se
0.0105
0.0000
0.0000
sum
2.00
2.02
2.01

AT1321
carbonatite
Tapira
65.58
33.53
0.00
0.00
0.09
0.05
0.00
0.12
0.00
0.04
0.12
0.00
0.00
99.52

average
#=34

66.62
33.40
0.18
0.00
0.05
0.06
0.05
0.06
0.00
0.03
0.08
0.00
0.00
100.52

1.0109
0.0000
0.0027
0.0048
0.0037
0.0023
0.0000
0.0000
0.0012
0.0000
0.0000
0.9899
0.0000
2.02

1.0245
0
0.0019
0.0026
0.0018
0.0026
0.0016
0
0.0009
0
0
0.9836
0.0038
2.02

Thecompositionalrangeoftheanalysedsulphidesisverynarrow,ascanbeobservedfromfigure
3.19,wheredatafromall354availableanalysesareincludedandplotveryclosetoeachother,closeto
eachsulphidespeciesidealcomposition.

38

Figure3.19ClassificationofsulphidesaccordingtoCuSFeinatomicproportions(Klein,2002).

The variation between complexes is also small, as shown in figure 3.20 where sulphur and ion
rangesforeachsulphidetypewereplottedaccordingtotheirrespectivealkalinecomplex.

Figure3.20Comparedmajorelementvariationsinthestudiedsulphidesforeachcomplex.

Trace elements detected in pyrite, pyrrhotite and chalcopyrite include Cu (major for
chalcopyrite),Pb,Co,Ag,Zn,Ni,Pt,Pd,AsandSe.Cobaltisalwayspresentinpyriteandcanreachup
to2.7wt%.ItisalsoimportanttonotethepresenceofNiandPbatpercentagelevels(upto0.7wt.%

39

and0.8wt.%,respectively)inthepyriteanalyses.Inpyrrhotite(Fe1xS)thexparameter,representing
Fe omission solid solution varies from 0.07 to 0.15. The trace elements found in pyrrhotite are the
same as in pyrite, although generally in smaller amounts. Chalcopyrite usually shows the smallest
traceelementscontents.Manycore/rimanalyseswereconducted,butnonehasdetectedsignificant
changesincompositionthatcouldsuggestzonning.
Barite also has a very steady composition. Strontium and selenium were the only significant
traceelementsinatotalof34analyses(upto1.87wt%ofSrOand1.08wt%ofSeO2).Otherdetected
elementsincludeCa,Si,Al,P,Fe,Mg,MnandSe.

5.2.SulfurisotopevariationsintheAPIPcomplexesandJacupiranga

Sulphurisotopedataaredetailedforeachstudiedcomplexinfigure3.21andcomparedwiththe
assumedprimarymantlevalueof0.Thefigurealsoemphasizesthedifferencebetweentheisotopic
composition of sulphides and sulphates. The occurrence of sulphide and sulphate in the complexes,
sometimesinthesamerock,indicatevariableoxidizing/reducingconditionsduringmagmaevolution.
SamplesfromCataloIIyielded34Srangesof12.31to4.24,peakingat4forsulphides,
andhighpositivevalues(7.22to12.16)forbarite.Theanalysesofpyriteandbaritefromthesame
samplehaveyielded,respectively34S=9.17and12.16,aca.21difference.
TwotypesofsulphidesmaybedistinguishedinCataloIonthebasisofpetrographicfeatures
and 34S results. Sulphides from samples lacking evidence of hydrothermal alteration range from
10.92 to 2.2, peaking at 6. These are dominantly pyrite, with one pyrrhotite analysis. In
metasomatised rocks the analysed sulphide is also pyrite, and yielded substantially depleted 34S
results (17.36 to 24.55). Barite from Catalo I has a high positive 34S, ranging from 3.27 to
12.88, as expected for sulphates. Coexisting pyrite and barite were analysed in two samples, one
freshandoneshowingevidenceofmetasomatism.Inthefirstcase,weobtained34Spyrite=7.04and
34Sbarite=5.70,adifferenceofca.13.Thealteredsampleyielded34Spyrite=24.55and34Sbarite
=11.00,astriking35difference.Thelargediferencebetweenthereducedandoxidizedformof
sulphur in the altered sample probably indicates crystallization at different times, as observed by

40

Gomideet al.(2010)o
or,alternatiively,coevaalcrystallizaationbutattverylowteemperaturee(Miyoshieetal
1984).

n=17

Higher

Higher

n=25
5

n=
=18

Higher

Higher

n=4

Higher

Higher

n
n=19

n=17

Higher

n=18

Figure3.21.SSulphurisotop
pedataforalkkalinecarbon
natitecomplexxesfromtheA
APIPandPonttaGrossaPro
ovince.Redba
ars
representsulp
phidedataan
ndbluebarsreepresentsulph
hatedata.

41


SerraNegraisthecomplexwiththefeweranalysesinourdataset:only4samples,whichvary
between8.78and7.61.Thisisalsothenarrowestobservedrange,butthisprobablyreflectsthe
lackofalargernumberofanalyticaldeterminations.
SulphidesfromtheAraxcomplex(pyrite,chalcopyriteandpyrrhotite)plotbetween11.69
and 4.4, with the most abundant values between 10 and 8. The Arax complex is
characterized by intense carbonatite metasomatism, similarly to Catalo I, but this was not
representedinthesamplesetavailableforthiswork.Therefore,more 34Sdepletedresultswouldbe
expectedshouldthesemetasomaticrocksbeanalysedinthefuture.
Salitrehasarangefrom8.77to2.84withanisolatedresultat12.36,representinga
fresh carbonatite, which suggests that the primary sulphur composition range extends to this value.
Salitre barite shows a narrow 34S range (2.14 to +0.51). Among the studied complexes Salitre
showed the smallest sulphidesulphate fractionation. We obtained 34S values for pyrite and barite
coexistinginthesamesampleof5.7and2.14,respectively.
Sulphides from Tapira samples show a 34S range from 13.15 to 2.19, whereas barite
variesfrom3.94to1.31,withasinglevalueof+16.75inasamplewherebariteshowstextural
evidence of secondary origin. Two coexisting sulphidesulphate pairs were analysed in carbonatites.
Onesampleyelded34Spyrrhotite=11.59and34Sbarite=3.94andtheother34Spyrrhotite=
8.15 and 34Sbarite = 1.31. The sulphatesulphide fractionation in these two cases is of similar
magnitude(7.65and6.84respectively).
Jacupirangahasa34Srangefrom6.09to0.84,peakingat4.Ithasa34Sdistribution
similartoArax,butsuggestinglessreducingconditions.Comparedtotheotheranalyzedcomplexes,
Jacupirangashowsamuchnarrowerrangeof34Svalues.

5.3.Sulfurisotopevariationsbyrocktype

Figure 3.22 illustrates the difference between carbonatite, phoscorite, nelsonite and
bebedouriteforeachcomplex.Overall,carbonatitesshowthewiderSisotoperangeofallrocktypes.
Sulphidesfromphoscoritestendtovaryinarestrictedrangeineachcomplex,withtheexceptionof
CataloInelsonitesandTapirabebedourites.

42

Figure3.22.SulphurisotopedataforsulphidesandsulphatesfromtheAPIPandJacupirangaalkalinecarbonatitecomplexes,by
hostrocktypeandcomplex.

SulphidesinnelsonitesfromCataloIIshowamorerestricted34Srange(7.08to4.24)
thancarbonatites(12.31to5.09).NelsonitesfromCataloIseemtospanasimilarrange(9.6

43

to 2.58) to the majority of the associated carbonatites, while phoscorites are very restricted (
6.37to4.56).Salitrecarbonatitesvaryinawiderange(12.36to2.84)whilebebedourite(
5.03 to 4.66) and phoscorite (5.98 to 5.72) have very restricted isotope compositions.
CarbonatitesfromAraxalsospanarelativelywiderange(11.69to4.40).Inthiscomplexthere
isonlyoneanalysedphoscoritesample,whichdoesnotallowtoestimatestableisotopevariationsin
thisrocktype.Tapirashowswiderangesforbothcarbonatite(13.15to3.95)andbebedourite(
9.55to2.19).Jacupiranga,theonlycomplexthatdoesnotbelongfromAPIP,istheonewiththe
leastSisotopevariationineachrocktype,withvaluesconcentratedclosertozerothanintheother
studiedexamples.Jacupirangacarbonatitesrangein34Sfrom6.09to3.15,andultramaficrocks
from1.70to0.84,whichisconsistentwiththehighlypreservedcharacteroftheprimaryrocks
inthiscomplexanditsdeeperlevelofintrusion(e.g.SantosandClayton,1995).
Bebedourites/jacupirangitesandphoscoriteshavevaluesof34Ssystematicallycloserto0(the
primary mantle composition) compared to carbonatites for all complexes where data could be
obtainedfortheserocktypes.Thissuggeststhat34Sbecomesprogressivelymorenegativewiththe
evolution of the complex. The fact that carbonatites (and possibly nelsonites) show a much wider
range than other rocks may result of their genesis involving other petrogenetic processes besides
crystalfractionation(e.g.liquidimmiscibilityanddegassing)allowustodeducethatwithevolutionof
the complex, 34S show more negative values until carbonatites that shows a large range because
evolvesothermagmaticprocessbeyondfractionation(nelsonitesprobablyhaveasimilarbehavior).

5.4.Sulfurisotopevariationsfromrimtocore

The core and rim of some samples show different isotopic compositions, especially for Catalo I
pyritegrains.Thecoreisconsistentlymoredepletedin34Sthantherim.Thisindicatesthatatthetime
ofcrystallizationoftherim,themagmawasmoreoxidized(orlessreduced)thenatanearlierstage
whenthecorecrystallized(figure3.23).Inadditiontotheinsituvariation,CataloIsamplesshowa
systematic change in isotopic composition, increasing in 34S from around 8 to values close to 0.
Figure3.23illustratesthecompositionalvariationandtable3.04shows34Sresultsfromcoreandrim.

44

Figure3.23.Sulphurisotopedataforsampleswithevidenceofdegassing,showingdifferentvaluesfromcoretorim.Note
thatboththevariationinsinglegrainsandthecomparisonbetweendifferentrocktypesindicateincreasingvaluesof34S
withprogressivedegassing.

Thisvariationcanbecorrelatedwiththedegassingofvolatilespeciescontainingsulfur,alteringnot
only the oxygen fugacity of the residue but its S isotopic composition as well. When the magma
undergoesdegassing,crystallizationconditionschangeabruptly,immediatelygeneratingaquenchlike
fabric(JunqueiraBrodetal.inpreparation).Thecrystallizedphasesregisterthedifferenceinisotopic
composition, since the core/border have not achieved equilibrium. Therefore it is reasonable to
assume that magma evolves from an originally higher concentration of

32

S towards a heavier

composition, richer in 34S, as degassing takes place. This is evident by the 34S evolution depicted in
figure3.23.ComparativelytheTapirasampleshowninthediagramrecordedinitialtoearlystagesofS
degassinginmagmaevolution.
Anotherimportantfeatureobservedinfigure3.23isthatsamplesrelatedwithlatestagesofthe
complex evolutionorwithmetassomaticalteration havevery negative 34S,between25and 10,
butstillshowdifferencesfromrimtocore.

45

Table3.04Sulphurisotopedataforthesamplesthatpresentdifferencesbetweenrimandcore.

Sample
rock
complex
core
rim
CB04

nelsonite

CataloI

4.48

2.83

CB14

foscorite

CataloI

6.37

4.56

AC328,30I

nelsonite

CataloI

6.41

3.69

07C1CO3

Mgcarbonatite

CataloI

8.05

4.31

07C1CO3

Mgcarbonatite

CataloI

9.54

5.80

AC32830

nelsonite

CataloI

8.21

7.57

C1SH1

carbonatite

CataloI

17.46

12.98

C1SH3

carbonatite

CataloI

23.45

20.55

AT135

Mgcarbonatite

Tapira

13.58

8.87

5.5.Sulphidesulphideisotopicvariation
Figure 3.24 shows histograms for 34S in the different sulphide types. The distribution is slightly
asymmetric towards lower 34S for pyrite data, symmetric for chalcopyrite, and slightly asymmetric
towardshigher34Sforpyrrhotite.Sulphurisotopedataforchalcopyrite,pyriteandpyrrhotiteplotat
differentvalues(figure3.24).Chalcopyriteismoredepletedin 32Sthanpyrite(smallrange)andthis,in
turn,ismoredepletedthanpyrrhotiteintheAPIPresults.ForJacupiranga,thereisasmallernumberof
analyses and the ranges of pyrite and chalcopyrite overlap largely, although the latter extends to
slightly more 34Sdepleted values. The overall sense of the progressive shift in 34S is in good
agreement with pyritechalcopyrite and pyritepyrrhotite fractionation of S stable isotopes (e.g.
KajiwraandKrouse,1971).
Metasomatic sulphide samples show a very depleted 34S signature (34S(VCDT)=25 to 14),
whereassulphidefromrockswithoutevidenceofmetasomaticalterationyieldisotopedataof34S(V
CDT)=11to0,althoughamorerestrictedrangeisobservedwithinindividualcomplexes.

Pairsofcoexistingsulphidespeciesoccurinsomeoftheanalysedsamples,butthissulphideswere
not found to be in textural equilibrium. On the other hand, in many of the samples that did include
more thanonesulphidephaseinequilibrium, onormoreofthephasesweretoofinegrainedtobe
reliably analysed by LAMCICPMS. These features prevent us from establishing a more detailed
discussiononthesulphidesulphidefractionationandcrystallizationtemperaturesatthisstage.

46

Su
ulphides

Pyrrhotitte
Pyrite
Chalcopyyrite

30
28
26
24
22
20
18
18
16
14
12
10
10
8
6
4
2
0
2
4
6
8
10
12
14
16
Higher

20
0
18
8
16
6
14
4
12
2
10
0
8
6
4
2
0

Figure 3.24. Sulphur isoto

ope data forr sulphidesfro
om the studieed alkaline carbonatitic
c
ccomplexes. Bllack solid
horizontalbar:magmaticssulphide;Unfilledhorizonta
albar:sulphid
defromfenitess.

5.6.Sullphidesulphateisotop
picvariation
nandfractionation

Figure3
3.25shows theisotopiicdiferenceebetweenssulphidean
ndsulphate inthesam
mesample.O
Only
samples fro
om Catalo
o I, Salitre e Tapira were
w
analyssed for both minerals. Catalo I shows a laarge
difference betweensu
ulphurisoto
opecompossitionofpyriteandbarite,whereeasSalitresamplesyiellded
thesmallesstfractionattionvalues..Tapirasho
owsaninterrmediatebeehaviour,exceptforonesamplew
with
alargefracctionationbetweenpyrrrhotiteand
dbarite.

Figuree3.25.Sulphu
urisotopecom
mpositionforssulphideandssulphateintheesamesamplle.

47

Weanalysedsulphidesulphateassemblagesfromeightcarbonatitesamples:onefromCataloII,
two from Catalo I, one from Salitre and four from Tapira. However, in three of these samples the
texturalcharacteristicsofbaritesuggestthatitissecondary,particularlyinsomeoftheTapirasamples.
The remaining five samples were used to model the crystallization temperatures as a function of
sulphidesulphateisotopefractionation,usingtheparametersofMiyoshietal.(1984).Theresultsare
showninfigure3.26.

Figure3.26.Modellingofsulphidesulphatefractionation(Miyoshietal.,1984)forthestudiedsamples.

Catalo II fractionation temperature plots about 550oC, compatible with the temperature of
carbonatiteformation(e.g.Wyllie,1966).
CataloIyieldedtemperaturescloseto750oCforonesampleofpreservedcarbonatiteand475oC
foronesampleoflatecarbonatite.InlatestageBaandREErichcarbonatitemagmastheliquidphase
canpersisttolowertemperatures(543oC,JonesandWyllie,1983)thenthenormalcarbonatitesolidus,
and temperatures measured in the erupting Oldoynio Lengai lavas were as low as 490oC (Kraft and
Keller,1989).Thompsonetal.(2002)reportedtemperaturesaslowas420oCfromtheSwartbooisdrif
ankeritecarbonatite,Namibia.

48

Tapira shows a calculated temperature of 950oC. The Salitre sample plots at 1400oC, which is an
exceedingly high temperature for this system. We could find no textural reason for this since the
mineralassemblagesappeartobeintexturalequilibrium,andthecauseofthisresultisnotyetclear.

5.7.Comparisonwithothercarbonatites

Sulphur isotope rangesobservedin the APIP and Jacupiranga are broadly comparable with other
carbonatiteprovincesandlocalities.
Farreletal(2010)foundamorerestrictedsulphurisotoperangeintheSuperiorProvince,Canada,
where 34S from carbonatitic sulphides plot between 4.5 and +3.4 and sulphides from
carbonatites have lighter S than the associated silicate rocks. In a compilation by Mitchell & Krouse
(1975) of sulphur isotope data of some world carbonatites (Mountain Pass, Bearpaw, Magnet cove,
OkaandPhalabora),sulphides(exceptforgalena)plotinarangeof11to+5andsulphatesfrom
+2 to +12. Druppel et al (2006) studied the Swartbooisdrif carbonatite and 34S for the
carbonatites are3.3to +5.1.Figure5 compares the APIP complexes withother carbonatites in
theworld.
Sealetal.(2006)reportedasulphurisotoperangeforigneousrocksthatvariesfromapproximately
5to+15.ThesulphurisotoperesultsfromAPIPandJacupirangacomparedwiththesedatabases,
evidenceasimilaritywithotherworldcarbonatites,althoughtheAPIProcksspanaconsiderablywider
rangeofsulphurisotopecompositions.
SulphurisotopedatafromAPIPisillustratedinthehistogramandtherangeofothercarbonatites
values are plotted below, as bars. The Oka alkalinecarbonatite complex, Quebec, shows the closest
similarities with the APIP range. Russian Carbonatites also possess a similarly wide range, but this is
shiftedtowardsmorepositivevalues.
Otherprovinceshavemorerestrictedand/ornearto0compositions.Despitethevariatonswithin
each complex/province in figure 3.27, there is a clear trend of decreasing 34S of sulphides with
decreasing age, which may suggest a longterm evolution of the sulphur isotope composition of the
mantle.Availablebaritedataaretoofew(MountainPassandTuva)fortheirbehaviortobeassessed,

49

figure3.28presentsthesubsetof34Sforsulphidesonly,versuscarbonatitesage(logscale)todepictS
vatiationthroughage.

30
25
20

APIP(85M.y.)

15
10
5

Tuva (118M.y.)
Jacupiranga (131M.y.)
Kola Province (300M.a.)
Swartbooisdrif (750M.y.)
Moutain Pass (1400M.y.)

HIGHER

16

14

12

10

34S(VCDT)

10

12

SuperiorProvince (1490M.y.)
Phalaborwa (2020M.y.)

14

16

18

20

22

24

Alkaline Carbonatitic Complexes

inthe Word

Bear Paw Mountain (48M.y.)

Magnet Cove (99M.y.)
Oka (117M.y.)

Figure3.27.SulphurisotopedatafromalkalinecarbonatitecomplexesintheWorld.APIPresults(thiswork)areshownas
verticalbarsinthetopsectionofthefigureblueandredbarsrepresentbariteandsulphides,respectively.Thehorizontal
bars (green = sulphides, light blue = barite) in the bottom section represent other worldwide complexes, in order of
increasing age from top to bottom: Bearpaw Mountain (Mitchell & Krouse 1975; ~48Ma Duke, 2009), Magnet Cove
(Mitchell & Krouse, 1975; 99Ma Wooley & Kjarsgaard, 2008), Oka (Mitchell & Krouse 1975; 117Ma Wooley &
Kjarsgaard,2008),Tuva(118Ma,Nikiforovetal.2006),Jacupiranga(thiswork;131MaWooley&Kjarsgaard,2008#),Kola
Province(Mitchell&Krouse1975,Shin&Lee2007;~250340MaDownesetal2005),Swartbooisdrif(Druppel2006;750Ma
Wooley & Kjarsgaard, 2008), Mountain Pass (barite data only) (Mitchell & Krouse 1975; 1.4Ga Wooley & Kjarsgaard,
2008),SuperiorProvince(Farreletal.2010;1,897Mato1,093MaFarreletal.2010),Phalaborwa(Mitchell&Krouse1975;
2.02GaWooley&Kjarsgaard,2008)

50

34S(VCDT) for
Alkaline Carbonatitic Complexesinthe Word
40

Bear Paw Mountain (48M.a.)

APIP(85M.a.)
Magnet Cove (99M.a.)
Tuva (118M.a.)
Jacupiranga (131M.a.)

100

age(M.a.)

Oka (117M.a.)

Kola Province (300M.a.)

Swartbooisdrif (750M.a.)
1000

SuperiorProvince (1490M.a.)
Phalaborwa (2020M.a.)

34S(VCDT)

10

12

14

4500

Figure3.28.Correlationofsulphurisotopecompositionofworldwidecarbonatiteswiththerespectiveages.Notethelog
scaleoftheageaxis.Datasourcesasinfigure3.27.

6. Conclusions

Inthisworkwe presentedpetrographic,chemicalandthe firstsulphur isotopicdataforalkaline

carbonatitecomplexesoftheAltoParanabaIgneousProvinceandfortheJacupirangacomplex,inthe
PontaGrossaProvince.

51

Somekeytexturalfeaturesallowedustomonitortherelationshipsbetweenmagmadifferentiation
processes and sulphur isotope variations. The presence of bladed carbonate and sulphide crystals in
somecarbonatitesindicatesquenching,withrapidcrystallizationoftheseminerals(e.g.Gomideetal.,
2008, JunqueiraBrod et al., in preparation). This is consistent with the presence of "dusty',
microgranular to cryptocrystalline masses of carbonate, sulphide and barite interstitial to bladed
carbonatecrystals.Furthermore,thecoexistenceofsulphidesandbariteindicatesimportantvariations
intheoxygenfugacityduringcrystallization.Weinterpretthesetexturesasquenchfabric,formedby
rapid crystallization of a supercooled carbonatite magma during degassing. This process has
consequences for the sulphur (see below) and carbon and oxygen (JunqueiraBrod et al., in
preparation)stableisotopevariations.
Microprobe analyses of the studied sulphides did not show wide deviations from the respective
ideal compositions. Some trace elements may be present in significant amounts in pyrite and, to a
lesserextent,inpyrrhotite,whereaschalcopyriteanalyseswerealwaysveryclosetostoichiometry.No
significantchemicalchangeswerenotedbetweencoreandrimintheanalysedsulfidegrains.
Barite also shows little chemical variation: only strontium and selenium are significant trace
substitutions. Sr is a common solid solution in sulphates (barite/celestine) and Se usually replaces
sulphurinsulphidesandsulphatesstructures(Deeretal.1992).OurresultsshowthatSereplacement
ismoreexpressiveinsulphatethaninsulphidestructure.
SerraNegra(onthebasisofonlyafewanalyses),Salitre,AraxandJacupirangashownarrow34S
ranges, and Salitre and Jacupiranga are characterized by values closest to primary mantle. Catalo I,
Catalo II and Tapira show a wide range which may represent the effect of more variable
differentiationprocessinvolvedintheformationoftheserocks.
Thisinterpretationisalsoconsistentwiththesulphurisotopecompositionofbarite,whichshows
widerrangesinCataloIandCataloII,butanarrow(nearto0)rangeforSalitreandTapira.
Bebedourites/Jacupirangitesandphoscoriteshavevaluesof34Ssystematicallycloserto0than
thoseofcarbonatitesinallcomplexeswheretheserocktypeswereanalysed.Wheredataisavailable
for both ultramafic silicate rocks and phoscorites, theformer are even closer to 0 than the latter.
This suggests that, in each complex, 34S shifts toward more negative values with magma evolution.
Also, latestage rocks, such as carbonatites and, probably, nelsonites, tend to undergo other

52

differentiation processes (e.g. liquid immiscibility and degassing) in addition to fractional

crystallisation,whichmaypartiallyexplainthewiderobserved34Srangesintheserocks.
Metasomatic sulphides show distinctly negative 34S values as shown by Drppel et al. (2006) in
fenitesfromSwartbboisdrif.
In a few of our nelsonite and carbonatite samples, the studied phases register differences in
isotopiccompositionbetweencoreandrimofcrystals,indicatingthatequilibriumwasnotachieved.In
all cases the rim isotopes are heavier than in the corresponding core. Many of these samples show
petrographicevidenceofquenching,leadingustoconcludethatthisdifferenceiscausedbydegassing,
andthatmagmaevolvesfromahigh 32Scontenttowardsaheavier 34Srichcomposition,asdegassing
takesplace.Comparatively,thesamplefromTapirarecordedsulphurdegassingatanearlierstagein
magmaevolutionthanthoseofCataloI.
TheexperimentalworkbyZheng(1990)showedthattheRayleighdistillationduringoutgassingof
either SO2 or H2S can considerably change the isotopic composition of sulfur remaining in the melt,
dependingonthesulphate/sulphideratio,whichiscontrolledbyO2,thefractionofsulfurremaining
andthetemperatureatthetimeofoutgassing.Inthesamestudy,Zheng(1990)arguedthat,athigh
O2,the34Softhesolidifiedrockswillbedriveninthepositivedirection,duetoequilibriumlossof
thelightgaseoussulfurspecies,whereasatlowO2,the34Softhecrystallizedrockswillshiftinthe
negative direction. In carbonatite systems, the redox stage is also strongly dependent on CO2
degassing,which greatly affects the O2 of the system (Gomide etal. 2009,JunqueiraBrodet al., in
preparation).Therefore,theredoxstateofsuchasystemwilldependonacomplexinterplayofdistinct
degassing events and conditions, in addition to fractional crystallization and, possibly, liquid
immiscibility.Thefullcomprehensionofthesecontrolsrequirescomplementarystudies.
The results presented in this work indicate that as magma differentiation progresses from
ultramafic rocks (jacupirangite, bebedourite) through phoscorites to nelsonites and carbonatites, it
consumes particullarly the heavier sulphur isotopes into the solid phases leaving a residual
magma/fluidenrichedin 32Srepresentedbylower34S.Ontheotherhand,theobservedcoretorim
variationsinsulphidesfromsampleswithpetrographicevidenceofdegassingshowedthattheresidue
ofdegassingevolvedtowardhigher34S,andthatsulphurlosshappenedathighO2.

53

Temperatures calculated using sulphidesulphate isotope fractionation for Catalo II (ca. 550oC),
Catalo I (ca. 750oC for an earlystage carbonatite and 475oC for a latestage carbonatite) arewithin
theexpectedrangesforthistypeofmagma.
Sulphur isotope ranges observed in the APIP and in the Jacupiranga complex are broadly
comparable with other carbonatite provinces and localities (Mitchell & Krouse 1975; Nikiforov et al.
2006;Shin&Lee2007;Druppel2006;Farreletal.2010)andwiththeexpectedvariationofsulphur
isotopesinigneousrocks(ca.5toca.+15,Sealetal.,2006),kimberlites(ca.13toca.+5,
Seal et al., 2006) and carbonatites (ca. 13 to ca. +2, Deines, 1989). The comparison of sulphur
isotopes results from carbonatites of different ages shows a general trend of decreasing 34S of
sulphides with decreasing age. This may suggest a longterm evolution of the sulphur isotope
compositionofthemantle/source.

54

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CAPTULO4
Concluses

A partir dos dados e argumentos expostos nos captulos anteriores, possvel obter algumas
caractersticas das rochas das sries bebedourtica, foscortica e carbonattica da APIP, e dos
carbonatitosejacupiranguitosdeJacupiranga(ProvnciaPontaGrossa)ecaracterizarseusrespectivos
sulfetosesulfatosdopontodevistapetrogrficoedacomposiodeistoposdeS.
Osmtodosdeanlisesdeistoposdeenxofre,jemrotinanoLaboratriodeGeocronologiada
Universidade de Braslia, desenvolvidos pelo professor Berhard Manfred Buhn, obtiveram bons
resultadoscomprecisoanalticaemtornode0,1a0,5.Apreparaodeamostrascomoauxlio
da microretfica com disco diamantado facilitou a separao das fases minerais de interesse e
melhorou o controle (posio do gro na amostra macro e/ou lmina delgada) dos gros a serem
analisados.
Algumas das caractersticas texturais permitiram monitorar as relaes entre processos de
diferenciao do magma e as variaes de istopos de enxofre. A presena de cristais alongados de
carbonato e sulfeto em alguns carbonatitos indica cristalizao destes minerais por resfriamento
rpido (Gomide et al., 2008, JunqueiraBrod et al., en preparao). A presena de massas
microgranularesacriptocristalinasdesulfeto,carbonatoebarita,intersticiaisaoscristaisalongadosde
carbonato refora a interpretao de cristalizao rpida. Alm disso, a presena de sulfeto e barita
nessasmassasindicaimportantesvariaesna fugacidadedeoxigniodurante acristalizao.Estas
texturas so interpretadas como de congelamento (quench), formadas pela cristalizao rpida de
ummagmacarbonatticosuperresfriadoduranteadesgaseificao.Esteprocessotemconseqncias
navariaodeistoposdeenxofre(estetrabalho)edecarbonoeoxignio(JunqueiraBrodetal.em
preparao).
Asanlisesdequmicamineraldossulfetosestudadosnomostraramumafastamentosignificativo
darespectivacomposioideal.Entretanto,algunselementostrao(Cu,Pb,Co,Ag,Zn,Ni,Pt,Pd,As,
Se) podem estar presentes na pirita, e em menores quantidades na pirrotita e calcopirita. Variaes
composicionaissistemticasousignificativasentrencleoebordanoforamobservadasnossulfetos
analisados.

62

Abaritatambmmostrapoucavariaoemsuacomposioqumica:apenasSreSesoelementos
trao relevantes, encontrados em pequenas quantidades. A soluo slida entre brio e estrncio
comumemsulfatos(barita/celestita)eSesubstitutodoSemsulfetosesulfatos(Deeretal.1992).Os
resultadosdequmicamineralobtidosnestetrabalhomostramqueasubstituiodeSporSemais
expressivanossulfatosdoquenossulfetos.
Serra Negra (com base em poucas amostras), Salitre, Arax e Jacupiranga apresentam menores
intervalosde34S,eSalitreeJacupirangatmosvaloresmaisprximosde0.CataloI,CataloIIe
Tapiramostramumintervalomaisamplo,quepoderepresentaroefeitodeprocessosdediferenciao
maisvariadosnaformaodessasrochas,taiscomodesgaseificaoeimiscibilidadedelquidos,alm
dacristalizaofracionada.EssainterpretaocoerentecomacomposioisotpicadeSdabarita,
que apresenta amplos intervalos em Catalo I e II, mas restritos e prximos de 0 para Salitre e
Tapira.
Emtodososcomplexosnosquaisbebedouritos/jacupiranguitosefoscoritosforamanalisados,essas
rochas exibem valores de 34S sistematicamente mais prximos de 0 do que os carbonatitos
associados. Nos complexos onde se obteve dados de rochas silicticas ultramficas e foscoritos, as
primeiras so ainda mais prximas de 0 que as ltimas. Esses dados sugerem que 34S tornase
progressivamente mais baixo com a evoluo do magma. Rochas tardias como carbonatitos e,
provavelmente,nelsonitostendemaserafetadasporoutrosprocessosdediferenciao(imiscibilidade
delquidosedesgaseificao)almdacristalizaofracionada,oquepodeestarrelacionadocomos
amplosintervalosdevalorespara34Sobservadosnessasrochas.
Ossulfetosmetassomticosmostramvaloresde34Sdistintamentenegativoscomomostradopor
Drppeletal.(2006)emfenitosdeSwartboisdrif.
Em algumas amostras de carbonatito e nelsonito, observouse diferenas sistemticas nas
composiesisotpicasentrencleoebordadoscristaisdesulfetos,indicandoquenofoialcanado
equilbrioisotpicoduranteacristalizao.Emtodososcasos,osistoposnabordasomaispesados
do que no ncleo correspondente. Muitas dessas amostras tm evidncias petrogrficas de
resfriamento rpido, levando a concluir que tal diferena causada por desgaseificao de espcies
volteiscontendoenxofre,equeomagmaevoluidealtocontedoem 32Sparaumacomposiomais
pesada, enriquecida em

34

S com a evoluo da desgaseificao. A amostra de Tapira mostra

63

desgaseificaodeenxofreemumestgioanteriordaevoluodomagmasecomparadasamostras
deCataloI.
Zheng(1990)fezclculosbaseadosemestudosexperimentaisemostrouqueadestilaoRayleigh
duranteadesgaseificao,tantodeSO2comodeH2Spodeafetardemaneiraimportanteacomposio
isotpica do enxofre que restou no magma, dependendo da razo sulfato/sulfeto, que controlada
pelaO2,dafraoquerestadeenxofreedatemperaturanomomentodadesgaseificao.Nomesmo
estudo, Zheng (1990) demonstrou que em alta O2 o 34S das rochas formadas ser desviado para
valores mais altos, devido perda do equilbrio por desgaseificao, enquanto que em baixa O2, o
34S das rochas cristalizadas deslocado para valores mais negativos. Alm disso, em sistemas
carbonatticosoestadodexidoreduoaltamentedependentedadesgaseificaodeCO2(Gomide
et al. 2009, JunqueiraBrod et al., em preparao). Portanto, o estado redox de um sistema vai
dependerdeumacomplexainteraoentrediferenteseventosecondiesdedesgaseificao,alm
de cristalizao fracionada e possivelmente imiscibilidade de lquidos. Estudos complementares so
necessriosparaumamelhorcompreensodessescontroleseinteraes.
Os resultados apresentados neste trabalho, indicam que medida que a diferenciao progride
desdeasrochasultramficas(jacupiranguito,bebedourito),passandoporfoscoritos,atnelsonitose
carbonatitos, ocorre consumo preferencial de istopos mais pesados de enxofre na fase slida,
deixando o magma residual enriquecido em 32S, o que se traduz em menor valor de 34S. Por outro
lado, as variaes observadas do ncleo para a borda dos gros em sulfetos, em amostras com
evidncias petrogrficas de desgaseificao mostraram que, neste processo, o resduo evoluiu para
maioresvaloresde34Seque,portanto,adesgaseificaodeenxofreaconteceuemaltaO2.
Ofracionamentoisotpicosulfetosulfatopermitiuoclculodetemperaturasdecristalizaopara
carbonatitos de Catalo II (aproximadamente 550oC) e Catalo I (aproximadamente 750oC para um
carbonatito pouco evoludo e 475oC para um carbonatito tardio) compatveis com as temperaturas
esperadasparaessetipodemagma.
Os intervalos de composio de istopos de enxofre nos complexos da PIAP e Jacupiranga so
comparveisaosdecarbonatitosdeoutrasprovnciaselocalidades(Mitchell&Krouse1975;Nikiforov
et al. 2006; Shin & Lee 2007; Druppel 2006; Farrel et al. 2010) e com as variaes esperadas para
istoposdeenxofreemrochasgneas(5a+15,Sealetal.,2006),kimberlitos(13a+5,Seal

64

etal.,2006)ecarbonatitos(13a+2,Deines,1989).Osdadosdeistoposdeenxofreexistentes
naliteratura,paradiversoscarbonatitosmundiais dediferentes idades(PaleoproterozoicoaEoceno)
indicamumaclaratendnciadediminuiodo34Semsulfetosdoscarbonatitosmaisantigosparaos
maisjovens,oquepodesugerirumaevoluodelongoprazodacomposiodosistoposdeenxofre
domanto.

65

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