winer—logi™—l w—g—zineD tune PHHPD †olF TT@QAD ppF QVS±RHU

winer—logy of ™omplex goExiEfi vein miner—liz—tionD

fie˜er depositD ƒpess—rtD qerm—ny

IDPD Q

„F ‡eqxi‚ B exh tF vy‚ix

I

winer—logis™hes snstitutD niversit—Èt ‡urz˜urgD em ru˜l—ndD hEWUHUR ‡urz˜urgD qerm—ny È È

P

hep—rtment of i—rth —nd €l—net—ry ƒ™ien™esD w™qill niversityD QRSH niversity ƒtreetD wontre—l g rQe PeUD

g—n—d—

Q

qr—slitzer ƒtrF SD hETQUWI u—rlstein —m w—inD qerm—ny

efƒ„‚eg„

€ostE†—ris™—n veinEtype goExiEfi ores of the fie˜er depositD ƒpess—rt mount—insD qerm—nyD whi™h —re

rel—ted to the €ermi—n uupfers™hieferD h—ve ˜een investig—ted ˜y ore mi™ros™opyD ˆEr—y powder

diffr—™tion —nd ele™tronEpro˜e mi™ro—n—lysisF „he s—mples ™ont—in — v—riety of ore miner—lsD not—˜ly

skutteruditeD n—tive ˜ismuthD ™o˜—ltiteD —llo™l—siteD ni™™oliteD m—u™heriteD gersdorffiteD r—mmels˜ergiteG

p—r—r—mmels˜ergiteD s—ffloriteD loellingite —nd emple™titeF „he ores displ—y stru™tures indi™—tive of

multiple ˜re™™i—tion —nd ™omplex zoned —rsenide —ssem˜l—gesF „hree sequenti—l st—ges of deposition —re

identifiedD whi™h —re @IA the gu st—geD @PA the m—in goExiEfi st—geD —nd @QA the l—te st—geF „he —rsenide

miner—lsD not—˜ly skutteruditeD di—rsenides —nd sulph—rsenidesD show — l—rge r—nge of ™omposition—l

v—ri—tion in goExiEpe sp—™eF e rel—tively limited num˜er of skutterudite —nd di—rsenide ™ompositions

lie outside the ™omposition—l fields est—˜lished in the liter—tureF ƒkutterudite —nd di—rsenides —re

™h—r—™terized ˜y — signifi™—nt su˜stitution of es ˜y ƒ up to HFRR —FpFfFuF —nd HFQI —FpFfFuFD respe™tivelyD

whi™h is l—rger th—n the r—nge previously reported for these miner—lsF ƒulph—rsenide ™ompositions ™—n

˜e grouped into three popul—tionsD whi™h ™onform to ™o˜—lti—n —rsenopyriteD ™o˜—ltite —nd gersdorffiteF

„hey displ—y highly v—ri—˜le esGƒ r—tios ˜etween HFWSXIFHH —nd IFPWXHFUQD ™onsistent with experiment—l

d—t—F istim—tes of the form—tion temper—turesD ˜—sed on the presen™e of dendriti™ n—tive ˜ismuth —nd

emple™titeD —re in the r—nge IHHÿQHHVgD simil—r to different postE†—ris™—n miner—liz—tion styles

widespre—d in gentr—l iuropeF gomp—rison of the goExiEfi vein —ssem˜l—ge with the fr—mework of

—v—il—˜le p—r—geneti™ inform—tion —nd r—diometri™ —ge d—t— for region—l miner—liz—tion events indi™—tes

—n —ge of miner—liz—tion of ~ISHÿITH w— for the fie˜er depositF

ui‰‡y‚hƒX goExiEfi oresD fie˜erD ƒpess—rtD skutteruditeD di—rsenidesD sulph—rsenidesF

type miner—liz—tions of goD xiD fi —nd esF wost of sntrodu™tion

the re™ent studies h—ve fo™used on the str—t—˜ound

miner—liz—tion styleD emph—sizing the import—n™e eƒi met—l deposits rel—ted to the €ermi—n f

of postEdeposition—l pro™esses @di—geneti™ to uupfers™hiefer —re widespre—d in ™entr—l iurope

epigeneti™A for the met—l —™™umul—tion —nd reE —nd h—ve ˜een the su˜je™ts of extensive minerE

distri˜ution within the uupfers™hiefer deposits —logi™—lEgeo™hemi™—l investig—tion @eFgF †—ugh—n

@eFgF ƒun —nd €uttm—nnD IWWUAF „hese investig—E et —lFD IWVWY ƒpe™zikD IWWSAF „he uupfers™hiefer È

tions h—ve fo™used on ore miner—logyD tr—™e hosts two different types of miner—liz—tionX @IA

element —n—lysisD st—˜le isotope —nd org—ni™E str—t—˜ound miner—liz—tions of guD egD esD eu

geo™hemi™—l studies @eFgF fe™htel —nd €uttm—nnD —nd €qiD —nd @PA ™ross™utting epigeneti™ veinE È

IWWIY ƒun —nd €uttm—nnD PHHHAF „he epigeneti™ È

veinEtype goExiEfi miner—liz—tions h—ve not ˜een

studied to the s—me extentD —nd only limited

miner—logi™—lEgeo™hemi™—l d—t— —re —v—il—˜le for B iEm—ilX w—gnerdepsFm™gillF™—

this miner—liz—tion style @eFgF qerl—™hD IWWPAF hysX IHFIIVHGHHPTRTIHPTTQHHQT

5 PHHP „he winer—logi™—l ƒo™iety

„F ‡ eq x i ‚ e x h t F vy‚ i x 

yrogen @‡e˜erD IWWSAF „he ™ryst—lline ˜—sement „he present study reports the results of

™—n ˜e divided into sever—l ƒ‡ÿxiEstriking miner—logi™—l investig—tions ™—rried out on veinE

te™tonoEmet—morphi™ unitsD whi™h —reX type goExiEfi ores of the fie˜er depositD whi™h

@IA elzen—u form—tion @˜iotite —nd horn˜lende ˜elongs to — sm—ll —re— of uupfers™hieferErel—ted

gneissesD —mphi˜olitesAY @PA qeisel˜—™h form—tion ˜—se met—l miner—liz—tions lo™—ted in the x‡ p—rt

@qu—rtzitesD mi™— s™histsD —mphi˜olitesAY of the ƒpess—rt mount—ins @pigF IAF „he fie˜er

@QA woÈm˜ris form—tion @st—uroliteEg—rnetEpl—gioE deposit is the type lo™—lity of the r—re supergene

™l—se gneissesD mus™oviteE˜iotite gneissesAY miner—ls ˜ie˜eriteD goƒy ´U r yD —nd roÈssleriteD R P

@RA ƒ™hweinheim form—tion @mi™— s™histsD ˜iotite wgr‘esy “´U r yY s—mples origin—ting from the R P

gneissesAY —nd @SA ilterhof form—tion @—mphi˜oE goExiEfi veins —re held ˜y most of the import—nt

litesD ™—l™sili™—te gneissesD m—r˜lesD horn˜lende miner—logi™—l museums throughout iurope

gneissesAF €erv—sive deform—tion —nd pe—k met—E @in™luding wuseum fur x—turkundeD ferlinD È

morphism o™™urred during the †—ris™—n orogeny x—tur—l ristory wuseumD vondonD —nd i™ole

—t ~QPHÿQQH w— @‡e˜erD IWWSAF „he met—sediE des winesD €—risAF „he ore —ssem˜l—ges of the goE

ment—ry ro™ks —re ™ross™ut ˜y sever—l l—mproE xiEfi veins —re simil—r to other epigeneti™

phyri™ dykes @‡ro˜elD PHHHA —nd intruded ˜y l—te uupfers™hieferErel—ted depositsD eFgF ‚i™helsdorfD

€ermi—n rhyoliti™ m—gm—sF w—nsfeld —nd ƒ—ngerh—usen @u—utzs™hD IWSQY

„he ™ryst—lline ˜—sement is un™onform—˜ly ‚entzs™h —nd unitzs™hkeD IWTVY „o˜s™h—ll et —lFD

overl—in ˜y €ermi—n sediment—ry ro™ks of the IWVTY qerl—™hD IWWPAD ˜ut show some distin™t

e™hstein @e™hstein ID ‡err— ™y™leAD whi™h fe—turesD su™h —s the presen™e of l—rge —mounts of

™omprises ™onglomer—tesD the uupfers™hiefer n—tive ˜ismuth —nd very ™omplex intergrowths of

—nd ˜ituminous dolomites @pigF IAF „he lowerE goExi —rsenides —nd sulph—rsenidesF „he m—jor

most unit of the e™hstein is ™omposed of o˜je™tives of this investig—tion —re @IA to est—˜lish

™omponentEsupported ™onglomer—ti™ s—ndstonesD — miner—logi™—l ™h—r—™teriz—tion of the goExiEfi

IÿP m thi™kD whi™h h—ve — predomin—ntly ore —ssem˜l—gesD —nd @PA to pl—™e some ™onstr—ints

dolomiti™ ™ementF „hese ™onglomer—ti™ s—ndE on the geneti™ evolution of the fie˜er depositF

stones —re overl—in ˜y the uupfers™hieferD whi™h

represents —n inter™—l—tion of ˜ituminous —rgill—™E

‚egion—l geologi™—l setting

eous to siltEri™h sh—lesD dolomiteEri™h siltstones

—nd dolostonesF „he uupfers™hiefer re—™hes — „he ƒpess—rt mount—ins ™onstitute — p—rt of the

m—ximum thi™kness of PFP m @me—n of HFU mA —nd widEqerm—n gryst—lline ‚iseD whi™h ˜elongs to

is followed ˜y the e™hstein dolomite unitF „he the intern—l zone of the midEiurope—n †—ris™—n

psqF IF qeologi™—l sket™h m—p of the northern p—rt of the ƒpess—rtD showing the lo™—tions of the fie˜er goExiEfi

deposit —s well —s of sever—l other goExi —nd gu depositsF ‚edr—wn —nd modi®ed —fter w—tthes —nd ykrus™h @IWTSAF QVT

gyExsEfs †isx wsxi‚evse„syxD qi‚wex‰

o™™ur in ™lose —sso™i—tion with n—tive —rseni™D lowermost p—rt of the e™hstein dolomite is

n—tive ˜ismuth —nd sever—l —™™essory miner—ls ™omposed of pl—ty ˜ituminous dolostones with

@vorenzD IWWID IWWSAF qeo™hronologi™—l investiE mmEthi™k interl—yers of silty dolostonesD where—s

g—tions h—ve demonstr—ted th—t the onset of the middle —nd upper p—rts —re pure dolostones

miner—liz—tion w—s —t ~IVH w—Y hydrotherm—l @ƒ™hmittD IWWPD IWWQ—AF „he sediment—ry ro™ks of

—™tivity o™™urred —t sever—l distin™t st—ges —nd the e™hstein —re overl—in ˜y the sili™i™l—sti™

™ontinued until ~IHH w— @r—utm—nn et —lFD IWWWAF su™™essions of the vowerD widdle —nd pper

funter @„ri—ssi™AD whi™h represent — ™omplex

sequen™e of s—ndy sh—lesD s—ndstones —nd

„he fie˜er goExiEfi deposit

™onglomer—ti™ s—ndstonesF

wining —™tivities in the fie˜er —re— were ®rst foth the †—ris™—n ™ryst—lline ˜—sement —nd the

re™orded in ISRPD when e—rly workings ™on™enE sediment—ry ro™ks of the postE†—ris™—n ™over —re

tr—ted on str—t—˜ound guE€˜Eeg miner—liz—tions ™ross™ut ˜y x‡ÿƒiEstriking f—ult systems

in the uupfers™hieferF „he m—jor mining periodD @pigs IDPAD whi™h were —™tiv—ted —s — ™onsequen™e

whi™h fo™used on the ™o˜—lt ores of the goExiEfi of the postE†—ris™—n extension—l regime in gentr—l

vein depositsD w—s from IUQI to IVTW @preym—nnD iurope @eFgF ieglerD IWVUAF „hese f—ult systemsD

IWWIAF wost of the s—mples held within museums whi™h dip RSÿVHV tow—rds the ƒ‡ —nd xiD —re

were ™olle™ted during this periodF „he goExiEfi frequently miner—lized with ˜—ryte —nd qu—rtz

miner—liz—tion of the fie˜er deposit ™omprises @wur—wskiD IWSRY rofm—nnD IWUWAD —nd ™—rry

four distin™t vein systemsD whi™h —reX @IA the lo™—l enri™hments of fi miner—lsD whi™h —re

fu™hel˜—™h go veinsY @PA the ‚oÈhrig go veinsY domin—ted ˜y emple™tite —nd n—tive ˜ismuth È

@QA the vo™h˜orn go veinsY —nd @RA the fismuth @ƒ™hmittD IWWQ˜AF †einEtype goExiEfi —ssemE

vein @pigF PAF ell vein systems represent minerE ˜l—ges o™™ur only in ™lose ™ont—™t with the

—lized p—rts of the postE†—ris™—n f—ult zonesD sediment—ry ro™ks of the e™hsteinF e more

whi™h were still —™tive during ore form—tionD —s ™omplex miner—liz—tion style h—s ˜een reported

demonstr—ted ˜y ˜re™™i—tion —nd p—rti—l myloniE from — stru™tur—lly simil—r f—ult zone exposed in

tiz—tion of the older ore —ssem˜l—gesF wost of the the vower €ermi—n rhyolite of ƒ—il—ufD where wn

veins displ—y — x‡ÿƒi strike in the r—nge ore —ssem˜l—ges @wn oxides —nd ™—r˜on—tesA

psqF PF het—iled geologi™—l m—p of the fie˜er goExiEfi depositD ƒpess—rtD qerm—nyD showing the prin™ip—l

—rr—ngement of the vein systemsF ‚edr—wn —nd modi®ed —fter hiederi™h —nd v—emmlen @IWTRAF QVU

„F ‡ eq x i ‚ e x h t F vy‚ i x 

s™opyD ele™tronEpro˜e mi™ro—n—lysis —nd ˆEr—y IPHÿISHVD —nd dip RHÿUHV tow—rds the ƒ‡ —nd

powder diffr—™tionF yre miner—l —ssem˜l—ges xiF ynly the m—jor vein of the fu™hel˜—™h ™o˜—lt È

from IT represent—tive s—mples —re listed in vein system shows — diverging iÿ‡ strike

„—˜le IF „he veinEtype goExiEfi ores o™™ur —s @pigF PAF „he vein dimensions r—nge from — few

lo™—l enri™hments —nd impregn—tions in — g—ngue ™m to ~T mD with me—n v—lues in the r—nge

™omposed of t—˜ul—r ˜—ryte ™ryst—ls —nd m—ssive HFISÿIFSH m @preym—nD IWWIAF „he miner—lized

sideriteF wost of the goExi —rsenide —ssem˜l—ges f—ult zonesD whi™h —re exposed in the ™ryst—lline

—re present —s ™omplex zoned rosettesD ˜otryoid—l ˜—sementD the e™hstein sediments —nd the

m—sses —nd idiomorphi™ ™ryst—lsD whi™h were overlying vower funterD —re m—inly ®lled with

su˜sequently overgrown ˜y sideriteF „he vein ores ˜—ryteD siderite —nd stronglyE—ltered w—llro™k

were su˜je™ted to sever—l st—ges of te™toni™ fr—gmentsF st is import—nt to note th—t the

movement —long the f—ult zonesD whi™h resulted o™™urren™e of goExiEfi oresD whi™h form lo™—l

in extensive fr—™turing —nd ˜re™™i—tion of the ™on™entr—tions in the veinsD is restri™ted to the

older —ssem˜l—gesF yn the ˜—sis of the miner—l ™ryst—lline ˜—sement —nd the lowermost p—rt of the

—ssem˜l—ges —nd textur—l rel—tionshipsD three e™hstein sediments @uupfers™hiefer —nd lower

sequenti—l st—ges of deposition ™—n ˜e distinE p—rt of the dolomite unitAF w—jor ™omponents of

guishedX @IA the gu st—geY @PA the m—in goExiEfi the goExiEfi ores —re skutteruditeD ni™™oliteD

st—geY —nd @QA the l—te st—ge @pigF QAF s—f¯oriteD r—mmels˜ergiteGp—r—r—mmels˜ergite

„he miner—liz—tion sequen™e initi—ted with the —nd n—tive ˜ismuthF elthough most of the veins

form—tion of qu—rtzD whi™h is — rel—tively ™ont—in n—tive ˜ismuth in ™lose —sso™i—tion with

su˜ordin—te g—ngue miner—lF u—rtz is present —s the goExi oresD the most import—nt enri™hments of

idiomorphi™ prism—ti™ ™ryst—lsD whi™h —re n—tive ˜ismuth o™™ur within — p—rti™ul—r veinD in

™ommonly en™losed in t—˜ul—r ˜—ryte sF „he the ƒi p—rt of the deposit @the ˜ismuth veinAF

˜—ryte h—s ˜een overgrown ˜y the prin™ip—l ore

miner—ls of the gu st—geD m—inly ™h—l™opyrite —nd

winer—logy of the goExiEfi ores

tenn—ntiteF gh—l™opyriteD g—len— —nd sph—lerite —re

present —s —nhedr—l in™lusions within tenn—ntiteD wost of the s—mple m—teri—l investig—ted in this

whi™h forms ˜oth m—ssive —ggreg—tesD up to study w—s o˜t—ined from museum ™olle™tionsY

QÿR ™m in sizeD —nd idiomorphi™ ™ryst—lsF —ddition—l m—teri—l w—s ™olle™ted from dumps of

„enn—ntite ™lose to f—ult zones h—s ˜een strongly the vo™h˜orn —nd ‚oÈhrig go veinsF e tot—l of TV

˜re™™i—tedF „he intensity of the ˜re™™i—tion s—mples w—s studied ˜y re¯e™tedElight mi™roE

„efvi IF hes™ription of represent—tive s—mples from the fie˜er goExiEfi depositF

ƒ—mple ƒour™eGlo™—tion yre —ssem˜l—ge

fsiEP es™h—ffen˜urg n—tur—l history museum w—u™heriteD ni™™oliteD n—tive ˜ismuth

fsiEQP es™h—ffen˜urg n—tur—l history museum go˜—ltiteD ™o˜—lti—n —rsenopyriteD skutteruditeD n—tive ˜ismuth

fsiEUW es™h—ffen˜urg n—tur—l history museum qersdorf®teD r—mmels˜ergiteD s—f¯oriteD skutterudite

fsiEIPR niversity of ƒtr—û˜urg imple™titeD loellingiteD skutteruditeD n—tive ˜ismuth

fsiEIPW niversity of ƒtr—û˜urg ƒkutteruditeD n—tive ˜ismuth

fsiEIQP˜ niversity of ƒtr—û˜urg ƒ—f¯oriteD skutteruditeD n—tive ˜ismuth

fsiEIRW niversity of ƒtr—û˜urg „enn—ntiteD ™h—l™opyriteD pyriteD sph—leriteD g—len—

fsiEISI— niversity of ƒtr—û˜urg imple™titeD s—f¯oriteD skutteruditeD n—tive ˜ismuth

fsiEPRQ niversity of ƒtr—û˜urg xi™™oliteD gersdorf®teD s—f¯oriteD r—mmels˜ergiteD loellingiteD

n—tive ˜ismuth

fsiEPSR ‚oÈhrig ™o˜—lt vein ello™l—siteD skutterudite

fsiEPTR ‚oÈhrig ™o˜—lt vein qersdorf®te

fsiERRV— fie˜erD not further spe™i®ed ƒkutteruditeD n—tive ˜ismuth

fsiERSP— niversity of u—rlsruhe „enn—ntiteD skutteruditeD m—r™—siteD pyrite

fsiERST niversity of ƒtuttg—rt go˜—ltiteD s—f¯oriteD loellingiteD skutterudite

fsiERSU niversity of u—rlsruhe x—tive ˜ismuthD ˜ismuthiniteD loellingiteD tetr—hedrite

fsiERTH niversity of u—rlsruhe ƒ—f¯oriteD loellingiteD skutterudite QVV

gyExsEfs †isx wsxi‚evse„syxD qi‚wex‰

psqF QF €—r—geneti™ sequen™e of the fie˜er goExiEfi miner—lis—tionD —s determined through textur—l o˜serv—tionsF

„he verti™—l lines indi™—te ˜re™™i—tion eventsF

n—tive ˜ismuth —re surrounded ˜y — l—yer of de™re—ses with in™re—sing dist—n™e from the f—ultsF

skutteruditeD whi™h shows idiomorphi™ termin—E ƒu˜sequent to the ˜re™™i—tion eventD skutterudite s

tionsF ƒkutterudite hosting dendriti™ n—tive pre™ipit—ted within the mi™rofr—™tures of the

˜ismuth is en™losed ˜y m—ssive ˜—ryte ss or h—s tenn—ntite ˜re™™i— @pigF R—AF „his skutterudite is

idiomorphi™—lly grown upon this ˜—ryteD whi™h ™omposed of numerous very minute @SÿPH mmA

indi™—tes th—t deposition of skutterudite ss w—s idiomorphi™ ™ryst—lsD whi™h displ—y — signi®™—nt

—pproxim—tely ™ontempor—neous with ˜—ryte ssF growth zon—tion —nd hopper ™ryst—l morphologyD

gomplex di—rsenideGsulph—rsenide rosettesD indi™—tive of r—pid depositionF ƒkutterudite s is

™omposed of r—mmels˜ergiteGp—r—r—mmels˜ergiteD —lso present —s stronglyEfr—™tured —nd ˜re™™i—ted

gersdorf®teD s—f¯orite —nd loellingiteD h—ve formed skelet—l ™ryst—lsD whi™h were overgrown —nd

su˜sequent to skutteruditeF „wo distin™t textur—l en™losed ˜y l—ter emple™tite @pigF R˜AF

types ™—n ˜e distinguishedD whi™h —reX sn ™ontr—st to skutterudite sD the l—ter skutterE

@IA r—mmels˜ergiteGp—r—r—mmels˜ergiteEri™h udite ssD whi™h m—kes up most of the m—ssive goE

—ssem˜l—ges surrounding ni™™oliteY —nd xiEfi oresD does not show eviden™e of extensive

@PA s—f¯oriteEri™h —ssem˜l—ges surrounding skutE ˜re™™i—tionF ƒkutterudite ssD whi™h w—s deposited

teruditeF xi™™oliteD whi™h is present —s —nhedr—l su˜sequent to ™o˜—ltite —nd n—tive ˜ismuth sD is

gr—insD —nd r—rely —sso™i—ted with m—ssive present —s idiomorphi™ ™u˜oEo™t—hedr—l ™ryst—lsD

m—u™herite @pigF S—AD ™onstitutes the ™ore of the HFPÿVFS mm in size @pigF R™AD —nhedr—l m—ssive

xiEri™h rosettesF xi™™olite ™ont—ins —nhedr—l —nd —ggreg—tes @pigF RdAD dendriti™ —ggreg—tes

dendriti™ in™lusions of n—tive ˜ismuthD ˜ut no @pigF ReA —nd ™omposite idiomorphi™ ™ryst—ls

in™lusions of skutteruditeD indi™—ting more or less whi™h displ—y — signi®™—nt growth zon—tion

™ontempor—neous form—tion of ni™™olite —nd @pigF RfAF x—tive ˜ismuthD up to S mm in sizeD is

skutteruditeF „he xiEri™h di—rsenideGsulph—rsenide ™ommonly found ˜oth —s l—rge dendriti™ —ggreE

rosettes —re ™h—r—™terized ˜y — ™omplex growth g—tesD whi™h —re en™losed in skutterudite @pigF RdA

zoningF xi™™olite h—s ˜een overgrown ˜y —lterE —nd emple™tite @pigF R˜AF †ery ™ommonlyD the

n—ting ˜—nds of gersdorf®te —nd r—mmels˜ergiteG dendriti™ ˜ismuth is surrounded ˜y r—di—l mi™roE

p—r—r—mmels˜ergiteD whi™h were followed ˜y l—ter fr—™turesD — texture initi—lly des™ri˜ed ˜y ‚—mdohr

idiomorphi™ s—f¯orite —nd loellingite @pigF S˜AF @IWVIAF enhedr—l gr—ins of n—tive ˜ismuth —re

„he sequen™e of gersdorf®te —nd r—mmels˜ergiteG r—rely found —s in™lusions within ™o˜—ltite —nd

p—r—r—mmels˜ergite is found to ˜e repe—ted twi™eD ™o˜—lti—n —rsenoypriteD whi™h ˜oth displ—y euheE

whi™h indi™—tes os™ill—ting pre™ipit—tion ™ondiE dr—l to su˜hedr—l gr—in sh—pesY ™o˜—ltite —nd

tionsF st is import—nt to note th—t the presen™e of ™o˜—lti—n —rsenopyrite were su˜sequently overE

˜oth r—mmels˜ergite —nd p—r—r—mmels˜ergite grown —nd en™losed ˜y m—ssive skutterudite

@pleetD IWUPA h—s ˜een ™on®rmed ˜y ˆEr—y @pigF RdAF „he l—rger dendriti™ —ggreg—tes of QVW

„F ‡ eq x i ‚ e x h t F vy‚ i x 

psqF RF €hotomi™rogr—phs in re¯e™ted light showing v—rious represent—tive textures of the fie˜er goExiEfi oresF

@—A fre™™i—ted tenn—ntite @tenA ™lose to — f—ult zone h—s ˜een in®lled ˜y skutterudite s @skdAF ƒ—mple fsiERSP—F ‡idth

of ®eldX IFIS mmF @˜A ƒkutterudite s @skdA h—s ˜een strongly ˜re™™i—tedF ƒu˜sequentlyD n—tive ˜ismuth s @˜iA h—s

pre™ipit—ted —s —nhedr—l gr—insF foth skutterudite —nd n—tive ˜ismuth h—ve ˜een overgrown ˜y prism—ti™ emple™tite

@eplAF ƒ—mple fsiEISI—F ‡idth of ®eldX IFQW mmF @™A x—tive ˜ismuth s @˜iAD present —s dendriti™ —ggreg—tesD h—s ˜een

overgrown —nd en™losed ˜y —n idiomorphi™ ™ryst—l of skutterudite ss @skdAF sn ™ontr—st to skutterudite sD skutterudite ss

does not show extensive ˜re™™i—tionF sdiomorphi™ ™ryst—ls of loellingite @loeA h—ve grown upon the ™ryst—l f—™es of

skutteruditeF ƒ—mple fsiEIPRF ‡idth of ®eldX PFTS mmF @dA ƒu˜hedr—l ™ryst—ls of ™o˜—ltite @™o˜A —nd —nhedr—l gr—ins

of n—tive ˜ismuth @˜iA —re ˜oth present —s in™lusions within m—ssive skutterudite ss @skdAF ƒ—mple fsiEQPF ‡idth of

®eldX SHH mmF @eA ƒkutterudite ss @skdAD hosted ˜y ˜—ryte @˜—AD h—s overgrown —nd en™losed dendriti™ n—tive ˜ismuth s

@˜iAF ƒ—mple fsiERRV—F ‡idth of ®eldX IFH mmF @fA ƒkutterudite ss @skdA showing ™omplex growth zoningD h—s ˜een

en™losed ˜y l—ter siderite @sidAF ƒ—mple fsiEIPWF ‡idth of ®eldX PFQS mmF QWH

gyExsEfs †isx wsxi‚evse„syxD qi‚wex‰

psqF SF €hotomi™rogr—phs in re¯e™ted light showing v—rious represent—tive textures of the fie˜er goExiEfi oresF

@—A xi™™olite @ni™A h—s ˜een overgrown ˜y m—u™herite @m—uAF ƒu˜sequentlyD mi™rofr—™tures within m—u™herite were

®lled ˜y n—tive ˜ismuth ss @˜iAF ƒ—mple fsiEPF ‡idth of ®eldX STH mmF @˜A e typi™—l ni™™oliteEri™h rosetteD showing —

™omplex os™ill—tory growth zoningF xi™™olite @ni™A h—s ˜een overgrown ˜y —ltern—ting ˜—nds of gersdorf®te @gerA —nd

r—mmels˜ergiteGp—r—r—mmels˜ergite @r—mAD whi™h were followed ˜y l—te s—f¯orite @s—fA —nd idiomorphi™ ™ryst—ls of

loellingite @loeAF ƒ—mple fsiEPRQF ‡idth of ®eldX IFUS mmF @™A het—il of — gersdorf®te ˜—nd in — goEri™h rosetteD

showing idiomorphi™ termin—tions of ˜oth s—f¯orite @s—fA —nd gersdorf®te @gerAF ƒ—mple fsiERSTF ‡idth of ®eldX

IFHU mmF @dA w—rgin—l zone of — goEri™h rosetteD whi™h en™loses — ™ore of skutteruditeF „he di—rsenide rosette is

™omposed of s—f¯orite @s—fAD whi™h h—s — highly v—ri—˜le ™ompositionF ƒ—mple fsiEIQP˜F ‡idth of ®eldX QFH mmF

@eA ƒiderite @sidA h—s ˜een p—rti—lly repl—™ed ˜y —llo™l—site @—llAF ƒ—mple fsiEPSRF ‡idth of ®eldX PFPH mmF

@fA pr—™tures in siderite @sidA h—ve ˜een in®lled ˜y n—tive ˜ismuth ss @˜iAF „he n—tive ˜ismuth en™loses —ggreg—tes of

loellingite @loeA ™ryst—lsF ƒ—mple fsiERSUF ‡idth of ®eldX IFSH mmF QWI

„F ‡ eq x i ‚ e x h t F vy‚ i x 

˜e—m size of IÿP mm —nd ™ounting times of PH s powder diffr—™tion in sever—l ni™™oliteEri™h

on „e€G€i„ —nd QH s on vipF ƒt—nd—rds —nd s—mplesD ˜ut it is very dif®™ult to distinguish

r—di—tions used were —s followsX ƒe @v—AD „e @v—AD ˜etween them ˜y re¯e™tedElight mi™ros™opy —nd

gd @v—AD eg @v—AD fi @w—AD eu @w—AD gu @u—AD ele™tronEpro˜e mi™ro—n—lysisF „hereforeD the term

go @u—A —nd xi @u—AD q—es @esEv—AD peƒ r—mmels˜ergiteGp—r—r—mmels˜ergite is used for @peE P

simpli™ityD referring to ˜oth miner—lsF „he goEri™h u—D ƒEu—AD nƒ @nEu—AD ƒ˜ ƒ @ƒ˜Ev—AD €˜ƒ P Q

rosettesD whi™h most ™ommonly en™lose — ™ore of @€˜Ew—AD rgƒ @rgEw—AD ƒny @ƒnEv—A—nd P

skutteruditeD —re found to ˜e ™omposed of wn„iy @wnEu—AF nder the ™urrent —n—lyti™—l Q

s—f¯orite —nd gersdorf®teF foth s—f¯orite —nd ™onditionsD the dete™tion limit for these elements

gersdorf®te show idiomorphi™ termin—tions is in the r—nge of HFI wtF7Y the —n—lyti™—l

@pigF S™AD indi™—ting rel—tively slow deposition of pre™ision is ~I7 for —ll m—jor elementsF „he

˜oth miner—ls within open fr—™ture zonesF „he tot—l num˜er of —n—lyses performed for e—™h

m—rgin—l zones of the goEri™h rosettes —re miner—l or miner—l group is given in ˜r—™kets in

™h—r—™terized ˜y sever—l individu—l growth zones the following p—r—gr—phsF

of s—f¯orite @pigF SdAF foth textur—l types of

di—rsenideGsulph—rsenide rosettes —re overgrown

xi —rsenides

˜y m—ssive sideriteD whi™h h—s ®lled most of the

rem—ining open sp—™e within the goExiEfi veinsF „he ™ompositions of the two xi —rsenide miner—lsD

€ortions of the m—ssive siderite show extensive ni™™olite @n a PPA —nd m—u™herite @n a PRAD —re

˜re™™i—tion —nd in®lling ˜y the l—te st—ge ™h—r—™terized ˜y rel—tively limited v—ri—˜ilityF

—ssem˜l—gesF sn pl—™esD the fr—™tured siderite h—s xi™™olite —nd m—u™herite displ—y go in™orpor—E

˜een repl—™ed ˜y —llo™l—siteD whi™h is present —s tion in the r—nge HFPVÿHFTP wtF7 —nd

—™™umul—tions of rhom˜Esh—ped idiomorphi™ HFTSÿIFIW wtF7D respe™tivelyD where—s the

™ryst—ls @pigF SeAF ello™l—site is ™losely —sso™i—ted ™on™entr—tion of pe is gener—lly `HFI wtF7

with — l—te gener—tion of skutteruditeD whi™h forms @„—˜le PAF winor su˜stitution of es ˜y ƒ is only

isol—ted ™u˜eEsh—ped ™ryst—ls en™losing idioE dete™t—˜le in m—u™herite @HFPHÿHFPS wtF7AD

morphi™ —llo™l—siteF vo™—l enri™hments of n—tive where—s the ƒ ™on™entr—tions in ni™™olite —re

˜ismuth —re rel—ted to extensively ˜re™™i—ted ˜elow the dete™tion limitF

sideriteF pr—™tures —nd mi™roEf—ults in siderite

h—ve ˜een in®lled ˜y m—ssive n—tive ˜ismuth ssD

ƒkutterudite

whi™h hosts in™lusions of rhom˜Esh—ped idioE

morphi™ ™ryst—ls of loellingite —nd —nhedr—l gr—ins ƒkutterudite @n a ISWA displ—ys — ˜ro—d r—nge of

of ˜ismuthinite @pigF SfAF sn™lusions of loellingite ™omposition—l v—ri—tionF „he most import—nt

—re —lso present within the sideriteD indi™—ting fe—ture is — su˜st—nti—l su˜stitution of go ˜y xi

loellingite form—tion during pre™ipit—tion —nd —nd peD whi™h is in the r—nge HFIIÿIRFQW wtF7

su˜sequent ˜re™™i—tion of the sideriteF —nd HFRTÿUFWU wtF7D respe™tively @„—˜le QAF „he

imple™tite is —pp—rently — l—te miner—l in the skutterudite ™ompositions dete™ted in the fie˜er

sequen™e of depositionD ˜e™—use —ggreg—tes goExiEfi ores in™lude ˜oth skutterudite —nd xiE

™omposed of —™i™ul—r to prism—ti™ ™ryst—ls of skutteruditeD whi™h ™on®rms the results of ˆEr—y

emple™tite —re ™ommonly found in vugs within powder diffr—™tion —n—lysesF ‚e®nement of the

sideriteF w—ssive emple™tite hosts in™lusions of ˆ‚h d—t— indi™—tes th—t two types of skutterudite

™orroded sideriteD n—tive ˜ismuth —nd ˜re™™i—ted —re presentD whi™h h—ve ™ell p—r—meters of

Ê Ê skutterudite @pigF R˜AF „he m—ssive —nhedr—l VFIUPÿVFPPS e —nd VFPSWÿVFPTS eF„hese

Ê n—tive ˜ismuth ss is r—rely ™ross™ut ˜y l—te ™onform to the v—lues of VFPHR —nd VFQHQ e

mi™rofr—™turesD whi™h h—ve ˜een p—rti—lly ®lled listed for skutterudite —nd xiEskutterudite in the

˜y tetr—hedriteF tg€hƒ powder diffr—™tion d—t— ®leF yn the ˜—sis

of their ™ompositions in peEgoExi sp—™eD two

distin™t types of skutterudite ™—n ˜e distinguishedF

winer—l ™hemistry

wost of the —n—lyti™—l d—t— f—ll within — l—rge ®eld

„he ™hemi™—l ™omposition of the miner—l ph—ses ™orresponding to the known ®eld of skutterudite

w—s determined ˜y w—velengthEdispersive ele™E solidEsolution @‚ose˜oomD IWTPY ulemmD IWTS—Y

tronEpro˜e mi™ro—n—lysis using the gewige ‚osnerD IWUHAD where—s rel—tively few —n—lyses

ƒˆESH instrument in ‡urz˜urgF yper—ting ™ondiE de®ne — sep—r—te groupD ™h—r—™terized ˜y elev—ted È

tions were IS k† —t — ˜e—m ™urrent of IS neD — pe —nd xi ™on™entr—tions @pigF T—AF elthough QWP

gyExsEfs †isx wsxi‚evse„syxD qi‚wex‰

„efvi PF ‚epresent—tive ele™tron mi™ropro˜e —n—lyses of ni™™olite —nd m—u™heriteF

ƒ—mple fsiEP V fsiEP IU fsiEP RI fsiEP PP fsiEP PU fsiEP SH

ni™ ni™ ni™ m—u m—u m—u

‡tF7

go HFTP HFQR HFPV HFVH IFIW HFTS

xi RPFPT RQFQI RQFUU SHFTI SHFTI SIFPS

es STFSH SSFVW SSFWT RWFIR RVFWP RVFRQ

ƒ `HFI `HFI `HFI HFPH HFPQ HFPS

ƒe HFPT HFPW HFQR HFQS `HFI HFPV

„ot—l WWFTR WWFVQ IHHFQS IHIFIH IHHFWS IHHFVT

pormul—e

go HFHI HFHI HFHI HFIU HFPS HFIR

xi HFWV HFWW HFWW IHFVP IHFUR IHFVT

es IFHQ IFHH IFHH VFPQ VFIQ VFHR

ƒ H H H HFHV HFHW HFIH

snterestinglyD the peE —nd xiEri™h skutterudites most of the ™ryst—ls —nd —ggreg—tes of skutterudite

de®ning — sep—r—te group in peEgoExi sp—™e displ—y — signi®™—nt growth zon—tionD it is not

displ—y the lowest ƒ ™on™entr—tionsF „he possi˜le to ™orrel—te the o˜served ™omposition—l

weX@esCƒA r—tios of the skutterudites r—nge trends with — distin™t zon—tion p—tternF „he

˜etween IXPFWH —nd IXQFHQ —nd —re very ™lose to ™omposition—l v—ri—tions ˜etween different —ggreE

the ide—l stoi™hiometryF st is noted th—t the g—tes —nd gr—ins —re simil—r to those ˜etween

skutterudite ™ompositions displ—ying elev—ted individu—l growth zonesF sn —ddition to the

levels of ƒ su˜stitution tend to ˜e ™loser to the v—ri—tion of skutterudite in peEgoExi sp—™eD —

ide—l weX@esCƒA v—lueF „he extent of devi—tion of signi®™—nt su˜stitution of es ˜y ƒ in the r—nge

skutterudite from ide—l stoi™hiometry h—s ˜een the HFISÿSFRQ wtF7D ™orresponding to HFHIÿHFRR

su˜je™t of mu™h dis™ussionF ƒyntheti™ skutterudite —toms per formul— unit @—FpFfFuFAD h—s ˜een

™orresponding to the go endEmem˜er w—s found dete™ted @pigF U—AF „he es ™on™entr—tions —re

to ˜e —lmost stoi™hiometri™ with weXes r—tios in neg—tively ™orrel—ted with the ƒ ™on™entr—tions

P

the r—nge IXPFWS to IXPFWU @‚ose˜oomD IWTPAF over the entire ™omposition—l r—nge @‚ a HFVTAF

psqF TF gomposition—l represent—tions @molF7A of skutterudites —nd di—rsenidesF foth di—gr—ms show — summ—ry of

Egoes Exies F „he sh—ded —re— indi™—tes the d—t— from —ll s—mples —n—lysedF @—A ƒkutterudites in the system pees Q Q Q

m—ximum ®eld of solidEsolution —t VHHVg @‚ose˜oomD IWTPAD whi™h ™onforms to the known r—nge of n—tur—l

Egoes Exies F „he sh—ded —re— shows skutterudite ™ompositions @‚osnerD IWUHAF @˜A hi—rsenides in the system pees P P P

the ®eld of n—tur—l di—rsenides @‚ose˜oomD IWTQAF QWQ

„F ‡ eq x i ‚ e x h t F vy‚ i x 

psqF UF †—ri—tion of es —nd ƒ —FpFfFuF in @—A skutteruditesD —nd @˜A di—rsenides from the fie˜er depositF

@„—˜le RD „—˜le SAF sn ™ontr—stD eviden™e of solidE ƒystem—ti™ mi™ropro˜e studies of n—tur—l skutterE

solution ˜etween s—f¯orite —nd r—mmels˜ergiteG udite ˜y ulemm @IWTS—A found — ™omposition—l

p—r—r—mmels˜ergite tends to ˜e more restri™tedF v—ri—tion ˜etween IXIFW —nd IXQFQD whi™h ™ould

„he in™orpor—tion of go into r—mmels˜ergiteG not ˜e ™on®rmed in su˜sequent studies @eFgF

p—r—r—mmels˜ergite is in the r—nge ‚osnerD IWUHY €etruk et —lFD IWUIY sxer et —lFD

HFTRÿIQFUV wtF7 @™orresponding to IWUWY —krzewski et —lFD IWVHY yen et —lFD IWVRAF

HFHPÿHFRT —FpFfFuFAD where—s xi su˜stitution in „he nonEstoi™hiometri™ skutterudite —n—lyses

s—f¯orite is limited to — m—ximum of WFHW wtF7 reported in the liter—ture m—y rel—te to very ®neE

@™orresponding to HFPQ —FpFfFuFAF wost of the gr—ined intergrowths with different di—rsenides or

—n—lyti™—l d—t— plot within the known ®eld of the presen™e of signi®™—nt —mounts of ƒ

di—rsenide ™ompositions in peEgoExi sp—™e su˜stituting for esD ™omp—r—˜le to skutterudite

@‚ose˜oomD IWTQY ‚—d™liffe —nd ferryD IWTVAD of the fie˜er depositF

where—s — limited num˜er of peE —nd xiEri™h

s—f¯orites h—ve ™ompositions outside this est—˜E hi—rsenides

lished ®eld @pigF T˜AF „he di—rsenides displ—y —

su˜stitution of es ˜y ƒ in the r—nge HFIIÿ „he different di—rsenide miner—ls @n a IQQAD

SFIQ wtF7D ™orresponding to HFHIÿHFQI —FpFfFuF ™omprising s—f¯oriteD loellingite —nd r—mmels˜erE

@pigF U˜AY the es ™on™entr—tions —re neg—tively giteGp—r—r—mmels˜ergiteD —re ™h—r—™terized ˜y

P

™orrel—ted with the ƒ ™on™entr—tions @‚ extensive ™omposition—l v—ri—˜ility in peEgoExi a HFWPAF

sp—™e @pigF T˜AF wost of the —n—lyti™—l d—t— plot st is noted th—t the rel—tive proportion of ƒ

—long the join ™onne™ting s—f¯orite —nd loellingite su˜stituting for esD expressed —s ƒG@esCƒA is very QWR

gyExsEfs †isx wsxi‚evse„syxD qi‚wex‰ QF ‚epresent—tive ele™tron mi™ropro˜e —n—lyses of skutteruditeF efvi „

‡tF7 gupegoxi `HFIesƒ IFUTƒe IUFVV„ot—l IFSR `HFI UVFSSpormul—e @™—l™ul—ted IPFQI PFHU to HFIS IHHFIV Ipe met—lA HFQHgo TFVU UTFUVxi HFQQes WWFUV UFRI UFWU IFPRƒ HFSI HFHW UVFIR HFVR SFTQ `HFI HFHU IHHFUP PFWH WFQS HFRT HFWH HFQR HFIH USFQI HFHI IIFHQ HFSU `HFI WVFVI HFQP PFVI TFPV HFSR PFPW UUFTP HFQU HFQW IRFQW HFII IHHFIH HFQR HFPI HFPT IPFVS PFVP SFQS USFVT HFVV HFQW HFHP PFTV WWFSR HFHV HFRS `HFI HFSQ IUFHV UPFVI PFVQ QFRI PFHP WWFUV HFSU HFHQ IFUP HFPH HFQH HFPI IUFIH HFTV UPFTS PFVU RFPS RFSP WVFWR HFPR HFPT HFII HFHV HFTH IWFHS HFIW UPFPW HFIQ IHHFPT PFUW IFWQ RFRH HFPP HFIT IFIQ HFIU PHFTW HFUT `HFI UIFUV HFHV WWFUV PFSS IFPW SFRQ HFPR HFPH HFPS HFQU HFUV HFHH PFTI SFPV HFRW HFHW HFQU HFVS HFHS PFSQ HFHT HFRR HFWQ HFHI PFSQ HFRQ ƒ—mple fsiEQP IR fsiEUW PU fsiEIPR QI fsiEIPW PV fsiEIQP˜ QW fsiEISI— PU fsiEPSR Q fsiERRV— R fsiERSP— SS fsiERST SH QWS „F ‡ eq x i ‚ e x h t F vy‚ i x  RF ‚epresent—tive ele™tron mi™ropro˜e —n—lyses of s—f¯oriteF efvi „

‡tF7 gupegoxies HFIPƒ PFRUƒe PQFRI„ot—l QFRT TTFST HFIWpormul—e @™—l™ul—ted IWFUS PFRT to QFHP Ipe WWFPT met—lA HFPPgo TFIV TVFWWxi HFRVes IUFQH IHFWW IFQT WWFQTƒ HFRQ HFHW `HFI UIFQT HFUW HFPS HFIP PRFHU IHHFSP RFWT IFUT HFIV HFPI HFHW TUFVI HFIW `HFI HFTW IHHFHV ISFUT HFRW HFPP WFHI IFVW PFTH TVFSS HFQW HFQW HFHW IHHFPP QFUV HFSW PSFSW `HFI HFHH HFWS IFWI UHFWS PFQR IHHFTT HFPW HFIV HFHI PTFUT PFQR HFVI `HFI HFHH IFTU UHFPR IFVH IHHFVR HFQS HFRV HFQP HFIT ISFHQ HFTW HFSQ `HFI HFIQ IPFWI UHFQU WWFPS IFVQ IFIU HFQI IRFRS HFHQ HFIS `HFI HFVV `HFI IHHFQV TRFUW HFHV TFUP IFWP HFRQ IPFWW HFSI HFHT HFHP IHHFPS WFHW HFWI `HFI TVFTT HFHP WFQQ IFVW SFIQ HFPH HFRU HFHU TFTV HFSP HFHH IFWQ PFRT HFIQ HFPQ HFHQ HFRU HFQH IFTT HFQQ HFQI HFRR HFPQ IFVP HFIS ƒ—mple fsiEUW IR fsiEUW QT fsiEIQP˜ I fsiEIQP˜ IU fsiEISI— PP fsiEPRQ IH fsiEPRQ IQ fsiERST QI fsiERTH QS fsiERTH QT QWT

gyExsEfs †isx wsxi‚evse„syxD qi‚wex‰ SF ‚epresent—tive ele™tron mi™ropro˜e —n—lyses of r—mmels˜ergite —nd loellingiteF efvi „ r—m r—m r—m r—m r—m loe loe loe loe loe

‡tF7 gupegoxies `HFIƒ HFIRƒe RFPR PRFVS„ot—l `HFI TTFTPpormul—e @™—l™ul—ted HFIW to QFQI IHFVP Ipe WWFRS met—lA HFPW IWFITgo TRFSI `HFIxies `HFI IQFUV RFRV WWFRHƒ ISFVT HFPR HFHI UIFPS HFIR `HFI HFVS IHIFTW `HFI IFUV HFTR PVFQW HFPW HFSI HFHI UIFUP HFPI HFQT `HFI IHIFIV HFTQ `HFI PIFUS IFTU TFTS HFII UIFQW HFQP HFHH HFPU IHHFQT HFRT HFIT HFSR `HFI PVFQR `HFI IFVW TUFWU HFIT HFRI HFHH WWFWW HFHP HFHP `HFI PRFVQ HFWV PFSQ UIFSI IFWQ HFQU QFIP IHHFQP HFRH HFHH HFHI HFPQ `HFI PQFHH HFUU UIFUW QFRQ IFWU HFTH WWFSP HFUI HFQU IFHH HFHI HFHH `HFI PSFRQ UIFWI HFHH `HFI WWFTW IFUV IFQS HFQV HFQP HFWH HFIW PIFQH HFHI `HFI UIFSS HFHW WWFVW HFRI IFWP TFHP HFVV HFIP HFVS HFHR HFHP HFIP IFWW HFPH HFRI HFWS HFHP HFHS HFHH IFWT HFUV HFHT HFPI HFHI IFWS HFHI ƒ—mple fsiEUW T fsiEUW IH fsiEPRQ PH fsiEPRQ PS fsiEPRQ PT fsiEIPR QH fsiEPRQ Q fsiEPRQ S fsiERSU PU fsiERTH IR QWU

„F ‡ eq x i ‚ e x h t F vy‚ i x 

indi™—ting th—t ˜oth pe —nd xi su˜stitute for go in simil—r for ˜oth the di—rsenides @HFITA —nd the

— ®xed r—tioF e simil—r solidEsolution trend s—f¯orites @HFISAF wost of the s—f¯orite m—king up

˜etween ™o˜—ltite —nd goE —nd peEri™h gersdorf®te the m—rgin—l zones of goEri™h di—rsenideGsulph—rE

h—s ˜een reported from the „un—˜erg sk—rn senide rosettes displ—ys — signi®™—nt ™omposiE

depositD ƒweden @ho˜˜e —nd yenD IWWRAF „he tion—l zon—tionD whi™h is ™h—r—™terized ˜y

sulph—rsenides from —ll other s—mples investig—ted —ltern—ting peEri™h —nd peEpoor ˜—nds @pigF WAF

—re lo™—ted on — trend ™onne™ting ™o˜—ltite with „he weX@esCƒA r—tios of the di—rsenides r—nge

gersdorf®te @pigF V˜AY the dete™ted ™ompositions ˜etween IXIFWI —nd IXPFHPD whi™h is very ™lose to

r—nge ˜etween go the stoi™hiometri™ v—lueF xi pe es ƒ —nd HFWP HFHI HFHU IFHV HFWH

go xi pe es ƒ @„—˜le UAF „his HFIH HFVV HFHP IFIR HFVT

™omposition—l trend in™ludes ™o˜—ltiteD —llo™l—site

ƒulph—rsenides

—nd gersdorf®teD —s shown ˜y ˆEr—y diffr—™tion

„he different sulph—rsenide miner—ls @n a IIUA —n—lysesF „he different sulph—rsenide miner—ls

present in the goExiEfi ores ™—n ˜e grouped into show highly v—ri—˜le esGƒ r—tios ˜etween

three different popul—tionsD ˜—sed on their HFWSXIFHH —nd IFPWXHFUQD whi™h is ™onsistent with

™omposition—l trends in peEgoExi sp—™eF „wo of the experiment—llyEdetermined ™omposition—l

these ™omposition—l popul—tionsD whi™h ™orreE r—nge @ulemmD IWTS˜Y f—ylissD IWTWAF

spond to ™o˜—lti—n —rsenopyrite —nd ™o˜—ltiteD —re

found ex™lusively —s in™lusions in m—ssive

„enn—ntite —nd tetr—hedrite

skutterudite in s—mple fsiEQP @„—˜le TD

pigF V—AF „he textur—l —nd ™omposition—l ™l—ssi®E „enn—ntite @n a QQAD whi™h is the domin—nt f—hlore

™—tion of these two distin™t sulph—rsenide ph—ses miner—l in the fie˜er goExiEfi oresD h—s —

h—s ˜een ™on®rmed ˜y ˆEr—y powder diffr—™tion ™omposition ™lose to the es endEmem˜erD with

—n—lysesF go˜—lti—n —rsenopyrite displ—ys — esG@esCƒ˜A r—tios in the r—nge HFUUÿHFWV

rel—tively limited go su˜stitution @pigF V—AD @„—˜le VD pigF IHAF „he nG@nCpeA r—tios —re in

whi™h is in the r—nge SFIWÿIIFPQ wtF7D ™orreE the r—nge HFIWÿHFQVD —nd —re only very we—kly

P

sponding to HFISÿHFQP —FpFfFuFY the —mount of xi ™orrel—ted with the esG@esCƒ˜A r—tios @‚ a HFPQAF

in™orpor—tion is insigni®™—nt —nd r—nges ˜etween „he eg ™on™entr—tions —re rel—tively lowD in the

HFRT —nd IFSP wtF7F go˜—ltiteD present in the s—me r—nge HFITÿHFQR wtF7D where—s most —n—lyti™—l

s—mpleD is ™h—r—™terized ˜y extended su˜stitution d—t— displ—y — signi®™—nt su˜stitution of es ˜y fi

˜y ˜oth pe —nd xi @pigF V—A in the r—nge in the r—nge HFPRÿPFSS wtF7F „he tenn—ntite

PFIWÿVFHR wtF7 —nd IFHUÿIPFQP wtF7D respe™E ™ompositions ™orrespond well with —n—lyti™—l

tively @™orresponding to HFHTÿHFPR —nd d—t— reported for tenn—ntite from str—t—˜ound

HFHQÿHFQS —FpFfFuFAF „he xi ™on™entr—tions —re miner—liz—tions in different types of e™hstein

positively ™orrel—ted with the pe ™on™entr—tions sediments in the ƒpess—rt @ƒ™hmittD IWWQ—AF

P

over the entire ™omposition—l r—nge @‚ „etr—hedrite @n a TAD present —s in®lling of l—te a HFWUAD

psqF VF gomposition—l represent—tions @molF7A of sulph—rsenides in the system peesƒEgoesƒExiesƒF @—A go˜—ltite

—nd ™o˜—lti—n —rsenopyriteD s—mple fsiEQPF @˜A go˜—ltiteD —llo™l—site —nd gersdorf®teD s—mples fsiEUWD fsiEPRQD

fsiEPSRD fsiEPTR —nd fsiERSTF „he sh—ded —re— indi™—tes the m—ximum ®eld of solidEsolution —t TSHVg —fter

ulemm @IWTSAF QWV

gyExsEfs †isx wsxi‚evse„syxD qi‚wex‰ TF ‚epresent—tive ele™tron mi™ropro˜e —n—lyses of ™o˜—lti—n —rsenopyrite —nd ™o˜—ltiteF efvi „ —sp —sp —sp —sp —sp ™o˜ ™o˜ ™o˜ ™o˜ ™o˜

‡tF7 gupegoxies `HFIƒ PPFRWƒe IHFVU„ot—l HFWH `HFI RWFUR PIFRIpormul—e ITFQI @™—l™ul—ted IIFPQ to IHHFSV Ipe met—lA HFPUgo HFUH RWFURxi PTFPT HFIR ITFVV IHHFIUes TFHQƒ HFPI HFTU RWFQQ HFQI IFSP PUFVT `HFI IHHFQU ITFVS HFHQ IFIH SFIW HFPR HFTS RVFPU HFVR PTFRI HFQP HFRT WWFRH `HFI IUFRR HFHP IFIQ TFIP RUFVP HFIV HFUV HFWH WWFIT PFUS HFIU HFTS IUFWR `HFI HFHR QHFTS IFHW RRFSW IHHFVI HFPP HFVR HFVU IWFVI RFWH HFIS PFVS `HFI HFHI PRFUS RSFIP IFHV WWFWR HFIT HFVH IWFPH HFWI PFIW HFIV SFUP `HFI QQFQI HFHP RRFRQ IHHFWS IFHW IWFUR HFPS HFHV HFWS TFQU HFVR IFHU `HFI PHFPP IHHFTP RSFWP HFHV HFWT IVFUV HFPI HFIR IFHH IHHFUQ IRFWQ VFHR HFTW WFIT `HFI RTFTH HFIT HFWW IVFTW HFIU HFHT HFWW IPFQP HFWI HFHQ HFWS HFIS HFIW HFWW HFST HFPS IFHH HFPR HFWS HFRP HFQS IFHP HFWT ƒ—mple fsiEQP V fsiEQP W fsiEQP PH fsiEQP PW fsiEQP RW fsiEQP I fsiEQP R fsiEQP IS fsiEQP TP fsiEQP TS QWW

„F ‡ eq x i ‚ e x h t F vy‚ i x 

psqF WF ƒ™hem—ti™ se™tion through — ™omplex zoned goExi di—rsenide rosetteD showing the ™omposition—l v—ri—tion

—long the tr—verseF ƒ—mple fsiEIQP˜F

fi miner—ls mi™rofr—™turesD is ™h—r—™terized ˜y rel—tively low

„he ™omposition of n—tive ˜ismuth @n a IHA of the es ™on™entr—tions in the r—nge HFWWÿPFPU wtF7

different textur—l types @—nhedr—l gr—insD dendriti™ —nd the —˜sen™e of eg @„—˜le VAF „he nG@nCpeA

—ggreg—tesD m—ssive enri™hmentsA ™onforms to the r—tios v—ry ˜etween HFTS —nd HFWT @pigF IHAF

pure elementD with only very minor ™on™entr—E

tions of gu dete™t—˜leF entimonyD whi™h is —

™ommon su˜stituent in n—tive ˜ismuthD w—s not

dete™t—˜le ˜y the ele™tron mi™ropro˜e @„—˜le WAF

imple™tite @n a ISA —nd ˜ismuthinite @n a SA h—ve

™ompositions ™lose to stoi™hiometryY su˜stitution

of fi ˜y ƒ˜ @HFIVÿHFST wtF7A in emple™tite

—ppe—rs to ˜e insigni®™—ntF

his™ussion —nd ™on™lusions

„emper—tures of ore form—tion

gomp—rison of the sulphideE—rsenide —ssem˜l—ges

with —v—il—˜le experiment—l d—t— on ph—se

rel—tions en—˜le ™onstr—ints to ˜e pl—™ed on the

form—tion ™onditions —nd the geneti™ evolution of psqF IHF gomposition—l represent—tions of tenn—ntite —nd

the fie˜er oresF ixperiment—l studies h—ve tetr—hedriteD expressed —s — plot of esG@esCƒ˜A vsF nG

demonstr—ted th—t dendriti™ fiD textur—lly ™omp—rE @nCpeAF RHH

gyExsEfs †isx wsxi‚evse„syxD qi‚wex‰ UF ‚epresent—tive ele™tron mi™ropro˜e —n—lyses of ™o˜—ltiteD —llo™l—site —nd gersdorf®teF efvi „ ™o˜ ™o˜ —ll —ll ger ger ger ger ger ger

‡tF7 gupegoxies `HFIƒ PFRQƒe QIFWW„ot—l HFIP RUFVH HFIUpormul—e IUFHR @™—l™ul—ted QHFSV QFUQ to Ipe WWFSS met—lA HFIUgo IFIT RTFRP `HFIxi IVFSPes IVFQW IHHFVH IFUIƒ HFPP HFHU ISFTU RSFUT HFWP `HFI IVFVV HFHI IHHFSV PTFTQ IFHV PFWV HFIU HFII RTFPI HFWH SFTS HFVS IHHFHW `HFI IVFRR HFHQ QFTR IFHP HFSQ RWFST HFIV HFHS PWFVR HFWS WWFUS HFSI ISFWR `HFI IRFSW HFRR `HFI IFHH RVFUP PHFHP IHHFHQ HFPR HFHW HFWT ITFRW HFUS `HFI IQFPH HFIT RWFPR IFHP IHHFRQ HFIQ PIFQT HFPI HFHP ITFQI HFWS HFIH `HFI TFSU HFVV IHHFRR SHFPH PTFVH IFIR HFTI ISFWU HFIW HFHH HFVT PIFHV HFRP `HFI IHHFQU RVFSW HFSV IIFSW IFIH IFWI ITFWI HFPW HFHH HFVU IHFHW WWFWP HFQV `HFI SQFVW PIFTR HFTP IFII IQFHU IFHR HFPW HFHP HFVT HFIW HFUW IFIT HFIW HFHT HFVT HFTI HFQQ IFIH HFHQ HFVW HFQI HFTT IFPW HFUQ ƒ—mple fsiERST V fsiERST QU fsiEPSR IU fsiEPSR QH fsiEUW I fsiEPRQ QI fsiEPRQ QT fsiEPTR S fsiEPTR IS fsiEPTR IT RHI „F ‡ eq x i ‚ e x h t F vy‚ i x  VF ‚epresent—tive ele™tron mi™ropro˜e —n—lyses of tenn—ntite —nd tetr—hedriteF efvi „ ten ten ten ten ten ten ten ten tet tet

‡tF7 guegpenrg RIFVRes HFPIƒ˜ RFWTfi IFWS RQFIIƒ HFTSƒe `HFI ISFUT„ot—l TFQV SFTV RQFHI IFSR HFRQ `HFIpormul—e PUFTU @™—l™ul—ted PHFIV to `HFI ITgu WWFVS ™—tionsA HFPQeg HFUQ SFUI RPFUHpe IFTP HFPR PVFHIn IWFPS HFPU WWFRW `HFIes IHFHR HFITƒ˜ RIFQH HFHQ IFIQ SFSWfi IFSW HFPR PUFWP IFQS IVFIWƒ HFIS WWFSI HFRT IHFHR HFIQ QFPI HFQR RPFPU HFHH HFVH QFTU RFTS `HFI PVFHW IRFVS HFHQ PFSS IFSI IHHFIR IHFHT HFIT IQFIT HFQS `HFI QFWW HFPI RPFHI HFHQ HFHW UFIT SFPU PUFHQ ITFTR WVFTV HFHP HFTR PFII IFSP IHFHP IPFWQ HFIU HFQU `HFI RIFUW QFVP HFQH PUFTQ HFHP HFIR ISFVV RFHH RFWT WWFVQ IHFHQ HFHP IFRP IPFWR PFIU IFRW HFIS HFQT QWFSV HFII QFTP HFPR PUFIW ITFWQ WWFRP HFHS HFRS RFPI RFQQ IHFHU IQFHU HFHH PFSS QFIS IFPW `HFI QWFRP HFTH `HFI `HFI PUFSR QFHT WVFVV HFWW HFHQ HFWI IHFII RFPS IQFHI HFWU HFHS HFTS SFVH IFRQ `HFI HFRW `HFI `HFI PSFHP IHHFIU QFQT PFPU IHFHI PUFTQ IQFHR HFHR HFSH IFWS HFIH HFIV RFIW IFQT `HFI HFSI PSFHP WVFVS `HFI QFPR IHFPQ PSFST IPFWU HFHQ HFSQ HFIW HFQP IFIV HFUQ HFIP IHFQI IQFHV QFRR HFHH HFSQ HFHS HFPV IFRT IPFVP HFPP HFHH QFUQ HFHI HFSV IFHU IPFWU HFSH QFRW HFHQ ƒ—mple fsiEIRW S fsiEIRW IH fsiEIRW IT fsiEIRW PQ fsiERSP— IH fsiERSP— IQ fsiERSP— IR fsiERSP— RS fsiERSU Q fsiERSU S RHP

gyExsEfs †isx wsxi‚evse„syxD qi‚wex‰

„efvi WF ‚epresent—tive ele™tron mi™ropro˜e —n—lyses of emple™tite —nd n—tive ˜ismuthF

ƒ—mple fsiEIPR S fsiEISI— IH fsiEIPR V fsiERRV— IS fsiEIPW IR fsiEIPW QR

epl epl ˜i ˜i ˜i ˜i

‡tF7

gu IWFRV IWFPI HFIR `HFI HFIQ `HFI

ƒ˜ HFIV HFST `HFI `HFI `HFI `HFI

fi TIFIP THFPV IHHFRT IHHFPW WWFPV WWFIW

ƒ IWFSR IWFQS `HFI `HFI `HFI `HFI

pormul—e

gu IFHP IFHI HFHI HFHH HFHI HFHH

ƒ˜ HFHH HFHP HFHH HFHH HFHH HFHH

fi HFWU HFWU HFWW IFHH HFWW IFHH

ƒ PFHQ PFHP HFHH HFHH HFHH HFHH

fehr et —lFD IWVUY vuders —nd woÈllerD IWWPY fehr —˜le to n—tur—l —ssem˜l—gesD ™ommonly pre™ipiE È

et —lFD IWWQY wu™hez et —lFD IWWRY ulingD IWWUA t—tes from hydrotherm—l solutions —t temper—tures

h—ve demonstr—ted th—t most of the postE†—ris™—n ˜elow the melting pointF e˜ove PUIVgD n—tive

veinEtype miner—liz—tions @eFgF €˜EnE¯uoriteE ˜ismuth is formed —s liquid dropletsD whi™h ret—in

˜—ryte veins widespre—d in gentr—l iuropeA h—ve this morphology when solidi®ed @qodovikov —nd

formed in — n—rrow temper—ture interv—l ˜etween uoloninD IWTTAF „he r—di—l fr—™tures surrounding

IHH —nd PHHVgY only — few d—t— show slightly most of the dendriti™ fi —ggreg—tes in the fie˜er

higher temper—turesD up to QHHVgF s—mples result from exp—nsion of the fi upon

™oolingF e signi®™—nt ™h—nge of the line—r

exp—nsion ™oef®™ient of pure fi met—l o™™urs —t

we™h—nisms of ore deposition

~USVg @qodovikov —nd uoloninD IWTTAD whi™h

wost of the ™on™eptu—l models developed for the provides — minimum temper—ture estim—te for the

postE†—ris™—n veinEtype ˜—ryteE€˜En miner—liz—E fie˜er goExiEfi ore —ssem˜l—gesF sn —dditionD

tion in gentr—l iurope invoke deposition of ˜—ryte form—tion temper—tures ˜elow QHHVg —re indiE

—s — ™onsequen™e of mixing ˜etween deepE ™—ted ˜y the presen™e of emple™tite —s the m—jor

sour™ed met—lE˜e—ring ˜—sement ˜rines —nd fi sulphide miner—l —sso™i—ted with n—tive

™ooler sulph—teEri™h form—tion w—tersF „he ˜ismuthF ixperiment—l studies of the guEpeEfiEƒ

sulph—teEri™h form—tion w—ters were pro˜—˜ly system show th—t emple™tite is st—˜le —t

derived from €ermi—n or wesozoi™ ™—r˜on—te temper—tures ˜elow QPHVgD where inversion to

ro™ksD whi™h ™ont—in —˜und—nt inter™—l—tions of the highEtemper—ture ph—se ™upro˜ismuthite

—nhydrite @eFgF fehr et —lFD IWVUY vuders et —lFD o™™urs @ƒug—ki et —lFD IWVIY ‡—ngD IWWRAF †ery È

IWWQY heng —nd roefsD IWWQAF ‚e™ent studies low ƒ ™on™entr—tions dete™ted in ni™™olite

h—ve shown th—t the pre™ipit—tion of sulphide @`HFI wtF7A —nd m—u™herite @HFP wtF7A from the

miner—ls in these vein systems is pro˜—˜ly rel—ted fie˜er goExiEfi ores —lso indi™—te temper—tures

to thermo™hemi™—l sulph—te redu™tion pro™esses well ˜elow QHHVgF et QHHVgD ni™™olite ™—n

during inter—™tion of the hydrotherm—l ¯uids with —™™ommod—te —s mu™h —s SFH wtF7 xiƒD

org—ni™ m—tter in the w—llro™ks @to™humD PHHHAF where—s the m—ximum sulphur ™ontent of

„he distin™t sp—ti—l —sso™i—tion of the goExiEfi m—u™herite is only PFH wtF7 —t UHHVgF „he

enri™hments in the fie˜er veins with the solidEsolution rel—tionships of ni™™olite —nd

sediment—ry ro™ks of the uupfers™hiefer @˜oth m—u™herite in the xiEesEƒ system show — strong

verti™—lly —nd l—ter—llyA suggests — geneti™ link de™re—se of ƒ su˜stitution into ˜oth miner—ls with

˜etween the miner—liz—tion style —nd this de™re—sing temper—ture @‰undD IWTPAF „he

p—rti™ul—r hostEro™k lithologyF „he —˜und—nt temper—ture estim—tes @IHHÿQHHVgA o˜t—ined for

org—ni™ m—tter in the uupfers™hiefer ™ould h—ve the fie˜er goExiEfi ores —re in good —greement

—™ted —s — redu™ing —gent for dissolved oxidized with the typi™—l temper—ture r—nge of different

sulphur —nd —rseni™ spe™ies in the hydrotherm—l styles of postE†—ris™—n miner—liz—tion in gentr—l

¯uidsD whi™h would h—ve resulted in the iuropeF ƒystem—ti™ ¯uid in™lusion studies @eFgF RHQ

„F ‡ eq x i ‚ e x h t F vy‚ i x 

well —s different gener—tions of white mi™—F „he deposition of goExi —rsenides —nd sulph—rsenides

rel—tive —ge rel—tionships ˜etween different in ™lose vi™inity to the ™ont—™t ˜etween the

gener—tions of peEwn oxides —nd the m—jor ˜—sement ro™ks —nd the uupfers™hieferF e model

gener—tion of ˜—ryte in the ƒpess—rt distri™t of thermo™hemi™—l redu™tion of —rsenites —nd

@™orresponding to ˜—ryte s of the fie˜er depositA sulph—tes w—s origin—lly proposed ˜y fl—ir @IWWUA

h—ve ˜een est—˜lishedD ˜—sed on det—iled textur—l to expl—in the unusu—l miner—l —ssem˜l—gesD the

investig—tionF w—ng—nite —nd — ®rst gener—tion of geologi™—l setting —nd the stru™tur—l distri˜ution

˜r—unite pred—te the deposition of t—˜ul—r ˜—ryteD of the ™l—ssi™—l goExiEfiEegEes @®veEelementA

whi™h h—s ˜een su˜sequently overgrown ˜y veins of go˜—ltD ynt—rioF sn — series of redu™tion

spe™ul—riti™ hem—tite —nd h—usm—nniteF „he experiments ™—rried out with —rseniteE —nd

onset of miner—liz—tion in the vein systems of sulph—teE˜e—ring hydrotherm—l solutions —t

the ƒ—il—uf rhyolite w—s —t IUVÿIVH w— @illiteD temper—tures of PHHVg —nd QHHVgD xiEgo

uEerAD where—s sever—l st—ges of deposition of sulph—rsenides were pre™ipit—tedD together with

oxide miner—ls —nd mi™—s h—ve ˜een d—ted n—tive silver —nd eg ƒ @fl—irD IWWUAF „he results P

˜etween ITI —nd WV w— @r—utm—nn et —lFD of these experiments suggest th—t the pro™ess of

IWWWAD using uEer @illiteD ™el—doniteA —nd thermo™hemi™—l —rsenite redu™tion is likely to

@ C„hAEre ™hronometry @oxidesAF „he ®rst o™™ur under f—vour—˜le ™onditions in oreEforming

gener—tion of ˜r—unite @preE˜—ryteA h—s —n environmentsF ixperiment—l studies —nd —n—lyE

@ C„hAEre —ge of ISUÿITI w—D where—s the ti™—l d—t— from —™tive geotherm—l systems

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miner—liz—tionD ‚henish w—ssifD qerm—nyX eviden™e „un—˜ergD fergsl—genD ƒwedenF xeues t—hr˜u™h fur È

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gontri˜utions to winer—logy —nd €etrologyD PVD vorenzD tF @IWWSA winer—lis—tionen —us dem ‚hyolithE

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f—rytg—Èngen des ƒpess—rtsF eufs™hlussD RRD solutions in the r—rz wount—insX — summ—ry of ¯uid

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