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S T Ef A N O Sa L V I

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Er Bez I A T

Da M I En G U I L L A U M E

Mi C H El

Ra K Ot On

D Ra Z A F Y 2 A N D Bern A Rd Moi N E

PROSPER AN

Keywords: A rch aean mesoth ermal gold, aq u eou s-carbonic flu ids, B I F, flu id immiscibility, Maev atanana, Madagascar

su l p h id e v eins c r o ssc u t t ing b a nd ed ir o n f o r m a t io n ( B IF ) w it h in a m et a m o r p h o sed 2. 5 G a g r eenst o ne b el t . Th e h o st r o c k s a r e d o m ina t ed b y a seq u enc e o f

m ig m a t it es, g neisses, a m p h ib o l it es, m a g net it e-r ic h q u a r t z it es a nd so a p st o nes, int r u d

Textural and fluid inclusion constraints on the origin of the banded-iron-formation-hosted gold deposits at Maevatanana, central Madagascar Introduction

Ver y l it t l e is k n ow n abou t t h e gol d p ot en t ial of Mad agascar , bu t t h e cou n t r y ' s est im at ed gol d p r od u ct ion is ap p r ox im at el y 3-4 t on n es/ y r an d cou l d easil y be d ou bl ed ( Min in g An n u al Rev iew 1995). Th is is a l ar ge am ou n t con sid er in g t h at al l of it p r esen t l y com es fr om ar t isan al m in in g of m ain l y al l u v ial d ep osit s. An est im at e of Mad agascar ' s t ot al gol d p r od u ct ion sin ce l at e l ast cen t u r y is a r esp ect abl e 70 t on n es. To t h is d ay , t h er e is n o or gan ised or in d u st r ial gol d ex p l oit at ion . F r om w h at is k n ow n , m ost of t h e p r im ar y gol d d ep osit s of Mad agascar bel on g t o t h e m esot h er m al l od e-gol d cl ass of d ep osit s as d efin ed by Hod gson ( 1993) ( Ram bel oson 1999; N aw ar at n e an d Dissan ay ak e 2001). Th e Maev at an an a gol d d ist r ict con sist s m ain l y of p r im ar y d ep osit s in w h ich m in er al isat ion occu r s as q u ar t z -su l p h id e-gol d v ein s. G ol d is al so fou n d in al l u v ial sed im en t s t h r ou gh ou t t h e r egion , w h er e it is ex p l oit ed by l ocal s. Th e Au -bear in g v ein s cr osscu t fer r u gin ou s q u ar t z it e w h ich is in t er p r et ed by Ran d r iam an an t en asoa ( 1992) as ban d ed ir on for m at ion ( BI F ). Ban d ed ir on for m at ion s con t ain a m aj or p or t ion of t h e w or l d ' s ir on or es an d , esp ecial l y in Ar ch aean t er r an es, h ost gol d d ep osit s ( e.g. G il l igan g an d F ost er 1987; G r ov es 1983; Pr et or iu s et al . 1988;Hod gson 1993;Hagem an n an d Cassid y 2000). G ol d m in er al isat ion in t h ese set t in gs is d ebat ed as of an ep igen et ic ( e.g. Ph il l ip s et al . 1984al . , Br ow n in g et al . 1987)), v er su s a sy n gen et ic or igin ( e.g. F r ip p 1976). At Maev at an an a, t h e m in er al isat ion is cl ear l y ep igen et ic becau se: 1) it occu r s in a z on e of d efor m ed r ock associat ed w it h a l ar ge r egion al sh ear -z on e st r u ct u r e; 2) it is r est r ict ed t o z on es of in t en se fr act u r in g w it h d iscor d an t q u ar t z -su l p h id e v ein s; 3) t ex t u r al ev id en ce in d icat es r ep l acem en t of p r im ar y m agn et it e by p y r it e. I n t h is p ap er w e p r esen t p et r ogr ap h ic, m icr ot h er m om et r ic an d Ram an sp ect r ogr ap h ic d at a on fl u id in cl u sion s in v ein q u ar t z associat ed w it h t h e gol d m in er al isat ion . Ch ar act er ist ics of t h e fl u id s p r ov id e con st r ain t s on P-T con d it ion s an d m ech an ism s for gol d p r ecip it at ion . Based on t h ese d at a w e su ggest a gen et ic m od el for t h e for m at ion of t h e gol d m in er al isat ion at Maev at an an a.

Geological setting

Mad agascar for m s a p ar t of t h e Moz am biq u e bel t , r esu l t in g of con t in en t al col l ision bet w een east an d w est G on d w an a. St r u ct u r es r el at ed t o t h is ev en t , su ch as v er t ical l it h osp h er ic-scal e sh ear z on es, ar e con sist en t w it h an east -w est h or iz on t al sh or t en in g ( Mar t el at et al . 2000). Pr ecam br ian r ock s for m abou t t w o-t h ir d s of Mad agascar . Pr esen t -d ay h y p ot h eses on t h e Pr ecam br ian basem en t of Mad agascar r ecogn ise sev en t ect on ic u n it s ( cf. Col l in s an d W in d l ey 2002; Col l in s et al . 2003) ( F ig. 1). Th e Ar ch aean An t on gil bl ock t o t h e east is r egar d ed t o be eq u iv al en t t o t h e Dh ar w ar cr at on in sou t h er n I n d ia, w h il e t h e An t an an ar iv o bl ock in t h e cen t r e h as an Afr ican affin it y . Bot h u n it s ar e sep ar at ed by t h e Bet sim isar ak a su t u r e, w h ich m ar k s t h e col l ision of I n d ia w it h Afr ica d u r in g t h e assem bl y of G on d w an a at abou t 550-500 Ma ( Col l in s an d W in d l ey 2002). Th e Tsar at an an a sh eet is a sy st em of gr een st on e bel t s ov er t h r u st ed on t h e An t an an ar iv o bl ock . Th e r em ain in g u n it s t o t h e w est , sou t h an d far n or t h ar e con sid er ed t o be Pr ot er oz oic in age, t h r u st ed ov er t h e Ar ch aean u n it s. Ou r st u d y ar ea is l ocat ed in t h e cen t r al p ar t of Mad agascar w it h in t h e Tsar at an an a sh eet ar ea, in t h e Maev at an an a bel t ( F ig. 2).

Figure 1 Figure 2

Th e Maev at an an a bel t is t h e w est er n m ost t on gu e of t h e fou r n or t h -sou t h t r en d in g gr een st on e bel t s of t h e Tsar at an an a ar ea. Th e l it h ol ogies ( e.g. Col l in s et al . 2003) con sist of an in fr acr u st al seq u en ce of m igm at it e an d a su p r acr u st al seq u en ce of gn eiss, am p h ibol it e ( d at ed at 2502 ± 2 Ma, U -Pb on z ir con , Tu ck er et al . 1999), m agn et it e-r ich q u ar t z it es an d m et abasic t o u l t r abasic r ock s ( soap st on es), in t r u d ed by l ar ge gr an it oid bat h ol it h s ( e.g. t h e Bean an a gr an od ior it e d at ed at 779 ± 2 Ma, U -Pb on z ir con , Tu ck er et al . 1999). Th ese seq u en ces w er e fol d ed an d m et am or p h osed u n d er u p p er -gr een sch ist t o am p h ibol it e facies con d it ion s, p r obabl y d u r in g a w id esp r ead ign eou s ev en t d u r in g t h e m id d l e ( ~800-770 Ma) or p ossibl y l at e N eop r ot er oz oic ( ~580-520 Ma) Pan -Afr ican ev en t , w h ich h as been r ecogn ised in al l of t h e Pr ecam br ian of Mad agascar . G ol d -bear in g q u ar t z v ein s ar e fou n d w it h in a l ar ge h igh -st r ain z on e in t er p r et ed as a r egion al br it t l e-d u ct il e sh ear -z on e t h at occu r r ed l at e in t h e st r u ct u r al ev ol u t ion of t h e bel t .

The Maevatanana gold district

Th e Maev at an an a gol d fiel d w as d iscov er ed in t h e l at e 19 t h cen t u r y , an d a d oz en sm al l m in es w er e op er at ion al by 1891. Ex p l oit at ion w as in it ial l y car r ied ou t by op en -p it an d u n d er gr ou n d m in in g; h ow ev er , by t h e ear l y 1900s al l u v iu m w as p r ov id in g t h e l ar gest p ar t of t h e gol d p r od u ct ion , w h ich r each ed h al f a t on n e in 1909. G ol d p r od u ct ion t h en d ecr eased r ap id l y , p ar t icu l ar l y aft er t h e st ar t of t h e F ir st W or l d W ar . Sin ce 1929, al l gol d ex t r act ed in t h e r egion is m in ed ex cl u siv el y by gol d p an n in g ( Besair ie 1966). Recen t est im at es in d icat e an av er age gol d gr ad e of abou t 0.1 g/ t on n e ( N aw ar at n e an d Dissan ay ak e 2001). Th e m ost p r od u ct iv e d ist r ict h as been d efin ed by t h e p ol y gon bet w een t h e I k op a, t h e Men av av a an d t h e Bet sibok a Riv er s, cov er in g an ar ea of abou t 7,500 k m 2 , w h er e at l east 44 gol d occu r r en ces h av e been r ecor d ed ( Besair ie 1966). I n t h is ar ea, gol d is ex p l oit ed m ain l y in " bl ack san d s" al l u v iu m s bu t al so by cr u sh in g t h e ex p osed q u ar t z v ein s at t h eir con t act w it h l at er it e.

Petrographic description of the lithologies

Pol ish ed sect ion s w er e p r ep ar ed fr om abou t fift y sel ect ed sam p l es col l ect ed n ear by t h e I k op a Riv er w it h in an d ar ou n d t h e or e bod ies, in cl u d in g bot h h ost r ock s an d au r ifer ou s an d / or n onau r ifer ou s q u ar t z v ein s. Al l sect ion s w er e st u d ied u n d er t r an sm it t ed an d r efl ect ed l igh t in or d er t o d et er m in e t h e m in er al associat ion s an d p ar agen eses. El ect r on m icr op r obe an al y ses on gol d , su l p h id es, sil icat es an d ox id es w er e p er for m ed w it h a Cam ebax SX 50 Micr obeam in st r u m en t ( CAMECA) at t h e U n iv er sit y Pau l Sabat ier in Tou l ou se, u sin g an accel er at in g v ol t age of 15 k V, a beam cu r r en t of 20 n A an d a 3 µm beam d iam et er for al l el em en t s. Measu r in g t im e w as 10 s for m aj or an d m in or el em en t s. N at u r al an d sy n t h et ic m in er al s an d p u r e m et al s w er e u sed as st an d ar d s.

Gneisses r ep r esen t t h e d om in an t l it h ol ogical facies in t h e Maev at an an a d ist r ict , an d can be su bd iv id ed in t o t w o m ain t y p es: 1) am p h ibol it e-biot it e gn eiss, con sist in g of 40% l igh t col ou r ed l ay er s ( q u ar t z , m icr ocl in e, or t h ocl ase, p l agiocl ase ( An 28 ), ap at it e) an d 60% d ar k er l ay er s ( am p h ibol e, biot it e, ir on an d t it an iu m ox id es, p l u s t it an it e an d z ir con ) an d 2) m u scov it e-biot it e gn eiss, w h ich con sist of 65% of l igh t col ou r ed l ay er s in t er bed d ed w it h l ay er s con sist in g al m ost en t ir el y of biot it e. Granitoid r ock s ar e w id esp r ead t h r ou gh ou t t h e ar ea an d occu r as sm al l l ay er s or l en ses w it h in t h e gn eisses. Th eir t ex t u r e is gr an obl ast ic an d t h ey ar e com p osed of q u ar t z , al k al i fel d sp ar s, p l agiocl ase an d m icas. Pegm at it ic q u ar t z -r ich l en ses, l ocal l y con t ain in g al k al i-fel d sp ar an d biot it e ( p l u s accessor y t it an it e, t ou r m al in e an d z ir con ), ar e com m on w it h in t h e gr an it es. Micr o sh ear z on es ar e w id esp r ead t h r ou gh ou t t h ese gr an it es an d affect t h e p egm at it ic l en ses as w el l . Mafic and u ltramafic rock s at Maev at an an a ar e r ep r esen t ed by m u l t i-m et r e t h ick r egu l ar l ay er s, w h ich ar e sq u eez ed in t o t h e gn eissic for m at ion s. Th ey com p r ise t w o d ist in ct facies: on e sh ow in g a m assiv e asp ect an d h av in g a d ar k gr een col ou r ( am p h ibol it e sensu strictu ) an d a sil k ier , l igh t l y col ou r ed r ock ( soap st on e). Min er al assem bl ages in t h ese r ock s in d icat e t h at p eak m et am or p h ism r each ed am p h ibol it e-facies con d it ion s. Th e am p h ibol it e con t ain s r el ict s of t h e am p h ibol it e-facies assem bl age, Mg-h or n bl en d e-al bit e-m agn et it e-m ica-q u ar t z -t it an it e. Th is assem bl age is ov er p r in t ed by t h e assem bl age ch l or it e-ep id ot e-cal cit e-h em at it e. I n t h e soap st on es, m et am or p h ic h or n bl en d e is r ep l aced by an assem bl age of t r em ol it e-al bit e-q u ar t z , w h ich is it sel f ov er p r in t ed by an t h op h y l l it e, t al c, ch l or it e or ser p en t in e. Th ese m in er al assem bl ages su ggest t h at gr een sch ist -facies con d it ion s p r ev ail ed , w h ich is con sisit en t w it h t h e br eak d ow n of Mg-h or n bl en d e t o ep id ot e an d ch l or it e, an d t h e p r esen ce of al bit e, w h ich is p r obabl y a r ep l acem en t of for m er p l agiocl ase ( ol igocl ase). Magnetite-rich q u arz ites ar e fou n d in t er cal at ed w it h in t h e gn eissic for m at ion s an d am p h ibol it es. Th ese u n it s com m on l y ex t en d on k il om et r e-l on g l ay er s, v ar y in g in t h ick n ess fr om a few cen t im et r es t o sev er al m et r es w id e. Th ey con sist of a su ccession of l igh t col ou r ed bed s m ad e u p p r im ar il y of q u ar t z an d d isp er sed m agn et it e, in t er cal at ed w it h d ar k bed s con sist in g m ain l y of m agn et it e an d ir on sil icat es ( F ig. 3). Th is l ay er ed asp ect l ed t o t h eir cl assificat ion as ban d ed ir on for m at ion ( BI F ) ( Ran d r iam an an t en asoa 1992). I n t h e l igh t l ay er s q u ar t z gr ain s ar e an h ed r al , w h it e col ou r ed an d r an ge fr om 0.1 t o 0.8 m m in siz e. L ocal l y , fibr ou s or acicu l ar am p h ibol e ( act in ol it e-t y p e) can be obser v ed w it h in t h e q u ar t z l ay er s. Magn et it e in t h ese l ay er s r an ges in d iam et er fr om ~20 µ m t o 0.2 m m an d occu r s eit h er as d isp er sed an h ed r al cr y st al s or in t er gr an u l ar t o t h e q u ar t z gr ain s. Th e d ar k l ay er s con sist m ain l y of m agn et it e an d am p h ibol e. Th e m agn et it e con t en t r an ges fr om 10 t o 40% of t h e w h ol e r ock ; m agn et it e occu r s as eu h ed r al in cl u sion s w it h in q u ar t z an d is com m on l y p seu d om or p h ed t o h em at it e. Am p h ibol e in t h e m agn et it e z on e d isp l ay s a su bh ed r al t ex t u r e an d bel on gs t o t h e cu m m in gt on it e-gr u n er it e ser ie. Q u ar t z v ein s can be com m on l y obser v ed in t h ese BI F s, an d t h ey can cr oss-cu t or be con cor d an t t o t h e bed d in g.

Figure 3

Gold mineralisation and alteration I n t h e Maev at an an a d ist r ict , gol d is h ost ed in q u ar t z v ein s w h ich occu r m ain l y in t h e m agn et it e-r ich q u ar t z it es ( BI F ) bu t w h ich can be al so fou n d in t h e cou n t r y r ock , i.e. gn eiss an d m afic-u l t r am afic l ay er s, ad j acen t t o con t act s w it h t h e BI F . G ol d bear in g q u ar t z v ein s gen er al l y cr osscu t t h e BI F bed d in g, w h er eas v ein s t h at p ar al l el t h e bed d in g ar e bar r en . Th e op p osit e is t r u e for v ein s t h at occu r in t h e cou n t r y r ock ; h er e, m in er al ised v ein s ar e m ost l y con cor d an t t o t h e sch ist osit y w h er eas d iscor d an t v ein s ar e bar r en . Th e m in er al ised v ein s ar e by an d l ar ge or ien t ed n or t h -sou t h an d d ip 70°E.

Table 1

Th e au r ifer ou s v ein s ar e m ad e u p of fin e-gr ain ed m il k y t o sm ok y q u ar t z w h ich d isp l ay s gr an obl ast ic t ex t u r es ( F ig. 3). Mod er at e t o st r on g u n d u l ose ex t in ct ion is al so ev id en t t oget h er w it h d efor m at ion l am el l ae. Q u ar t z gr ain s for m p ol y gon al aggr egat es of v ar iabl e siz e w h ich sh ow n o l at t ice-p r efer r ed or ien t at ion . Th ese gol d -bear in g q u ar t z v ein s al so con t ain a d ist in ct su it e of su l p h id es, an d l ess com m on l y , ch l or it e. Py r it e is t h e d om in an t su l p h id e in ad d it ion t o ch al cop y r it e an d gal en a ( Tabl e 1). I t occu r s m ain l y as a r ep l acem en t of m agn et it e ( ± h em at it e) in t h e w al l r ock im m ed iat el y ad j acen t t o t h e q u ar t z v ein s. I t d isp l ay s su t u r ed or ir r egu l ar su r faces in con t act w it h m agn et it e ban d s, bu t su bh ed r al t o eu h ed r al sh ap e in con t act w it h q u ar t z l ay er s. Ch al cop y r it e occu r s as 1-cm w id e, isol at ed su bh ed r al t o an h ed r al gr ain s ( F ig. 3) or in t er gr ow n w it h p y r it e. G al en a is com m on in t h e q u ar t z v ein s, w h er e it for m s < 4 m m an h ed r al gr ain s t h at ar e com m on l y in con t act w it h gr ey q u ar t z an d n at iv e gol d ( F ig. 4). Th e assem bl age p y r it e-ch al cop y r it e ± gal en a aft er m agn et it e ( ± h em at it e) is com m on al on g v ein m ar gin s, at con t act s w it h t h e w al l r ock , an d ap p ear s t o be con t em p or an eou s t o gol d m in er al isat ion ( F ig. 3).

Figure 4

At a h an d sam p l e scal e, gol d is fou n d w it h in t h e su l p h id e-r ich z on es an d occu r s as fr ee gol d in t er gr ow n w it h p y r it e ± ch al cop y r it e an d gal en a or as in v isibl e gol d w it h in p y r it e an d ch al cop y r it e ( abou t 2500 p p m ). Py r it e an d ch al cop y r it e com p osit ion s ar e h om ogen eou s. Py r it e con t ain s u p t o 5000 p p m Co an d 2400 p p m As ( Tabl e 1).

Table 2

G ol d in q u ar t z v ein s ( F ig. 4) is gen er al l y of m icr oscop ic siz e ( < 500 µm ), h ow ev er , sp ect acu l ar v ein sam p l es con t ain in g v isibl e gol d can be fou n d . El ect r on m icr op r obe an al y ses r ev eal t h at fr ee gol d is in t h e for m of el ect r u m , w it h an Ag con t en t of abou t 7 w t % ( Tabl e 2), w h ich is a com m on feat u r e of BI F -h ost ed m esot h er m al l od e-gol d d ep osit s ( < 10 w t % Ag, e.g. Viel r eich er et al . 1994).

Fluid inclusion study

Tw en t y -t w o d ou bl y -p ol ish ed t h ick sect ion s w er e p r ep ar ed fr om sel ect ed sam p l es an d ex am in ed by st an d ar d m icr oscop y befor e u n d er t ak in g fu r t h er an al y ses. Micr ot h er m om et r ic m easu r em en t s w er e p er for m ed at t h e U n iv er sit y Pau l Sabat ier in Tou l ou se, fol l ow in g t h e p r oced u r es ou t l in ed by Roed d er ( 1984)

Petrographic characterization of fluid inclusions

Th e Au -bear in g v ein s ar e com p osed essen t ial l y of q u ar t z ( > 90% v ol .), an d con t ain ad d it ion al p y r it e, ch al cop y r it e an d gal en a. Abu n d an t an d d iv er se fl u id in cl u sion s ar e p r eser v ed in q u ar t z . How ev er , w it h in m il k y an d cl ear q u ar t z it w as d ifficu l t t o cl ear l y id en t ify p r im ar y or secon d ar y in cl u sion s, becau se of t h e l ar ge n u m ber of in cl u sion s an d t h eir u n cl ear d ist r ibu t ion s. I n con t r ast , sm ok y q u ar t z cr y st al s w h ich su r r ou n d or bor d er su l p h id e-r ich or e z on es con t ain isol at ed in d iv id u al in cl u sion s an d in t er gr an u l ar t r ail s or cl u st er s of r an d om l y an d t h r ee-d im en sion al l y d ist r ibu t ed in cl u sion s. Th ese fl u id in cl u sion s h av e n egat iv e cr y st al t o ov oid sh ap es, r an ge fr om 5 t o 30 µm in siz e an d ar e con st r ain ed t o in d iv id u al q u ar t z cr y st al s ( F ig. 5). Th er efor e, t h ey ar e in t er p r et ed as p r im ar y or p seu d osecon d ar y in n at u r e, i.e. t h ey w er e t r ap p ed d u r in g v ein -q u ar t z cr y st al l iz at ion , an d t h u s w er e sel ect ed for fu r t h er st u d ies. Based on t h e n u m ber of p h ases obser v ed at r oom t em p er at u r e, fil l in g d egr ee, an d p h ase v ar iat ion s d u r in g h eat in g an d fr eez in g ex p er im en t s, t h r ee fl u id in cl u sion t y p es cou l d be id en t ified :

Figure 5 -TY PE-I fl u id in cl u sion s ar e CO 2 -fil l ed con t ain in g car bon ic l iq u id ( L ) an d v ap ou r ( V). Som e t y p e I in cl u sion s con t ain on l y on e p h ase ( L ) at r oom t em p er at u r e bu t n u cl eat e a v ap ou r p h ase bel ow am bien t t em p er at u r e. Ty p e-I in cl u sion s gen er al l y sh ow r egu l ar for m s ( n egat iv e cr y st al sh ap e), r an ge in siz e fr om ~5 t o 25 µm an d ar e isol at ed ( p r im ar y ), or l ess com m on l y occu r on p seu d osecon d ar y t r ail s.

-TY PE I I aq u eou s-car bon ic fl u id in cl u sion s p r ed om in at e in ou r sam p l es an d con t ain t h r ee p h ases at r oom t em p er at u r e ( H 2 O L , CO 2 L an d CO 2 V) ( F ig.

Table 3

Microthermometric determinations

Type-I and Type-II fluid inclusions

Th ese in cl u sion t y p es com p r ise m or e t h an 70% of t h e obser v ed fl u id in cl u sion s. Th e m el t in g t em p er at u r e of CO 2 ice ( T m CO 2 ) is cl ose t o t h e CO 2 t r ip l e p oin t ( -56.6°C) w it h a few m easu r em en t s r an gin g d ow n t o -57.1°C ( F ig. 6a). Desp it e t h e n ot or iou s d ifficu l t y of obser v in g cl at h r at e ( Roed d er 1984), cl at h r at e m el t in g ( T m cl at h ) d at a cou l d be obt ain ed fr om m an y Ty p e-I I in cl u sion s u sin g t h e d ou bl e-fr eez in g t ech n iq u e ou t l in ed by Col l in s ( 1979), w h ich al l ow ed cl at h r at e m el t in g t o be obser v ed in t h e absen ce of ice. I n al l aq u eou s-car bon ic in cl u sion s m easu r ed , cl at h r at e m el t ed at t em p er at u r es bet w een 6.9 an d 9.1°C w it h a m od e at 8.2 ± 0.1°C ( sal in it ies bet w een 1.8 an d 5.9 w t % eq . N aCl ; F ig. 7). Th e h om ogen isat ion of t h e car bon ic p h ase ( T h CO 2 ) al w ay s occu r r ed t o l iq u id , an d at t em p er at u r es fr om 7.

Figure 6

Type-III fluid inclusions

Th ese in cl u sion s d isp l ay in it ial ice m el t in g t em p er at u r es sl igh t l y l ow er t h an -24°C, w h ich is cl ose t o t h e eu t ect ic m el t in g t em p er at u r es for t h e sy st em N aCl -K Cl -H 2 O ( -22.9°C) an d N aCl -H 2 O ( -21.2°C). F in al ice m el t in g t em p er at u r es for aq u eou s in cl u sion s r an ge fr om -4.3 t o -0.5°C w it h a m od e at -2.3 ± 2°C ( sal in it ies bet w een 0.7 t o 7.8 w t % eq . N aCl ) ( F ig. 7). Tot al h om ogen isat ion t em p er at u r es w er e on l y r ecor d ed for Ty p e-I I I b in cl u sion s. Th ese in cl u sion s h om ogen ised t o t h e l iq u id p h ase bet w een 130 an d 270°C, w it h a m od e at 220 ± 40°C ( F ig. 8).

Figure 7

Figure 8 Laser Raman spectroscopy Th e m icr ot h er m om et r ic d at a w er e com p l em en t ed by l aser Ram an sp ect r oscop ic an al y ses t o obt ain q u an t it at iv e in for m at ion of t h e sol u t e com p osit ion of t h e fl u id s. Th ir t y -t w o car bon ic an d aq u eou s-car bon ic in cl u sion s ( Ty p es I an d I I ), h ost ed in q u ar t z in t im at el y in t er gr ow n w it h gol d an d su l p h id es, w er e sel ect ed for an al y sis. Ram an sp ect r a w er e r ecor d ed on a J obin Y v on -Hor iba Ram an Sp ect r om et er ( L abr am t y p e) at t h e U n iv er sit y H. Poin car é in N an cy , F r an ce. Th e in cl u sion s w er e il l u m in at ed w it h an ex cit in g r ad iat ion of 514.5 n m fr om an ion ised ar gon l aser , focu sed t h r ou gh an 80X Ol y m p u s obj ect iv e. Th e an al y t ical r esu l t s in d icat e t h at t h e car bon ic p h ase in bot h Ty p e-I an d Ty p e-I I in cl u sion s m ain l y con sist s of p u r e CO 2 . How ev er , t h e sp ect r a r ev eal ed t h at Ty p e-I in cl u sion s con t ain a p et r ogr ap h ical l y an d m icr ot h er m om et r ical l y u n d et ect abl e fil m of w at er ( < 5% ). Th er efor e, t h ese cou l d be cl assified as Ty p e-I I in cl u sion s w it h a h igh CO 2 con t en t . I n ad d it ion , sev er al of t h e t y p e I an d I I in cl u sion s t r ap p ed w it h in q u ar t z -su l p h id e or e z on es, con t ain t r aces of CH 4 ( < 1 m ol % ) an d H 2 S ( < 0.1 m ol % ) ( F ig. 9). I n on e case, w e r ecor d ed t h e p r esen ce of N 2 ( < 0.2 m ol % ) in a Ty p e-I in cl u sion . Th ese d at a ex p l ain t h e sl igh t d ep r ession of t h e CO 2 ice m el t in g t em p er at u r e obser v ed d u r in g cool in g r u n s. Th e t r ap p ed sol id s obser v ed in som e Ty p e-I I an d Ty p e-I I I in cl u sion s h av e been id en t ified by Ram an an al y ses an d con sist m ain l y of biot it e an d m or e r ar el y n ah col it e.

Figure 9

Th e com p u t ed bu l k com p osit ion of al l in cl u sion t y p es is su m m ar ised in Tabl e 4. Bu l k p r op er t ies of Ty p e-I an d Ty p e-I I in cl u sion s ( P-T-V-X ) w er e com p u t ed u sin g m icr ot h er m om et r ic d at a, assu m in g t h at t h e am ou n t of CH 4 ± H 2 S ( al w ay s ≤ 1 m ol % ) d et ect ed by Ram an sp ect r oscop y is n egl igibl e. Th e com p osit ion w as est im at ed assu m in g t h e m ol ar fr act ion of CO 2 in t h e car bon ic p h ase eq u al t o 100% ( Ram boz et al . 1985). F or Ty p e-I fl u id in cl u sion s w e fu r t h er assu m ed t h e p r esen ce of 5% H 2 O, u n d et ect ed op t ical l y an d d u r in g m icr ot h er m om et r ic r u n s, an d absen ce of sal t s.

Table 4 Discussion

Nature of the fluid and mechanisms of entrapment

Du r in g p et r ogr ap h ic ex am in at ion of t h e fl u id in cl u sion p op u l at ion s w e sep ar at ed a gr ou p of in cl u sion s t h at ap p ear ed t o con t ain on l y a car bon ic p h ase ( Ty p e-I ) fr om a secon d p op u l at ion t h at con t ain ed bot h aq u eou s an d car bon ic fl u id s, in v ar y in g p r op or t ion s ( Ty p e-I I ). How ev er , t h e r esu l t s of l aser Ram an sp ect r oscop y r ev eal ed t h e p r esen ce of " in v isibl e" w at er in Ty p e-I in cl u sion s. Th ese r esu l t s su ggest t h at Ty p e-I an d Ty p e-I I act u al l y r ep r esen t t h e sam e p op u l at ion of in cl u sion s, w h ich cov er s a w id e r an ge in car bon ic gas con t en t , i.e. fr om ~15% t o > 95% . I t fol l ow s t h at Ty p e-I an d Ty p e-I I in cl u sion s t r ap p ed m ix ed aq u eou s-car bon ic fl u id s, w h ich is con sist en t w it h t h e fact t h at t h ese t w o in cl u sion t y p es w er e obser v ed w it h in n ear l y al l sel ect ed sam p l es an d in cl u sion assem bl ages. Micr ot h er m om et r ic m easu r em en t s cor r obor at e t h is h y p ot h esis, as in d icat ed by t h e sim il ar it y of t h e d at a for bot h in cl u sion t y p es. Aq u eou s ( Ty p e-I I I ) in cl u sion s al so occu r in p r im ar y cl u st er s or l ess com m on l y in p seu d osecon d ar y t r ail s, w it h in t h e sam e assem bl ages as Ty p e-I I in cl u sion s. I n ad d it ion , sal in it ies of aq u eou s an d aq u eou s-car bon ic in cl u sion s ar e w it h in t h e sam e r an ge ( see abov e). Th er efor e, it is p r obabl e t h at Ty p e-I I I in cl u sion s r ep r esen t t h e w at er -r ich en d m em ber of t h e im m iscibl e aq u eou s-car bon ic fl u id , j u st as Ty p e-I in cl u sion s t r ap p ed t h e CO 2 -r ich en d . I n d eed , t h ese r esu l t s ar e in accor d an ce w it h t h e basic cr it er ia for ev id en ce of fl u id im m iscibil it y in fl u id in cl u sion s ( Ram boz et al 1982). As m en t ion ed abov e, m icr ot h er m om et r ic d at a d isp l ay u n im od al d ist r ibu t ion s ( sal in it ies, T m CO 2 , T h CO 2 ...) for al l in cl u sion t y p es, ex cep t for t ot al h om ogen isat ion t em p er at u r es ( cf. F ig. 8) w h ich sh ow a scat t er of abou t 60°C bet w een Ty p e-I I I ( ~220 ± 40°C) an d Ty p e-I I in cl u sion s ( ~280 ± 30°C). A sim il ar in con sist en cy w as al so obser v ed in fl u id in cl u sion s fr om t h e W il u n a l od e-gol d d ep osit in Au st r al ia ( Hagem an n an d L ü d er s 2003). Th er e, fl u id in cl u sion s in q u ar t z w er e al so in t er p r et ed t o h av e been t r ap p ed d u r in g fl u id im m iscibil it y , an d aq u eou s in cl u sion s d isp l ay ed a T h of abou t 70°C l ow er t h an t h at of aq u eou s-car bon ic in cl u sion s. Hagem an n an d L ü d er s ( 2003) at t r ibu t ed t h is d iscr ep an cy t o l oss of t h e CO 2 ( an d CH 4 ) d issol v ed in t h e w at er -r ich p or t ion of t h e im m iscibl e fl u id d u r in g p r essu r e fl u ct u at ion . I f p r essu r e d r op s, t h ese gases becom e l ess sol u bl e an d can sep ar at e fr om t h e w at er . A su bseq u en t p r essu r e r ise w ou l d cau se u n d er sat u r at ion of t h e r em ain in g aq u eou s fl u id w it h r esp ect t o CO 2 , an d t h u s in d u ce a l ow er h om ogen isat ion t em p er at u r e of t h e in cl u sion s.

T-P-depth conditions during gold mineralisation

As h et er ogen eou s t r ap p in g of im m iscibl e fl u id s w as su ggest ed by t h e d at a, t h e en t r ap m en t t em p er at u r e is giv en by t h e h om ogen isat ion t em p er at u r e of t h e aq u eou s-car bon ic ( Ty p e-I I ) in cl u sion s ( eg. Diam on d 1994). Becau se t h e p r essu r e-t em p er at u r e con d it ion s of t h e fl u id m u st l ie al on g t h e isoch or es for t h e fl u id in cl u sion s, w e can est im at e t h e p r essu r e d u r in g fl u id en t r ap m en t . F igu r e 10 sh ow s r ep r esen t at iv e isoch or es cov er in g t h e d en sit y r an ge of Ty p e-I ( cu r v es C-D) an d Ty p e-I I ( cu r v es A-B) in cl u sion s. Al so t r aced in t h is figu r e ar e t h e T h t ot av er age an d 1 σ st an d ar d d ev iat ion v al u es of Ty p e-I I in cl u sion s, at 250 ± 30°C. Th e p r essu r es obt ain ed r an ge ap p r ox im at el y fr om 500 t o 2100 bar s, w it h an av er age of 1300 bar s. Assu m in g t h at l oad con d it ion s m ay h av e v ar ied bet w een h y d r ost at ic an d l it h ost at ic p r essu r es, an d u sin g p r essu r e gr ad ien t s of ~1 an d 3.6 k m / k bar , r esp ect iv el y , w e can est im at e a d ep t h of for m at ion bet w een abou t 1. sep ar at ion h as been at t r ibu t ed t o fl u id p r essu r e fl u ct u at ion s t r igger ed by fr act u r e op en in g d u r in g cy cl ic fau l t m ov em en t ( e.g. Sibson et al . 1988;Hagem an n an d Cassid y 2000;Br ow n et al . 2003). G iv en t h e ev id en ce of st r u ct u r al con t r ol d u r in g for m at ion of t h e q u ar t z v ein s, it is p ossibl e t h at a sim il ar p r ocess t ook p l ace d u r in g gol d m in er al isat ion at Maev at an an a. Sev er al st u d ies h av e sh ow n cl ose sp at ial an d t em p or al l in k s bet w een fl u id im m iscibil it y in t h e sy st em H 2 O-CO 2 an d t h e p r ecip it at ion of gol d , an d p r ov id e ev id en ce t h at fl u id im m iscibil it y can be an effect iv e m ech an ism for gol d d ep osit ion in l od e-gol d d ep osit s. Sew ar d ( 1989) in t er p r et ed fl u id im m iscibil it y t o be t h e p r in cip al m ech an ism for gol d p r ecip it at ion in geot h er m al sy st em . Mik u ck i an d G r ov es ( 1990) su ggest ed t h at gol d d ep osit ion fr om a h y d r ot h er m al or e fl u id v ia fl u id im m iscibil it y p r ocesses w il l d ep en d on t h e in it ial fl u id com p osit ion s an d bot h t h e m agn it u d e an d r el at iv e r at es at w h ich p H, fO 2 an d t em p er at u r e v ar y d u r in g t h e ev en t . On t h e ot h er h an d , Mik u ck i ( 1998) n ot ed t h at h eat l oss an d fO 2 an d p H in cr ease d u r in g fl u id im m iscibil it y can act t o in h ibit gol d d ep osit ion , an d on l y t h e ch an ge in t h e su l p h u r act iv it y fav ou r s gol d p r ecip it at ion . Th e boil in g m od el is fu r t h er com p l icat ed by ex p er im en t al d at a of W il l iam s-J on es et al . ( 2002,2003) w h ich su ggest t h at m et al s su ch as Au ar e efficien t l y t r an sp or t ed in t h e v ap ou r p h ase. W it h in t h is scen ar io, sep ar at ion of a v ap ou r p h ase w ou l d p r obabl y en h an ce gol d sol u bil it y an d it s t r an sp or t w it h in t h e v ein sy st em . A feat u r e t h at is com m on t o m ost of t h ese d ep osit s is t h e t ect on ic con t r ol of v ein for m at ion an d t h e in fer r ed m et am or p h ic or igin of t h e fl u id s. Th e h igh CO 2 con t en t an d l ow sal in it y ( see abov e) of t h e fl u id s, t oget h er w it h t r aces of CH 4 an d N 2 fou n d in t h e in cl u sion s, su ggest a sim il ar or igin for t h e Au -bear in g fl u id s at Maev at an an a, i.e. t h at t h ey w er e p r obabl y p r od u ced by d ev ol at il isat ion r eact ion s d u r in g r egion al m et am or p h ism ( see al so K er r ich an d F y fe 1981; W y m an an d K er r ich 1988; Mik u ck i an d Rid l ey 1993; K er r ich et al . 2000). Th e fact t h at t h e m in er al ised v ein s cr osscu t t h e BI F l ay er in g bu t ar e p ar al l el t o r egion al sch ist osit y ( see abov e) is con sist en t w it h a sy n t ect on ic or igin of t h e fl u id . Th e abu n d an t basic an d u l t r abasic r ock s w it h in t h e Maev at an an a bel t m ost l ik el y p r ov id ed t h e sou r ce of Au t o t h ese h y d r ot h er m al fl u id s. Th e BI F s r h eol ogical ch ar act er ist ics an d h igh F e con t en t w er e p r obabl y t h e p r in cip al cau se for Au d ep osit ion . F ir st l y , q u ar t z it e is m or e com p et en t t h an t h e sch ist ose w al l r ock s ( soap st on e, am p h ibol it e, et c.). Sh ear in g cau sed it t o fr act u r e t h u s al l ow in g fl u id m igr at ion . Secon d l y , t h e h igh F e con t en t p r ov id ed a good ch em ical t r ap . Th e su l p h id e-ox id e r ep l acem en t t ex t u r es obser v ed in t h e or e z on es, t h e occu r r en ce of gol d w it h in p y r it e, an d t h e p r esen ce of H 2 S gas d et ect ed in t h e fl u id in cl u sion s t oget h er w it h t h e l ow sal in it y of t h e fl u id su ggest gol d t r an sp or t by su l p h id e com p l ex in g ( cf., Sew ar d 1973; Z ot ov an d Bar an ov a 1989; Ben n in g an d Sew ar d 1996;G iber t et al . 1998;Tagir ov et al . 2005). I t fol l ow s t h at w al l -r ock su l p h id at ion cou l d h av e been a p ot en t ial m ech an ism for gol d p r ecip it at ion , t h r ou gh t h e d est abil isat ion of gol d t h io-com p l ex es. F or t h e p u r p ose of t h is d iscu ssion an d in t h e absen ce of m or e p r ecise con t r ol on t h e p H of t h e fl u id s, w e assu m e H 2 S 0 t o be t h e st abl e su l p h u r sp ecies in sol u t ion , w h ich is r eason abl e in v iew of t h e fact t h at at abou t 250°C it p r ed om in at es ov er a w id e p H r an ge, fr om acid ic t o m od er at el y al k al in e con d it ion s ( e.g. Bar n es 1979). F u r t h er m or e, t h e p r esen ce of m u scov it e an d K -fel d sp ar in ad d it ion t o q u ar t z obser v ed in al t er ed w al l r ock s w ou l d fix t h e fl u id p H t o w eak l y acid ic con d it ion s ( Q F M bu ffer ).

Gold deposition model

Figure 11

Sy st em at ic r ep l acem en t of m agn et it e by h em at it e is obser v ed bot h in m in er al ised an d in u n m in er al ised BI F facies, su ggest in g t h at ox id isin g con d it ion s on l y occu r r ed aft er m in er al isat ion , p r obabl y d u r in g su p er gen e al t er at ion . W e t h er efor e assu m e t h at t h e r ed ox con d it ion s p r ev ail in g in t h e q u ar t z it e w er e bel ow t h ose of t h e m agn et it e-h em at it e bu ffer ( F ig. 11). I n ad d it ion , t h e fact t h at p y r it e occu r s as r ep l acem en t of m agn et it e in d icat es t h at t h e fl u id w as n ot in eq u il ibr iu m w it h t h e h ost r ock , bu t in t h e p y r it e st abil it y fiel d , w h er e Au sol u bil it y is m u ch h igh er ( F ig. 11). Rep l acem en t of m agn et it e by p y r it e d est abil ised t h e Au com p l ex es by r ed u cin g l igan d av ail abil it y , an d d r ov e t h e fl u id t o l ow er aH 2 S an d fO 2 con d it ion s, t h er eby d r ast ical l y l ow er in g gol d sol u bil it y ( ar r ow in F igu r e 11). W e bel iev e t h at t h is w as l ik el y t h e p r im ar y fact or in cau sin g Au m in er al iz at ion , h ow ev er , a fu r t h er d r iv e t o Au p r ecip it at ion w ou l d be t h e l oss of su l p h u r t h at t ook p l ace d u r in g fl u id p h ase sep ar at ion , d u e t o p r efer en t ial p ar t it ion in g of H 2 S in t o t h e ex sol v in g CO 2 p h ase.

Conclusions

Th e Maev at an an a gol d d ist r ict is an ex am p l e of an ep igen et ic l od e-gol d d ep osit t h at h as u n d er gon e m ed iu m -gr ad e m et am or p h ism d u r in g a br it t l e t ect on ic ev en t . Th e d ep osit s con sist of gol d -bear in g q u ar t z -su l p h id e v ein s cr osscu t t in g ban d ed ir on for m at ion h ost ed in a gr een st on e bel t . I n v est igat ion of fl u id in cl u sion s h ost ed in Au -bear in g v ein q u ar t z in d icat es h et er ogen eou s t r ap p in g of a l ow -sal in it y aq u eou s fl u id an d a car bon ic fl u id con t ain in g t r aces of H 2 S. F l u id in cl u sion t r ap p in g con d it ion s av er age at 250°C an d ~1 k bar . Th e fl u id w as m ost l ik el y of m et am or p h ic or igin , as in d icat ed by t h e abu n d an t CO 2 an d l ow sal in it y of t h e in cl u sion s. F l u id im m iscibil it y w as p r obabl y t r igger ed by t h e p r essu r e r el eased by fr act u r in g of t h e q u ar t z it es d u r in g fau l t m ov em en t s. Th e p r esen ce of H 2 S in t h e fl u id an d t h e sy st em at ic p y r it isat ion of t h e w al l -r ock in d icat e gol d t r an sp or t by t h io-com p l ex in g. F r act u r in g en h an ced fl u id cir cu l at ion t h r ou gh t h e BI F , w h er e r eact ion of t h e su l p h id e-bear in g fl u id s w it h t h e ir on ox id es cau sed p y r it e d ep osit ion . Au p r ecip it at ion w as t r igger ed by t h e t w o-fol d d ecr ease in l igan d con cen t r at ion of t h e fl u id , as a con seq u en ce of l ow er in g t h e aH 2 S an d fO 2 as t h e fl u id ev ol v ed t ow ar d s r ock -bu ffer ed con d it ion s d u r in g fl u id -r ock in t er act ion , an d sep ar at ion of a car bon ic p h ase in t o w h ich H 2 S p ar t it ion ed p r efer en t ial l y .

Roedder E (198 4 ) F luid inclusions. Rev Mineral 12, Mineral Soc Am, 6 4 4 pp Seward TM (197 3) Thio complex es of gold and the transport of gold in hy drothermal ore solutions. G eochim Cosmochim Acta 37 : 37 9-399 Seward TM (198 9) The hy drothermal chemistry of gold and its implications for ore formation; b oiling and conductiv e cooling as ex amples. In: K eay s RR, Ramsay W RH, G rov es DI (eds) The geology of gold deposits; the perspectiv e in 198 8 . E con G eol 6 3 , 19 7 3 ) . Fig. 3 Im a g es o f B IF l a y er s a nd a sso c ia t ed m iner a l isa t io n. a ) A h a nd sa m p l e sh o w ing a su l p h id e ( su l p h ) -r ic h q u a r t z b a nd c u t t ing a t a sh a l l o w a ng l e d a r k m a g net it e ( M a g ) -r ic h b a nd s ( M AE -I-3 L ) . b ) Sl a b sh o w ing a q u a r t z v ein c r o ss-c u t t ing B IF l a y er ing ( M AE -I-1C ) . c ) P h o t o m ic r o g r a p h s u nd er t r a nsm it t ed c r o ss-p o l a r iz ed l ig h t ( X P L ) a nd r ef l ec t ed p l a in-p o l a r iz ed l ig h t ( R L ) o f B IF l a y er ing c r o ss-c u t b y a q u a r t z v ein ( M AE -A-3 a ) . Th e inset s sh o w d et a il s o f a l t er ed B IF im m ed ia t el y a d j a c ent t o t h e q u a r t z v ein ( l o c a l iz ed in t h e l a r g e im a g e b y t h e w h it e b o x ) ; t h ey il l u st r a t e t h e p a r t ia l r ep l a c em ent o f m a g net it e ( M a g ) b y p y r it e ( P y ) a nd c h a l c o p y r it e ( C c p ) , a s w el l a s inc o m p l et e p seu d o m o r p h ism o f p r im a r y m a g net it e b y h em a t it e ( Hem ) . Fig. 4 P h o t o m ic r o g r a p h o f g o l d g r a ins w it h in a q u a r t z v ein ( R L ) ( M AE -8-2c ) . Th e g o l d g r a ins ( Au ) o c c u r a s inc l u sio ns w it h in q u a r t z ( Q t z ) , a nd in a sm a l l f issu r e a sso c ia t ed w it h g a l ena ( G n) . Th e l a r g est g o l d g r a in m ea su r es 10 0 µm . Fig. 5 P h o t o m ic r o g r a p h s sh o w ing : a ) Iso l a t ed p r im a r y Ty p e-II a nd Ty p e IIIb inc l u sio ns; b ) a t r a il o f sec o nd a r y f l u id inc l u sio n c r o ss-c u t t ing q u a r t z g r a in b o u nd a r ies; c ) c o ex ist ing Ty p e-II inc l u sio ns sh o w ing v a r ia b l e C O 2 / H 2 O r a t io s; d ) t r a il s o f p seu d o sec o nd a r y f l u id inc l u sio ns in q u a r t z g r a ins. Al l im a g es a r e in p l a in-p o l a r iz ed t r a nsm it t ed l ig h t ( P P L ) . Sa m p l es M AE -A-3 c ( a a nd c ) , M AE -8 ( b ) , M AE -28b ( d ) . 7 Sa l init y ( w t % eq . N a C l ) o f a q u eo u s a nd a q u eo u s-c a r b o nic f l u id inc l u sio ns. 0 5 ) . Th e so l id l ines sep a r a t e t h e st a b il it y f iel d s o f p y r it e, p y r r h o t it e, m a g net it e, a nd h em a t it e. Th e a r r o w is a sc h em a t ic il l u st r a t io n o f a p o ssib l e ev o l u t io n p a t h o f a g o l d u nd er sa t u r a t ed h y d r o t h er m a l f l u id r ea c t ing w it h a q u a r t z -m a g net it e b ea r ing r o c k .

Figure Captions

Table 1 -R e p r e s e n t a t i v e e l e c t r o n m i c r o p r o b e a n a l y s e s o f s u l p h i d e s a n d m a g n e t i t e .

Sulphides

  an d Sh ep h er d et al . ( 1985), u sin g a L in k am THMG S 600 h eat in g-fr eez in g st age m ou n t ed on a BX -51 Ol y m p u s m icr oscop e. Th e st age w as cal ibr at ed again st p u r e H 2 O sy n t h et ic in cl u sion s ( 0 an d + 374.1°C) su p p l ied by Sy n F l in c an d w it h p u r e CO 2 -bear in g n at u r al in cl u sion s ( -56.6°C) fr om Cam p eir io ( Ticin o, Sw it z er l an d ).Measu r em en t s bel ow 0°C ar e accu r at e t o ±0.1°C, w h er eas in h eat in g r u n s t em p er at u r es ar e accu r at e t o ±1°C. Cr y ogen ic ex p er im en t s w er e car r ied ou t befor e h eat in g r u n s, t o av oid t h e r isk of d ecr ep it at in g t h e in cl u sion s. Sal in it y ( ex p r essed as w t % eq . N aCl ), bu l k com p osit ion , an d d en sit y d at a w er e cal cu l at ed by r ed u cin g r aw t h er m om et r ic d at a w it h t h e MacF l in Cor soft w ar e p ack age of Br ow n an d Hagem an n ( 1995; cf. al so Bak k er an d Br ow n 2003). Eq u at ion s of st at e u sed w er e t h at of Bow er s an d Hel geson ( 1983) for t h e H 2 O-CO 2 -N aCl sy st em an d t h at of Z h an g an d F r an t z ( 1987) for t h e H 2 O-N aCl ± K Cl sy st em .

  5c). L ik e Ty p e I in cl u sion s, som e Ty p e-I I in cl u sion s on l y n u cl eat e a CO 2 v ap ou r bu bbl e u p on cool in g. I r r egu l ar , r ou n d ed , or n egat iv e cr y st al sh ap es ar e obser v ed for Ty p e-I I in cl u sion s. Th ey can be r an d om l y d ist r ibu t ed , cl u st er ed in t h e cen t r es of gr ain s, or occu r in p seu d osecon d ar y t r ail s. Th eir siz er an ge is sim il ar t o t h at of Ty p e-I in cl u sion s. Th e v ol u m et r ic p r op or t ion of t h e CO 2 -r ich p h ase v ar ies fr om 30 t o 70 v ol % , bu t is m ost l y bet w een 50 an d 70 v ol % . -TY PE-I I I fl u id in cl u sion s con t ain eit h er H 2 O l iq u id on l y ( Ty p e I I I a) or H 2 O l iq u id an d v ap ou r ( Ty p e I I I b) at r oom t em p er at u r e. Ty p e-I I I b in cl u sion s ar e m or e abu n d an t , an d d isp l ay a con st an t d egr ee of fil l in g ( L / V ~0.90-0.95). Th ey r an ge in d iam et er fr om 5 t o 35 µm an d v ar y in sh ap e fr om ir r egu l ar t o r ou n d or el l ip soid . F l u id in cl u sion assem bl ages com p r isin g bot h Ty p e-I an d Ty p e-I I in cl u sion s w it h in t h e sam e cl u st er or t r ail ar e com m on , as ar e Ty p e-I I in cl u sion s w it h v ar iabl e p r op or t ion s of CO 2 an d H 2 O. How ev er , t h e v ar iat ion in H 2 O/ CO 2 is l ess w it h in in d iv id u al gr ou p s an d t r ail s t h an am on g d iffer en t gr ain s. Ty p e-I in cl u sion s ar e on l y r ar el y associat ed w it h Ty p e-I I I in cl u sion s. Dau gh t er m in er al s h av e n ot been fou n d in an y of t h e fl u id in cl u sion s st u d ied , h ow ev er , on r ar e occasion s, w e h av e obser v ed Ty p e-I I an d Ty p e-I I I in cl u sion s con t ain in g an ap p ar en t l y an isot r op ic t r ap p ed sol id . Th e m ain com p on en t s an d t im in g of t r ap p in g of al l in cl u sion t y p es w it h r esp ect t o t h e h ost m in er al ar e su m m ar ised in Tabl e 3.

  3 t o 30.9°C an d fr om 25 t o 31°C for Ty p es I an d I I , r esp ect iv el y ( F ig. 6b). Th ese v al u es cor r esp on d t o bu l k d en sit ies of 0.65 t o 0.88 g/ cm 3 an d 0.73 t o 0.94 g/ cm 3 for Ty p es I an d I I , r esp ect iv el y . Ty p e-I I in cl u sion s d isp l ay t ot al h om ogen isat ion t em p er at u r es bet w een 210 an d 380°C w it h a p eak at 280 ± 30°C ( F ig. 8). I n d eed , t h e m aj or it y of Ty p e-I I fl u id in cl u sion s h om ogen ise in t o a l iq u id p h ase bet w een 250 an d 310°C, bu t som e in cl u sion s h om ogen ise t o t h e v ap ou r p h ase at abou t 310 ± 15°C ( n = 11).

  5 an d 5 k m . Su ch sh al l ow d ep t h s ar e t y p ical of Ar ch aean BI F -h ost ed m esot h er m al l od e-gol d d ep osit s ( e.g. Ph il l ip s an d Pow el l 1992; Hagem an n an d Cassid y 2000).

  Figure 10

  Th e Maev at an an a d ep osit s d isp l ay m an y sim il ar it ies t o ot h er Ar ch aean l od e-gol d d ep osit s su ch as Mt . Mor gan s an d Cl eo in W est er n Au st r al ia ( Viel r eich er et al . 1994; Br ow n et al . 2003, r esp ect iv el y ), Hol l in ger -McI n t y r e in On t ar io ( W al sh et al . 1988), F u m an i an d K al ah ar i G ol d r id ge in Sou t h Afr ica ( Pr et or iu s et al . 1988; Ham m on d an d Moor e 2006).

  04 Shepherd TJ, Ranking AH, Alderthon DHM (198 5 ) A practical guide to fluid inclusion studies. Blackie & Son L td., G lasgow & L ondon, 239 pp Sib son RH, Rob ert F , Poulsen K H (198 8 ) High angle rev erse faults, fluid-pressure cy cling, and mesothermal gold-q uartz deposits. G eology 16 : 5 5 1-5 5 5 Tagirov BR, Salv i S, Schott J, Baranov a N N (2005 ) E x perimental study of gold-hy drosulphide complex ing in aq ueous solutions at 35 0-5 00°C, 5 00 and 1000 b ars using mineral b uffers. G eochim Cosmochim Acta 6 9: 2119-2132 Tucker RD, Ashwal L D, Handke MJ, Hamilton MA, L e G range M, Ramb eloson R (1999) U -Pb geochronology and isotope geochemistry of the Archaean and Proteroz oic rocks of N orth-Central Madagascar. J G eol 107 : 125 -15 3 Vielreicher RM, G rov es DI, Ridley JR, McN aughton N J (1994 ) A replacement origin for the BIF -hosted gold deposit at Mt. Morgans, Y ilgarn Block, W .A. Ore G eol Rev 9: 325 -34 7 W alsh JF , K esler SE , Duff D, Cloke PL (198 8 ) F luid inclusion geochemistry of high-grade v ein-hosted gold ore at the Pamour Mine, Porcupine Camp, Ontario. E con G eol 8 1: 6 8 1-7 03 W illiams-Jones AE , Migdisov AA, Archib ald SM, Xiao Z (2002) Vapor-transport of ore metals. In: Hellman R, W ood SA (eds) W ater-Rock Interaction, Ore Deposits, and E nv ironmental G eochemistry : a Trib ute to Dav id A. Crerar, G eochem Soc Spec Pub l pp 27 9-305 W illiams-Jones AE , Migdisov AA, Archib ald SM (2003) Vapor transport of ore metals in hy drothermal sy stems. G eol Soc Am Ab stracts with Programs, 35 : 35 6 W y man D, and K errich R (198 8 ) Alkaline magmatism, maj or structures and gold deposits: Implications for greenstone b elt gold metallogeny . E con G eol 8 3: 4 5 4 -4 6 1 Z hang Y G , F rantz JD (198 7 ) Determination of the homogeniz ation temperatures and densities of supercritical fluids in the sy stem N aCl-K Cl-CaCl 2 -H 2 O using sy nthetic fluid inclusions. Chem G eol 6 4 : 335 -35 0 Z otov AV, Baranov a N N (198 9) Thermody namic properties of the aurochloride solute complex AuCl 2 -at temperatures of 35 0-5 00°C and pressures of 5 00-15 00 b ars. Sci G eol Bull 4 2:335 -34 2

Fig. 1 G

 1 Fig.1G eo l o g ic a l m a p sh o w ing t h e p r inc ip a l t ec t o nic u nit s o f M a d a g a sc a r ( m o d if ied a f t er C o l l ins et a l . 20 0 3 ) Fig.2G eo l o g ic a l m a p o f t h e M a ev a t a na na r eg io n b et w een t h e Ik o p a a nd B et sib o k a R iv er s, sh o w ing t h e d ist r ib u t io n o f g r a nit o id s, g r eenst o nes, p r o b a b l e f a u l t s a nd t h e M a ev a t a na na g o l d d ist r ic t ( m o d if ied a f t er B é sa ir ie 196 3 , 19 7 3 ) . Fig.3Im a g es o f B IF l a y er s a nd a sso c ia t ed m iner a l isa t io n. a ) A h a nd sa m p l e sh o w ing a su l p h id e ( su l p h ) -r ic h q u a r t z b a nd c u t t ing a t a sh a l l o w a ng l e d a r k m a g net it e ( M a g ) -r ic h b a nd s ( M AE -I-3 L ) . b ) Sl a b sh o w ing a q u a r t z v ein c r o ss-c u t t ing B IF l a y er ing ( M AE -I-1C ) . c ) P h o t o m ic r o g r a p h s u nd er t r a nsm it t ed c r o ss-p o l a r iz ed l ig h t ( X P L ) a nd r ef l ec t ed p l a in-p o l a r iz ed l ig h t ( R L ) o f B IF l a y er ing c r o ss-c u t b y a q u a r t z v ein ( M AE -A-3 a ) . Th e inset s sh o w d et a il s o f a l t er ed B IF im m ed ia t el y a d j a c ent t o t h e q u a r t z v ein ( l o c a l iz ed in t h e l a r g e im a g e b y t h e w h it e b o x ) ; t h ey il l u st r a t e t h e p a r t ia l r ep l a c em ent o f m a g net it e ( M a g ) b y p y r it e ( P y ) a nd c h a l c o p y r it e ( C c p ) , a s w el l a s inc o m p l et e p seu d o m o r p h ism o f p r im a r y m a g net it e b y h em a t it e ( Hem ) . Fig.4P h o t o m ic r o g r a p h o f g o l d g r a ins w it h in a q u a r t z v ein ( R L ) ( M AE -8-2c ) . Th e g o l d g r a ins ( Au ) o c c u r a s inc l u sio ns w it h in q u a r t z ( Q t z ) , a nd in a sm a l l f issu r e a sso c ia t ed w it h g a l ena ( G n) . Th e l a r g est g o l d g r a in m ea su r es 10 0 µm . Fig.5P h o t o m ic r o g r a p h s sh o w ing : a ) Iso l a t ed p r im a r y Ty p e-II a nd Ty p e IIIb inc l u sio ns; b ) a t r a il o f sec o nd a r y f l u id inc l u sio n c r o ss-c u t t ing q u a r t z g r a in b o u nd a r ies; c ) c o ex ist ing Ty p e-II inc l u sio ns sh o w ing v a r ia b l e C O 2 / H 2 O r a t io s; d ) t r a il s o f p seu d o sec o nd a r y f l u id inc l u sio ns in q u a r t z g r a ins. Al l im a g es a r e in p l a in-p o l a r iz ed t r a nsm it t ed l ig h t ( P P L ) . Sa m p l es M AE -A-3 c ( a a nd c ) , M AE -8 ( b ) , M AE -28b ( d ) . Fig. 6 Hist o g r a m s sh o w ing a ) m el t ing t em p er a t u r e o f C O 2 ic e ( T m C O 2 ) a nd b ) h o m o g enisa t io n t em p er a t u r e o f C O 2 ( T h C O 2 ) f o r Ty p e-I a nd Ty p e-II f l u id inc l u sio ns. Fig.7Sa l init y ( w t % eq . N a C l ) o f a q u eo u s a nd a q u eo u s-c a r b o nic f l u id inc l u sio ns. Fig.8Hist o g r a m o f t o t a l h o m o g enisa t io n t em p er a t u r e ( T h t o t ) f o r Ty p e-II a nd Ty p e-III inc l u sio ns. Fig. 9 R ep r esent a t iv e R a m a n sp ec t r a o f Ty p e-I a nd o f t h e c a r b o nic p h a se in Ty p e-II inc l u sio ns. Th e sp ec t r a c o nf ir m t h a t t h e c a r b o nic p h a se in b o t h inc l u sio n t y p es c o nsist s o f C O 2 a nd sh o w t h e o c c a sio na l p r esenc e o f t r a c es o f C H 4 ( < 1 m o l % ) a nd H 2 S ( < 0 . 1 m o l % ) .Fig. 10 R ep r esent a t iv e iso c h o r es f o r H2 O-N a C l -C O 2 ± C H 4 ± H 2 S fl u id inc l u sio ns t r a p p ed in q u a r t z -su l p h id e v eins. Iso c h o r es A-B a nd C -D c o v er t h e d ensit y r a ng e o f Ty p e-II a nd Ty p e-I inc l u sio ns, r esp ec t iv el y . Th e a v er a g e a nd 1 σ st a nd a r d d ev ia t io n o f t h e h o m o g eniz a t io n t em p er a t u r e o f Ty p e-II inc l u sio ns is sh o w n b y t h e v er t ic a l l ines. Fig.11C a l c u l a t ed so l u b il it y o f g o l d a t 25 0 °C a nd 1k b , c o m p u t ed a s a f u nc t io n o f fH 2( g ) a nd aH 2 S ( a q ) f o r a 1 m KC l a q u eo u s so l u t io n in eq u il ib r iu m w it h t h e q u a r t z -m u sc o v it e-K-f el d sp a r p H b u f f er . Th e d a sh ed l ines r ep r esent

Fig. 6

 6 Fig.1G eo l o g ic a l m a p sh o w ing t h e p r inc ip a l t ec t o nic u nit s o f M a d a g a sc a r ( m o d if ied a f t er C o l l ins et a l . 20 0 3 ) Fig.2G eo l o g ic a l m a p o f t h e M a ev a t a na na r eg io n b et w een t h e Ik o p a a nd B et sib o k a R iv er s, sh o w ing t h e d ist r ib u t io n o f g r a nit o id s, g r eenst o nes, p r o b a b l e f a u l t s a nd t h e M a ev a t a na na g o l d d ist r ic t ( m o d if ied a f t er B é sa ir ie 196 3 , 19 7 3 ) . Fig.3Im a g es o f B IF l a y er s a nd a sso c ia t ed m iner a l isa t io n. a ) A h a nd sa m p l e sh o w ing a su l p h id e ( su l p h ) -r ic h q u a r t z b a nd c u t t ing a t a sh a l l o w a ng l e d a r k m a g net it e ( M a g ) -r ic h b a nd s ( M AE -I-3 L ) . b ) Sl a b sh o w ing a q u a r t z v ein c r o ss-c u t t ing B IF l a y er ing ( M AE -I-1C ) . c ) P h o t o m ic r o g r a p h s u nd er t r a nsm it t ed c r o ss-p o l a r iz ed l ig h t ( X P L ) a nd r ef l ec t ed p l a in-p o l a r iz ed l ig h t ( R L ) o f B IF l a y er ing c r o ss-c u t b y a q u a r t z v ein ( M AE -A-3 a ) . Th e inset s sh o w d et a il s o f a l t er ed B IF im m ed ia t el y a d j a c ent t o t h e q u a r t z v ein ( l o c a l iz ed in t h e l a r g e im a g e b y t h e w h it e b o x ) ; t h ey il l u st r a t e t h e p a r t ia l r ep l a c em ent o f m a g net it e ( M a g ) b y p y r it e ( P y ) a nd c h a l c o p y r it e ( C c p ) , a s w el l a s inc o m p l et e p seu d o m o r p h ism o f p r im a r y m a g net it e b y h em a t it e ( Hem ) . Fig.4P h o t o m ic r o g r a p h o f g o l d g r a ins w it h in a q u a r t z v ein ( R L ) ( M AE -8-2c ) . Th e g o l d g r a ins ( Au ) o c c u r a s inc l u sio ns w it h in q u a r t z ( Q t z ) , a nd in a sm a l l f issu r e a sso c ia t ed w it h g a l ena ( G n) . Th e l a r g est g o l d g r a in m ea su r es 10 0 µm . Fig.5P h o t o m ic r o g r a p h s sh o w ing : a ) Iso l a t ed p r im a r y Ty p e-II a nd Ty p e IIIb inc l u sio ns; b ) a t r a il o f sec o nd a r y f l u id inc l u sio n c r o ss-c u t t ing q u a r t z g r a in b o u nd a r ies; c ) c o ex ist ing Ty p e-II inc l u sio ns sh o w ing v a r ia b l e C O 2 / H 2 O r a t io s; d ) t r a il s o f p seu d o sec o nd a r y f l u id inc l u sio ns in q u a r t z g r a ins. Al l im a g es a r e in p l a in-p o l a r iz ed t r a nsm it t ed l ig h t ( P P L ) . Sa m p l es M AE -A-3 c ( a a nd c ) , M AE -8 ( b ) , M AE -28b ( d ) . Fig. 6 Hist o g r a m s sh o w ing a ) m el t ing t em p er a t u r e o f C O 2 ic e ( T m C O 2 ) a nd b ) h o m o g enisa t io n t em p er a t u r e o f C O 2 ( T h C O 2 ) f o r Ty p e-I a nd Ty p e-II f l u id inc l u sio ns. Fig.7Sa l init y ( w t % eq . N a C l ) o f a q u eo u s a nd a q u eo u s-c a r b o nic f l u id inc l u sio ns. Fig.8Hist o g r a m o f t o t a l h o m o g enisa t io n t em p er a t u r e ( T h t o t ) f o r Ty p e-II a nd Ty p e-III inc l u sio ns. Fig. 9 R ep r esent a t iv e R a m a n sp ec t r a o f Ty p e-I a nd o f t h e c a r b o nic p h a se in Ty p e-II inc l u sio ns. Th e sp ec t r a c o nf ir m t h a t t h e c a r b o nic p h a se in b o t h inc l u sio n t y p es c o nsist s o f C O 2 a nd sh o w t h e o c c a sio na l p r esenc e o f t r a c es o f C H 4 ( < 1 m o l % ) a nd H 2 S ( < 0 . 1 m o l % ) .Fig. 10 R ep r esent a t iv e iso c h o r es f o r H2 O-N a C l -C O 2 ± C H 4 ± H 2 S fl u id inc l u sio ns t r a p p ed in q u a r t z -su l p h id e v eins. Iso c h o r es A-B a nd C -D c o v er t h e d ensit y r a ng e o f Ty p e-II a nd Ty p e-I inc l u sio ns, r esp ec t iv el y . Th e a v er a g e a nd 1 σ st a nd a r d d ev ia t io n o f t h e h o m o g eniz a t io n t em p er a t u r e o f Ty p e-II inc l u sio ns is sh o w n b y t h e v er t ic a l l ines. Fig.11C a l c u l a t ed so l u b il it y o f g o l d a t 25 0 °C a nd 1k b , c o m p u t ed a s a f u nc t io n o f fH 2( g ) a nd aH 2 S ( a q ) f o r a 1 m KC l a q u eo u s so l u t io n in eq u il ib r iu m w it h t h e q u a r t z -m u sc o v it e-K-f el d sp a r p H b u f f er . Th e d a sh ed l ines r ep r esent

Fig. 8

 8 Fig.1G eo l o g ic a l m a p sh o w ing t h e p r inc ip a l t ec t o nic u nit s o f M a d a g a sc a r ( m o d if ied a f t er C o l l ins et a l . 20 0 3 ) Fig.2G eo l o g ic a l m a p o f t h e M a ev a t a na na r eg io n b et w een t h e Ik o p a a nd B et sib o k a R iv er s, sh o w ing t h e d ist r ib u t io n o f g r a nit o id s, g r eenst o nes, p r o b a b l e f a u l t s a nd t h e M a ev a t a na na g o l d d ist r ic t ( m o d if ied a f t er B é sa ir ie 196 3 , 19 7 3 ) . Fig.3Im a g es o f B IF l a y er s a nd a sso c ia t ed m iner a l isa t io n. a ) A h a nd sa m p l e sh o w ing a su l p h id e ( su l p h ) -r ic h q u a r t z b a nd c u t t ing a t a sh a l l o w a ng l e d a r k m a g net it e ( M a g ) -r ic h b a nd s ( M AE -I-3 L ) . b ) Sl a b sh o w ing a q u a r t z v ein c r o ss-c u t t ing B IF l a y er ing ( M AE -I-1C ) . c ) P h o t o m ic r o g r a p h s u nd er t r a nsm it t ed c r o ss-p o l a r iz ed l ig h t ( X P L ) a nd r ef l ec t ed p l a in-p o l a r iz ed l ig h t ( R L ) o f B IF l a y er ing c r o ss-c u t b y a q u a r t z v ein ( M AE -A-3 a ) . Th e inset s sh o w d et a il s o f a l t er ed B IF im m ed ia t el y a d j a c ent t o t h e q u a r t z v ein ( l o c a l iz ed in t h e l a r g e im a g e b y t h e w h it e b o x ) ; t h ey il l u st r a t e t h e p a r t ia l r ep l a c em ent o f m a g net it e ( M a g ) b y p y r it e ( P y ) a nd c h a l c o p y r it e ( C c p ) , a s w el l a s inc o m p l et e p seu d o m o r p h ism o f p r im a r y m a g net it e b y h em a t it e ( Hem ) . Fig.4P h o t o m ic r o g r a p h o f g o l d g r a ins w it h in a q u a r t z v ein ( R L ) ( M AE -8-2c ) . Th e g o l d g r a ins ( Au ) o c c u r a s inc l u sio ns w it h in q u a r t z ( Q t z ) , a nd in a sm a l l f issu r e a sso c ia t ed w it h g a l ena ( G n) . Th e l a r g est g o l d g r a in m ea su r es 10 0 µm . Fig.5P h o t o m ic r o g r a p h s sh o w ing : a ) Iso l a t ed p r im a r y Ty p e-II a nd Ty p e IIIb inc l u sio ns; b ) a t r a il o f sec o nd a r y f l u id inc l u sio n c r o ss-c u t t ing q u a r t z g r a in b o u nd a r ies; c ) c o ex ist ing Ty p e-II inc l u sio ns sh o w ing v a r ia b l e C O 2 / H 2 O r a t io s; d ) t r a il s o f p seu d o sec o nd a r y f l u id inc l u sio ns in q u a r t z g r a ins. Al l im a g es a r e in p l a in-p o l a r iz ed t r a nsm it t ed l ig h t ( P P L ) . Sa m p l es M AE -A-3 c ( a a nd c ) , M AE -8 ( b ) , M AE -28b ( d ) . Fig. 6 Hist o g r a m s sh o w ing a ) m el t ing t em p er a t u r e o f C O 2 ic e ( T m C O 2 ) a nd b ) h o m o g enisa t io n t em p er a t u r e o f C O 2 ( T h C O 2 ) f o r Ty p e-I a nd Ty p e-II f l u id inc l u sio ns. Fig.7Sa l init y ( w t % eq . N a C l ) o f a q u eo u s a nd a q u eo u s-c a r b o nic f l u id inc l u sio ns. Fig.8Hist o g r a m o f t o t a l h o m o g enisa t io n t em p er a t u r e ( T h t o t ) f o r Ty p e-II a nd Ty p e-III inc l u sio ns. Fig. 9 R ep r esent a t iv e R a m a n sp ec t r a o f Ty p e-I a nd o f t h e c a r b o nic p h a se in Ty p e-II inc l u sio ns. Th e sp ec t r a c o nf ir m t h a t t h e c a r b o nic p h a se in b o t h inc l u sio n t y p es c o nsist s o f C O 2 a nd sh o w t h e o c c a sio na l p r esenc e o f t r a c es o f C H 4 ( < 1 m o l % ) a nd H 2 S ( < 0 . 1 m o l % ) .Fig. 10 R ep r esent a t iv e iso c h o r es f o r H2 O-N a C l -C O 2 ± C H 4 ± H 2 S fl u id inc l u sio ns t r a p p ed in q u a r t z -su l p h id e v eins. Iso c h o r es A-B a nd C -D c o v er t h e d ensit y r a ng e o f Ty p e-II a nd Ty p e-I inc l u sio ns, r esp ec t iv el y . Th e a v er a g e a nd 1 σ st a nd a r d d ev ia t io n o f t h e h o m o g eniz a t io n t em p er a t u r e o f Ty p e-II inc l u sio ns is sh o w n b y t h e v er t ic a l l ines. Fig.11C a l c u l a t ed so l u b il it y o f g o l d a t 25 0 °C a nd 1k b , c o m p u t ed a s a f u nc t io n o f fH 2( g ) a nd aH 2 S ( a q ) f o r a 1 m KC l a q u eo u s so l u t io n in eq u il ib r iu m w it h t h e q u a r t z -m u sc o v it e-K-f el d sp a r p H b u f f er . Th e d a sh ed l ines r ep r esent

Fig. 10 R

 10 Fig.1G eo l o g ic a l m a p sh o w ing t h e p r inc ip a l t ec t o nic u nit s o f M a d a g a sc a r ( m o d if ied a f t er C o l l ins et a l . 20 0 3 ) Fig.2G eo l o g ic a l m a p o f t h e M a ev a t a na na r eg io n b et w een t h e Ik o p a a nd B et sib o k a R iv er s, sh o w ing t h e d ist r ib u t io n o f g r a nit o id s, g r eenst o nes, p r o b a b l e f a u l t s a nd t h e M a ev a t a na na g o l d d ist r ic t ( m o d if ied a f t er B é sa ir ie 196 3 , 19 7 3 ) . Fig.3Im a g es o f B IF l a y er s a nd a sso c ia t ed m iner a l isa t io n. a ) A h a nd sa m p l e sh o w ing a su l p h id e ( su l p h ) -r ic h q u a r t z b a nd c u t t ing a t a sh a l l o w a ng l e d a r k m a g net it e ( M a g ) -r ic h b a nd s ( M AE -I-3 L ) . b ) Sl a b sh o w ing a q u a r t z v ein c r o ss-c u t t ing B IF l a y er ing ( M AE -I-1C ) . c ) P h o t o m ic r o g r a p h s u nd er t r a nsm it t ed c r o ss-p o l a r iz ed l ig h t ( X P L ) a nd r ef l ec t ed p l a in-p o l a r iz ed l ig h t ( R L ) o f B IF l a y er ing c r o ss-c u t b y a q u a r t z v ein ( M AE -A-3 a ) . Th e inset s sh o w d et a il s o f a l t er ed B IF im m ed ia t el y a d j a c ent t o t h e q u a r t z v ein ( l o c a l iz ed in t h e l a r g e im a g e b y t h e w h it e b o x ) ; t h ey il l u st r a t e t h e p a r t ia l r ep l a c em ent o f m a g net it e ( M a g ) b y p y r it e ( P y ) a nd c h a l c o p y r it e ( C c p ) , a s w el l a s inc o m p l et e p seu d o m o r p h ism o f p r im a r y m a g net it e b y h em a t it e ( Hem ) . Fig.4P h o t o m ic r o g r a p h o f g o l d g r a ins w it h in a q u a r t z v ein ( R L ) ( M AE -8-2c ) . Th e g o l d g r a ins ( Au ) o c c u r a s inc l u sio ns w it h in q u a r t z ( Q t z ) , a nd in a sm a l l f issu r e a sso c ia t ed w it h g a l ena ( G n) . Th e l a r g est g o l d g r a in m ea su r es 10 0 µm . Fig.5P h o t o m ic r o g r a p h s sh o w ing : a ) Iso l a t ed p r im a r y Ty p e-II a nd Ty p e IIIb inc l u sio ns; b ) a t r a il o f sec o nd a r y f l u id inc l u sio n c r o ss-c u t t ing q u a r t z g r a in b o u nd a r ies; c ) c o ex ist ing Ty p e-II inc l u sio ns sh o w ing v a r ia b l e C O 2 / H 2 O r a t io s; d ) t r a il s o f p seu d o sec o nd a r y f l u id inc l u sio ns in q u a r t z g r a ins. Al l im a g es a r e in p l a in-p o l a r iz ed t r a nsm it t ed l ig h t ( P P L ) . Sa m p l es M AE -A-3 c ( a a nd c ) , M AE -8 ( b ) , M AE -28b ( d ) . Fig. 6 Hist o g r a m s sh o w ing a ) m el t ing t em p er a t u r e o f C O 2 ic e ( T m C O 2 ) a nd b ) h o m o g enisa t io n t em p er a t u r e o f C O 2 ( T h C O 2 ) f o r Ty p e-I a nd Ty p e-II f l u id inc l u sio ns. Fig.7Sa l init y ( w t % eq . N a C l ) o f a q u eo u s a nd a q u eo u s-c a r b o nic f l u id inc l u sio ns. Fig.8Hist o g r a m o f t o t a l h o m o g enisa t io n t em p er a t u r e ( T h t o t ) f o r Ty p e-II a nd Ty p e-III inc l u sio ns. Fig. 9 R ep r esent a t iv e R a m a n sp ec t r a o f Ty p e-I a nd o f t h e c a r b o nic p h a se in Ty p e-II inc l u sio ns. Th e sp ec t r a c o nf ir m t h a t t h e c a r b o nic p h a se in b o t h inc l u sio n t y p es c o nsist s o f C O 2 a nd sh o w t h e o c c a sio na l p r esenc e o f t r a c es o f C H 4 ( < 1 m o l % ) a nd H 2 S ( < 0 . 1 m o l % ) .Fig. 10 R ep r esent a t iv e iso c h o r es f o r H2 O-N a C l -C O 2 ± C H 4 ± H 2 S fl u id inc l u sio ns t r a p p ed in q u a r t z -su l p h id e v eins. Iso c h o r es A-B a nd C -D c o v er t h e d ensit y r a ng e o f Ty p e-II a nd Ty p e-I inc l u sio ns, r esp ec t iv el y . Th e a v er a g e a nd 1 σ st a nd a r d d ev ia t io n o f t h e h o m o g eniz a t io n t em p er a t u r e o f Ty p e-II inc l u sio ns is sh o w n b y t h e v er t ic a l l ines. Fig.11C a l c u l a t ed so l u b il it y o f g o l d a t 25 0 °C a nd 1k b , c o m p u t ed a s a f u nc t io n o f fH 2( g ) a nd aH 2 S ( a q ) f o r a 1 m KC l a q u eo u s so l u t io n in eq u il ib r iu m w it h t h e q u a r t z -m u sc o v it e-K-f el d sp a r p H b u f f er . Th e d a sh ed l ines r ep r esent

Table 2 -

 2 M i c r o p r o b e a n a l y s e s o f g o l d . F i g u r e s i n p a r e n t h e s e s a r e ( 1 σ ) s t a n d a r d d e v i a t i o n s ; n = n u m b e r o f a v e r a g e d a n a l y s e s ; n . d . = n o t d e t e c t e d .

  n=12

T a b l e 4 -

 4 Q u a n t i t a t i v e d a t a f o r f l u i d i n c l u s i o n s f r o m g o l d -b e a r i n g s u l p h i d e -r i c h q u a r t z v e i n s . C a l c u l a t e d f r o m m i c r o t h e r m o m e t r i c a n d R a m a n d a t a a n d t h e M a c F l i n C o r s o f t w a r e o f B r o w n a n d H a g e m a n n ( 1 9 9 5 ) .

9 F i g .1 1

Acknowledgments

Th is st u d y w as su p p or t ed by t h e Cor u s p r oj ect n ° 98 518 221 " G é ol ogie d u socl e cr ist al l in d e Mad agascar et d e ses m in é r al isat ion s" . Th e au t h or s t h an k t h e Mal agasy gov er n m en t for fin an cial su p p or t t o PA d u r in g h is MSc in Tou l ou se. W e ar e gr at efu l for t h e t ech n ical assist an ce on t h e Ram an an d m icr op r obe an al y ses, w h ich w as p r ov id ed by Th é r è se L h om m e an d Ph il ip p e d e Par sev al , r esp ect iv el y . Th is w or k ben efit ed fr om v al u abl e d iscu ssion s w it h A.E. W il l iam s-J on es an d cr it ical r ev iew by Ber n d L eh m an n . 1 9 F i g . 1 2 0 F i g . 2 2 1 F i g . 3 2 2 F i g . 4 2 3 F i g . 5 2 4 F i g . 6 2 5 F i g . 7 2 6 F i g . 8 2 7

F i g . 9


B Ben Hassine

L Boudou

L Berquez

G Teyssedre

Photo-stimulated discharge current and charge distribution measurements on biaxially oriented polypropylene thin films

published or not. The documents may come

Photo-stimulated discharge current and charge distribution measurements on biaxially oriented polypropylene thin films

B Ben Hassine, Laurent Boudou, Laurent Berquez, G.

Introduction

The development of the market of polymer film capacitors (mainly bi-oriented polypropylene-BOPP) is leaded by many applications in different fields such as electronics, energy storage or electrical vehicle. The study of generation, transport and trapping of charges in relatively thin dielectrics is of specific interest here. Volume trapping is a weakness that introduces a local intensification of the local electric field. On the other hand, the experimental methods to study dielectric phenomena as charge trapping are not numerous. One expects notably methods giving access to the distribution of trap energy levels. Photo-stimulated discharge method (PSD) is among the most used. It consists in measuring the discharge current under light irradiation, making it possible to obtain spectra with wavelengths in the UV-visible range, giving theoretically access to the energy depth of occupied traps [START_REF] Boudou | Photostimulated discharge current measurements on biaxially oriented polypropylene thin films (BOPP)[END_REF]. Our objective is to analyse the PSD spectra on BOPP films, for the first time in conjunction with the density and position of the charges in the material. The later is achieved by Light Intensity Modulation Method (LIMM), suited for films of a few µm thickness.

Results and Discussion

The experimental work was realized with the following procedure: The 18µm thick BOPP films were provided with segmented electrodes [START_REF] Boudou | Photostimulated discharge current measurements on biaxially oriented polypropylene thin films (BOPP)[END_REF]. After applying a voltage of 1 kV for 30 min, a first measurement of the charge distribution is realized by LIMM. Then, the PSD spectrum is recorded while scanning the light from low (590 nm) to high energy (200 nm) at a scanning rate of 24 nm/min. Finally, a second LIMM measurement is achieved. This protocol is repeated for voltages of 2kV and 3kV. The PSD spectra shown in Fig. 1, present two current peaks, located at approximately 400 nm and 220 nm. The PSD intensity increases with the voltage applied during the polarization step; the intensity of the peak located at 220 nm rises when compared to the peak at 400 nm. One notices that the intensity is very weak for 1 kV polarization; it increases substantially for 2 and 3 kV, revealing that the threshold for massive charge injection has been reached. Figs. 2a)-b) show the LIMM current and the space charge distribution recorded after polarization under 3 kV. We note the presence of charges trapped in the sample. The LIMM results obtained after the PSD measurement (see Fig. 2c)-d)) reveal that charges have been partially released from the sample due to optical detrapping, particularly near the surface.

Conclusions

This paper presents a coupling between the PSD measurements with LIMM measurements in BOPP films. The methods will be used to probe the actual changes in charge distribution induced by the optical detrapping in order to better understand the related processes and to propose a quantitative analysis of charge trapping phenomena.

Figure 1 :

 1 Figure 1: PSD spectra of 18 µm-thick BOPP recorded after LIMM measurements with polarization voltage of 1 kV, 2 kV and 3 kV.

Figure 2 :

 2 Figure 2: Real and imaginary part of LIMM current: a) after 3kV, c) after PSD. Space charge profiles: b) after 3kV, d) after PSD.

Acknowledgements

The research is supported by the program IDEX Actions Thématiques Stratégiques ATS 2015 of the Université de Toulouse under project SEPHIR (2016-066-CIF-D-DRVD).